Renewable Energy 54 (2013) 241e247

Contents lists available at SciVerse ScienceDirect

Renewable Energy
journal homepage: www.elsevier.com/locate/renene

Non-isothermal pyrolysis of the mixtures of waste automobile lubricating oil

and polystyrene in a stirred batch reactor
Seung-Soo Kim a, *, Jinsoo Kim b, **, Jong-Ki Jeon c, Young-Kwon Park d, Chan-Jin Park e
a

Department of Chemical Engineering, Kangwon National University, 1 Joongang-ro, Samcheok, Gangwon-do 245-711, Republic of Korea
Department of Chemical Engineering, Kyung Hee University, Yongin, Gyeonggi-do 446-701, Republic of Korea
c
Department of Chemical Engineering, Kongju National University, Cheonan, Chungcheongnam-do 331-717, Republic of Korea
d
School of Environmental Engineering, University of Seoul, Seoul 130-743, Republic of Korea
e
School of Urban & Environmental Engineering, University of Incheon, Incheon 406-772, Republic of Korea
b

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 28 January 2012
Accepted 1 August 2012
Available online 24 August 2012

Kinetic tests on pyrolysis of the mixture of waste automobile lubricating oil (WALO) and polystyrene (PS)
were carried out with a thermogravimetric analysis (TGA) technique at a heating rate of 0.5
C/min,
1.0
C/min and 2.0
C/min in a stirred batch reactor. WALO and PS were mainly decomposed 400e455
C
and 370e410
C, respectively. The mixture of WALO and PS, however, was decomposed between 355
C
and 470
C, and decomposition proceeded in two broad steps. The apparent activation energies for
the pyrolysis of WALO/PS mixture were in the range of 176 kJ mol1e369 kJ mol1 at various conversions
of 1e100%. The effect of heating rate on the product distribution was studied. The carbon number
distribution of the produced oil shifted slightly to light hydrocarbons with a decrease in heating rate. The
selectivity of hydrocarbons corresponding to the styrene monomer was high for the pyrolysis of the
WALO/PS mixture.
2012 Elsevier Ltd. All rights reserved.

Keywords:
Pyrolysis
Waste automobile lubricating oil
Polystyrene
Stirred batch reactor
Carbon number distribution

1. Introduction
Renewable wastes such as waste polymeric materials are of
concern throughout the world. Despite their high potential as
renewable energy sources, waste plastics have generally been
disposed, resulting in serious environmental problems.
The consumption of plastics has been kept increasing in Korea.
However, only 25% of waste plastics are recycled and the rest are
landlled or incinerated [1]. Utilization of waste plastics as fuels or
chemicals is an attractive way to solve the problem, offering the
possibility of energy recovery from organic wastes at the same
time. The pyrolysis of waste plastics can play an important role in
converting this waste into economically valuable hydrocarbons,
which can be used either as fuels or as feed stock in the petrochemical industry. A lot of researches on pyrolysis have been widely
conducted in efforts to nd efcient means to convert waste
materials such as used tire [2,3], waste plastics [4e15], waste
lubricating oil [16e20], and waste cellulose materials [21e24] into
valuable liquid and gaseous hydrocarbons and a solid char. Polystyrene (PS) has widely been used for various purposes [25], due to
* Corresponding author. Tel.: 82 33 570 6544; fax: 82 33 570 6535.
** Corresponding author. Tel./fax: 82 31 201 2492.
E-mail addresses: sskim2008@kangwon.ac.kr (S.-S. Kim), jkim21@khu.ac.kr
(J. Kim).
0960-1481/$ e see front matter 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.renene.2012.08.001

its characteristics such as great rigidity, high surface gloss and

excellent transparency. Numerous studies for PS have been conducted to maintain the environmentally compatible economic
growth and to determine the kinetics of thermal degradation
[8e11].
Billions of gallons of waste automobile lubricating oil (WALO)
are generated every year globally. A number of studies to remove
various pollutants existing in the waste lubricating oil and simultaneously to reuse these resources as valuable products have been
undertaken [16e20]. WALO is a good source for renewable
resources because of its uniform composition. From an engineering
viewpoint, low heat transfer rates and high viscosity of the melting
polymer can hinder commercial applications of recycling waste
plastic by pyrolysis. When mixed waste plastics with WALO, that of
WALO also can be employed as a solvent to swell waste plastics,
showing improved heat transfer [6,7]. Thus, WALO might serve to
decrease the decomposition temperature of a mixture of waste
polymeric material. In this regard, Sato et al. [8] investigated
reaction properties of the thermal degradation of PS in various
kinds of solvents in the temperature range from 300
C to 450
C.
The main purpose of this work is to determine the global kinetic
parameters during the non-isothermal pyrolysis of a mixture of
WALO and PS. In this study, the pyrolysis of WALO/PS mixtures was
investigated by using a new and highly efcient technique. A stirred
batch reactor was used for the pyrolysis of the mixture WALO/PS

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S.-S. Kim et al. / Renewable Energy 54 (2013) 241e247

8
Nomenclature
pre-exponential factor, s1
activation energy, kJ mol1
pyrolysis rate constant, s1
reaction order
gas constant 8.314 kJ kmol1 K1
pyrolysis time, s
pyrolysis temperature, K
weight of sample at time t, g
initial weight of sample, g
nal weight of sample, g
conversion of sample material

6
9

10
4

A
E
k
n
R
t
T
W
W0
WN
X

11

13

5
and the global pyrolysis kinetic parameters were determined. The
effect of heating rate of the WALO/PS mixture on carbon number
distributions of pyrolysis products was investigated.

12
1

A schematic diagram of the autoclave (R-201, Reaction Engineering) for the pyrolysis of the mixture of WALO and PS is shown
in Fig. 1. The pyrolysis of the mixture of WALO and PS was carried
out in a stirred batch reactor, and the experiment was operated at
atmospheric pressure. The experimental process is characterized as
a semi-batch operation, because pyrolyzed products are evolved
continuously during the course of the reaction. A stainless steel
cylindrical pyrolysis reactor having a volume of 1000 cm3 was
employed. The reactor was equipped with a mechanical agitator to
minimize the temperature prole in the reactor. The temperature of
the pyrolysis reactor was adjusted by a PID temperature controller.
A standard thermocouple (chrome-nickel) was installed into the
sample material for accurate measurement of reactant temperature
during the reaction.
A sample mass of 300 g was employed for all experimental runs,
and the mixing ratio of WALO and PS was maintained at 1:1 in
weight. To create an oxygen-free atmosphere, nitrogen was introduced into the reactor at a large rate of ow; it was subsequently
cut off and the mixing rate was set at 100 rpm throughout the
remainder of the experiment. For non-isothermal pyrolysis, the
heating rate was controlled at 0.5
C/min, 1.0
C/min, or 2.0
C/min
in order to raise the pyrolysis temperature from 300
C to 500
C. At
temperatures below 300
C, the heating rate was set at 10
C/min,
because the mixture of WALO and PS did not decompose under
300
C. The deviation of temperature in the reactor was 1
C for
a pyrolysis temperature of 300
Ce500
C.
The decomposed gas was condensed with a cooling uid at
a temperature of 0
C in the condenser. The cooling uid was made
up of a mixture of ethanol and distilled water. The yields of the
liquid pyrolysis products were determined gravimetrically by
weighing condensed liquid product, while the volume of uncondensed gases was determined by using a wet gas-meter. The
experimental data were recorded every 10 s on a personal
computer during the entire period. The liquid products for the
pyrolysis of the mixture of WALO and PS were analyzed by gas
chromatography with a ame ionization detector (Young LinM600D). Helium (17 ml/min) was used as carrier gas. Initial and
nal temperatures of injector were 100
C and 400
C, respectively,
and that of heating rate was 10
C/min. A capillary column a HP-1
(0.53 mm i.d., 5 m length) was employed with a programmed
temperature from 50
C to 350
C with oven heating rate of
10
C/min. The peaks were identied by matching retention times
with those of reference compounds.

14

Oil

2. Experimental

16

17
15

1. Nitrogen bomb

9. Condenser

2. Flowmeter

10. Circulator

3. Ball valve

11. Solenoid valve

4. Heater

12. Cylinder

5. Pyrolysis reactor

13. Wet gas meter

6. Thermocouple

14. Reservoir

7. Stirrer

15. Balance

8. Temperature, pressure and

16. Computer

rpm controller

17. GC

Fig. 1. Schematic diagram of a stirred batch reactor.

Table 1 shows the characteristics of the WALO used in this study.

Table 2 shows the characteristics of the PS sample, the properties
which were characterized by DSC (PERKIN-ELMER 7 Series Thermal
Analysis System). The results of elemental analysis of WALO and PS
are given in Table 3. The atomic ratio (H/C) of WALO was higher
than that of PS.
3. Results and discussion
3.1. Thermogravimetric analysis of the mixture of waste automobile
lubricating oil and polystyrene in a stirred batch reactor
For all thermogravimetric experiments, the results are
expressed as a function of the degree of conversion X, which is
dened as Eq. (1).
Table 1
Properties of waste automobile lubricating oil (WALO).
Dynamic viscosity (m2/sec)
Density (at 20
C, g/cm3)
Gravity (15.4/4)
Parafn (wt%)
Naphthane (wt%)
C12eC25 (wt%)
>C25 (wt%)

0.50
0.8797
0.8833
58
42
16.58
83.42

S.-S. Kim et al. / Renewable Energy 54 (2013) 241e247

243

Table 2
Properties of polystyrene (PS).
Mw
PS
a
b

313,700

DCp [J/g
C]

Tg [
C]

Mn

169,500

101.48

0.29b

Hannam Chemical Co. [GP-150].

Measured by DSC [PERKIN-ELMER 7 Series Thermal Analysis System].

W
W0  W N

(1)

where W0 is the initial mass of sample; W is the mass of product oil;

WN is the nal residual mass corresponding to that of solid byproducts including an unpyrolyzed sample. When the mixture of
WALO and PS is pyrolyzed (i.e. heating to w500
C), it decomposes
to yield oil, gas, and solid by-products. As noted in the experimental
section, the condenser temperature was maintained at 0
C to
condense the products. For the pyrolysis of PS at the employed
heating rates, the efuent gas from the condenser was not detected
with a wet gas-meter [11]. The result reveals that the benzene does
not decompose in the repeating unit of PS under 500
C at the
heating rate of 0.5e2.0
C/min. In our previous work, WALO
produced gaseous products under the same conditions [16]. In that
case, the volume of gas was in the range of 0.87e2.81 [ for
0.5e2.0
C/min and that of produced oil was 91.64e93.28 wt%. In
this work, a sample mass of 300 g was employed for the pyrolysis of
WALO and PS, which were mixed with 1:1 weight ratio. The weight
of uncondensed gas was much smaller than that of the mixture of
WALO and PS and produced oil. Mass balance can be evaluated as
the difference between the mass of the reactant (the mixture of
WALO and PS), the mass of the produced oil, and the residual mass
in the reactor bottom. In this study, the calculation of conversion
was limited to produced oil and residual mass after reaction.
Fig. 2 shows the degree of conversion versus temperature for
dynamic experiments at different heating rate of 0.5
C/min,
1.0
C/min, and 2.0
C/min. Decomposition of the mixture of WALO
and PS was initiated at 350
C for 0.5
C/min. At the same reaction
conditions, pure WALO and PS decomposition was initiated at
a temperature of 380
C and 361
C, respectively. The mixture
decomposed at a lower temperature than either WALO or PS alone
at heating rates of 0.5
C/min, 1.0
C/min and 2.0
C/min. It is
considered that WALO played a role as a swelling agent for PS
chains, resulting in improved heat transfer in the mixture. PS could
be easily decomposed in a lower temperature after being swelled
with WALO. As such, the mixtures of WALO and PS could be
pyrolyzed in a lower temperature compared with each pure
component. The pyrolysis of PS was initiated at the temperature of
360
C, 370
C, and 384
C, respectively, at heating rates of
0.5
C/min, 1.0
C/min, and 2.0
C/min [9]. WALO was pyrolyzed at
a temperature of 362
C, 368
C, and, 386
C at heating rates of
0.5
C/min, 1.0
C/min, and 2.0
C/min, respectively. Although the
initiation temperature of pyrolysis of WALO and PS was quite
similar, the main regime of pyrolysis for WALO was higher than that
of PS.
The decomposition patterns of the mixture of WALO and PS
were different in comparison with those of WALO and PS,

Fig. 2. The effect of pyrolysis rate of the mixture of waste automobile lubricating oil
(WALO) and polystyrene (PS) on heating rate. aChemical Engineering Journal, 93
(2003) 225e231. bChemical Engineering Journal, 98 (2004) 53e60.

respectively, as indicated by the thermogravimetric curves. WALO

and PS showed a single slope in the region of main decomposition,
but the mixture of WALO and PS displayed two slopes. These results
indicate that the mixture of WALO and PS is pyrolyzed in two stages
in the temperature range of 300
Ce500
C in the stirred batch
reactor. The rst slope was revealed in the temperature of
360e390
C at 0.5
C/min and the second slope at 395e450
C. The
slope was changed when the conversion was 55% for each heating
rate in the mixture of WALO and PS. The mixture decomposed at
a lower temperature than either WALO or PS alone for the same
heating rates. All three heating rates yielded the same patterns of
thermal decomposition. It is considered that the rst stage is
attributed to the dominant decomposition of PS and the second
stage to the dominant decomposition of WALO.
An instantaneous rate of conversion, dX/dt, is obtained from
differential thermogravimetric analysis (DTG) at the given reaction
temperature. As shown in Fig. 3, the height of the peaks gradually
increases with increasing heating rates. Also, the position of the
maximum peak is shifted to higher temperature, and the peak

Table 3
Elemental analysis of waste automobile lubricating oil (WALO) and polystyrene (PS).
Element (wt%)

WALO
PS

H/C ratio

81.50
91.60

18.16
8.07

e
e

0.34
0.15

2.67
1.06

Fig. 3. Variation of the instantaneous reaction rate with temperature at different

heating rates for the mixture of waste automobile lubricating oil (WALO) and
polystyrene (PS). aChemical Engineering Journal, 93 (2003) 225e231. bChemical
Engineering Journal, 98 (2004) 53e60.

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S.-S. Kim et al. / Renewable Energy 54 (2013) 241e247

700

A function of conversion independent of temperature, f(X), is

expressed as

3.2. Activation energy

f X X n

(4)

 
dX
E1
ln
lnAX n 
dt
RT

(5)

Thermogravimetric analysis for the differential method and the

integral method has been extensively studied by other researchers
[11,16,22,26e30]. The derivation of pyrolysis kinetic data from
thermogravimetric analysis in this work followed the differential
method. The rate of conversion, dX/dt, in thermal decomposition is
expressed by

dX
kf X
dt

(2)

The reaction rate constant k is expressed by the Arrhenius

equation

 
E
RT

k A exp

(3)

Activation Energy ( kJ/mol )

height is directly proportional to the reactivity. Thus it appears that

higher instantaneous thermal energy is released into the reaction
system with increasing the heating rates, resulting in a higher rate
of conversion.
The results of Fig. 3 also indicate that a larger fraction of
WALO/PS mixture was pyrolyzed in the reaction temperature range
of 370
Ce460
C. Pyrolysis of a single component (WALO and PS,
respectively) displays bilateral symmetry in Fig. 3, and one
maximum peak occurs at a specic reaction temperature for each
heating rate. The mixture of WALO and PS, however, does not
display bilateral symmetry. In Fig. 2, there are two slopes in the
thermogravimetric curves for the mixture. The slope of the higher
temperature was considered for the degradation of WALO. Thus,
the at-tail section observed at temperature higher than 400
C,
410
C, and 430
C at the heating rates of 0.5
C/min, 1.0
C/min, and
2.0
C/min, respectively, is attributed to the thermal decomposition
of WALO. The maximum rate of the WALO/PS mixtures occurred at
373
C, 383
C, and 397
C for heating rates of 0.5
C/min,
1.0
C/min, and 2.0
C/min, respectively. The maximum rate of
WALO was 416
C, 420
C, and 425
C, and that of PS occurred at
376
C, 391
C, and 400
C for each heating rate [16]. The temperature of maximum peaks for the WALO/PS mixture was lower
compared to that of pure WALO or PS and conversions at maximum
peak were approximately 30% for each heating rate.

600

1 : WALO:PS = 1:1 wt ratio

2 : WALOa
2 : PSb

500
2

400
300

200
3

100
0
0.0

0.2

0.4

0.6

0.8

1.0

Conversion (X)
Fig. 5. Calculated activation energies at different conversions for pyrolysis of the
mixture of waste automobile lubricating oil (WALO) and polystyrene (PS).

Substituting Eqs. (3) and (4) into Eq. (2) and taking a natural
logarithm, the above equation yields

Apparent energy of activation E, based on Eq. (5), is determined

from the relationship between ln(dX/dt) and 1/T. Thus, a family of
parallel straight lines of slope eE/R is obtained. The apparent
activation energy (E) corresponding to the selected conversion is
obtained. More detailed explanation can be found in the literature
[11,16].
The intercept (ln(AXn)) can be calculated from Fig. 4 at each
conversion. The apparent order of reaction (n) and the preexponential factor (A) are obtained by curve tting based on Eq. (6).

lnA$X n lnA nlnX

(6)

90
WALO:PS = 1:1 wt ratio
Conversion :
5%
10%
20%
30%
40%
50%
60%
70%
80%
90%
95%

70

ln (dX/dt)

60
50
40
30
20

WALO:PS = 1:1 wt ratio

6.5

WALOa
PS

6.0
5.5

5.0
1
4.5
4.0

10

3.5

0
-10
0.00130

7.0

ln(A.Xn)

80

0.00135

0.00140

0.00145

0.00150

0.00155

0.00160

0.0016

-1

1/T [K ]

3.0
-1.1

-1.0

-0.9

-0.8

-0.7

-0.6

-0.5

-0.4

-0.3

-0.2

-0.1

0.0

ln(X)

C/min

Fig. 4. Application of Eq. (5) with heating rate of 0.5, 1.0 and 2.0
for the mixture
of waste automobile lubricating oil (WALO) and polystyrene (PS). The conversion
values are: 5, 10, 20, 30, 40, 50, 60, 70, 80, 90 and 95%.

Fig. 6. The overall reaction order for pyrolysis of the mixture of waste automobile
lubricating oil (WALO) and polystyrene (PS). aChemical Engineering Journal, 93 (2003)
225e231. bChemical Engineering Journal, 98 (2004) 53e60.

S.-S. Kim et al. / Renewable Energy 54 (2013) 241e247

and the activation energy is relatively low in the following order:

HDPE < LDPE < PP < PS. In our previous work, waste automobile
lubricating oil was pyrolyzed [17]. The greater activation energy
was observed in the later period of the conversions. The activation
energies were between 275 kJ mol1 and 450 kJ mol1 at the
conversion of 11e96%. The range of activation energies of PS was
between 164 kJ mol1 and 249 kJ mol1, and that of PP was
between 208 kJ mol1 and 288 kJ mol1 [11]. As the conversions
increased, activation energy also increased and seemed to be
approaching relatively stronger chemical bond dissociation energy.
The apparent activation energies for the mixture of WALO and PS
changed drastically with the variation of conversions, as indicated
in Fig. 5. In particular, those of activation energy slowly increased
until conversion of 55%, and then decreased. Greater apparent
activation energy was observed in the later period of the conversions. This indicates that degradation characteristics change with
the variations of conversion. The range of apparent activation
energies for the mixture of WALO/PS was between 176 kJ mol1 and
369 kJ mol1. As shown in Fig. 2, the slope of the TG curves

Table 4
Kinetic parameters of the mixture of waste automobile lubricating oil (WALO) and
polystyrene (PS) at the non-isothermal pyrolysis.
T [
C]

X [wt%] n

Mixture of WALO and PS 300e500 0e100

300e500 0e100
WALOa
300e500 0e100
PSb
a
b

E [kJ mol1]

0.46 103.31 176e369 Avg. 264

1.35 334.22 282e448 Avg. 323
0.32 60.60 164e249 Avg. 221

Chemical Engineering Journal, 93 (2003) 225e231.

Chemical Engineering Journal, 98 (2004) 53e60.

Oil fraction [ % ]

At low conversions, the decomposition of polymer proceeds to

cut the side chain in its repeating units, and then the main chain
decomposes with increase of conversions. That is, as the conversions are increased, E is also increased and appears to approach
relatively stronger chemical bond dissociation energy. Westerhout
et al. studied the pyrolysis of HDPE, LDPE and PS using TGA in the
temperature range of 345e450
C [31]. They explained that the
pyrolysis rate increased to the extent of branching. This means that
the polymer having a side chain decomposes at low temperature

40
35
30
25
20
15
10
5
0
40
35
30
25
20
15
10
5
0
40
35
30
25
20
15
10
5
0
40
35
30
25
20
15
10
5
0
40
35
30
25
20
15
10
5
0
40
35
30
25
20
15
10
5
0
0

245

WALO:PS=1:1 wt ratio, 0.5 C/min

WALO:PS=1:1 wt ratio, 1.0 C/min

WALO:PS=1:1 wt ratio, 2.0 C/min

PS : 0.5 C/min

WALO : 0.5 C/min

WALO(Waste automobile lubricating oil)

10

15

20

25

30

35

40

45

Carbon number
Fig. 7. The effect of heating rate on carbon number distribution for the mixture of waste automobile lubricating oil (WALO) and polystyrene (PS).

246

S.-S. Kim et al. / Renewable Energy 54 (2013) 241e247

displayed two steps; likewise, the apparent activation energies are

divided by two steps in Fig. 5. The apparent activation energies in
the rst step are mainly attributed to the decomposition of PS, and
the activation energies of the second step are attributed to the
WALO. The average apparent activation energy for WALO/PS
mixture was 264 kJ mol1, and those of WALO and PS were
319 kJ mol1 and 221 kJ mol1, respectively. The average apparent
activation energy for the WALO and PS mixture is lower than mean
value of the average apparent activation energy for WALO and PS.
The decomposition temperature of the WALO/PS mixture was
lower than that of WALO and PS, as indicated in Fig. 2. This indicates
that PS was decomposed in a lower temperature within the mixture
of WALO and PS, and decomposition rate could be increased,
resulting in a swelling effect of WALO. Thus, the average apparent
activation energy for WALO/PS mixture is lower than mean value of
the average apparent activation energy for WALO and PS. Aboulkas
et al. obtained activation energy of the mixture of Moroccan oil
shale, olive reside and plastics by thermogravimetic analysis
[32,33]. The activation energies of plastics in the mixture were
lower than the activation energies of plastic pure. Chowlu et al.
studied pyrolytic decomposition of mixture of PP and LDPE [34].
LDPE and PP are incompatible in the melt and the blend exits as
a two-phase mixture. As PP degraded at lower temperature than PP,
initially radicals from PP are formed in the case of the mixture
during pyrolysis. These produced radicals from PP then migrate
towards the PP/LDPE boundary and interact with LDPE. They
explained that these radicals accelerate the degradation of LDPE.
The order of reaction and pre-exponential factor can be obtained
from Fig. 6 and Eq. (6). Fig. 6 shows linear relations such that the
apparent order of reaction (n) of 0.46 is determined for the mixture
WALO and PS. The apparent orders of reaction of 1.35 and 0.32 were
determined for WALO and PS, respectively [11,16]. The average
activation energy (E), overall order of reaction (n), and preexponential factor (A) are listed in Table 4.
3.3. Carbon number distribution of product oil
To analyze the product oil, the samples were dissolved in CS2.
Pyrolyzed oil was quantitatively determined by GC. The product
distributions of the WALO/PS mixture in terms of carbon number
obtained at different heating rates are shown in Fig. 7. As shown
here, the major products of PS were the group of styrene monomer
and dimer hydrocarbons, which involved one aromatic and two
aromatics. Other products such as styrene trimer were formed to
only a limited extent [11].
The composition above C25 of WALO was 83.42%, and it contained 16.58% of light hydrocarbons below C25. It is thought that the
light hydrocarbons (<C25) in WALO are produced during the
lubrication in automobile engines. Specic characteristics for the
pyrolyzed products of WALO, in contrast with PS, were not found,
although carbon number distributions moved to light hydrocarbons after pyrolysis. At the WALO/PS mixture, the light hydrocarbons increased slightly with decreasing heating rates. This results
in an increase of retention time, because of lower heating rate at
limited temperature. Therefore, the energy required for decomposition of organic matter increases, causes light hydrocarbons to
increase. The selectivity of styrene monomer slightly increased
with decreasing heating rate. The light hydrocarbons in the mixture
were increased, particularly relative to WALO. As shown in Fig. 2,
the WALO/PS mixture decomposed at lower temperature than
WALO and PS for the same heating rates. This result was attributed
to the swelling effect of WALO on PS; in addition, heat transfer was
improved by WALO. It is thought that synergetic effects take place
for the production of light liquid hydrocarbons when WALO and PS
are mixed.

4. Conclusions
Kinetic tests on the pyrolysis of a mixture of waste automobile
lubricating oil (WALO) and polystyrene (PS) were carried out using
a thermogravimetric analysis (TGA) technique at the heating rate of
0.5
C/min, 1.0
C/min, and 2.0
C/min in a stirred batch reactor. The
apparent activation energy and the apparent order of reaction were
determined at conversions from 1 to 100%. The apparent activation
energies increased with the increase of conversions. The ranges of
apparent activation energies of the mixture were from 176 kJ mol1
to 369 kJ mol1 at conversions in the range of 1e100% and the
apparent order of reaction was 0.46.
The carbon number distributions of produced oil at a different
heating rate were analyzed. The carbon number distribution of the
produced oil shifted slightly to light hydrocarbons with decreasing
heating rates. The selectivity of hydrocarbons corresponding to the
styrene monomer was high for the pyrolysis of the WALO/PS
mixture.
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