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),
while the pores of HZSM-5 are smaller (about 5 !5 A
) and
it is known that the length of products is principally deter-
mined by the pore size. The greater the pore sizes the longer
the formed hydrocarbons. Also the geometrics of catalysts
are important. The acidity of catalysts mainly determinates
the cracking behaviour of CeC bonds and the probability of
b-scission. However, the amorphous part of catalysts fosters
the isomerisation and aromatisation reactions. Therefore the
HZSM-5 catalyst shows quite high selectivity in the formation
of parafns and olens and branched hydrocarbons and the
yield of gases is also high. As a matter of fact high yields of
both gases and lighter liquids are due to the great microporous
surface area and the high yield of gases observed with the use
of amorphous silicaealumina without 3D structural pores is
explained with its great acidity. Lots of experiments have
been performed on the investigation of clinoptilolite zeolite
or uid catalytic cracking (FCC) catalysts (fresh or
used) as a catalyst for this process. Clinoptilolite catalysts
usually have pore structure of monoclinic framework consist-
ing of a 10-membered ring (7.6 !3.0 A
) and an 8-membered
ring (3.3 !4.6 A
.
In the present paper, we report the thermal and thermo-
catalytic cracking behaviour of a waste high-density polyethyl-
ene (LDPE) and polystyrene (PS) over different acidic catalysts
(ZSM-5, equilibrium FCC, clinoptilolite) in a batch reactor un-
der isothermal conditions. The goal of our work was to inves-
tigate the cracking of an HDPE and PS mixture over different
catalysts and the effect of catalyst grain size on the properties
of products. Both gas and liquid products formed in cracking
reactions were analyzed by standardized and non-standardized
methods. The effect of the cracking parameters (temperature,
catalysts and their average grain size) on the yields and
structure of products were investigated. The apparent kinetic
parameters of reaction for the overall degradation are obtained
in dependence on temperature. Furthermore the possibility of
further utilization of fuel-like products was investigated.
2. Experimental
2.1. Raw materials
In our experiments commercial high-density polyethylene
(HDPE) and polystyrene (PS) from the packaging industry
were crushed to pieces of 4e7 mm and used as raw material.
The melt ow index (MFI) (at 190
C with 2160 g load) was
0.538 g/10 min, and 0.519 g/10 min in case of HDPE and PS
waste, respectively. The used raw materials had sulphur and
nitrogen content from additives (e.g. antioxidant, re-retardant
and antifuming additives). Waste polymers were used not in
their individual form, because 10% of polystyrene and 90%
of high-density polyethylene were mixed and cracked together.
2.2. Catalysts and their characterization
Three different cracking catalysts were used in thermo-
catalytic cracking: an equilibrium uid catalytic cracking catalyst
(FCC), a commercial ZSM-5 catalyst and a clinoptilolite
containing rhyolite tuff (Clin.). The Si/Al atomic ratio of the
samples was determined by X-ray spectrometry. Nitrogen
adsorptionedesorption isotherms at 77 K of the calcined
catalysts were obtained with a Micromeritics ASAP 2000 in-
strument. Firstly catalysts were degassed under vacuum at
160
C for 5 h, then the surface area of catalysts was calculated
by the application of BET procedure. The pore size distributions
were determined by an Analysette 22 type grain size analyzer
using laser ray according to the Fraunhofer angle deviation
theory. Table 1a and b shows the main properties of the
518 N. Miskolczi et al. / Polymer Degradation and Stability 91 (2006) 517e526
uncrushed catalysts. Macro- and microporous surface areas, Si/
Al ratios which are proportional to acidities and cationic compo-
sitions are signicantly different. The characteristic grain
sizes of uncrushed catalysts decrease in sequence of FCC O
Clin. OZSM-5. In order to compare the effect of the average
grain size of catalysts on the yields and characteristics of end
products, catalysts were crushed, and used also in their smaller
grain size. Apart from decreasing the average grain size of cata-
lysts, their other properties were not changed signicantly.
Fig. 1 represents the distribution of average grain size of
crushed and uncrushed catalysts. Uncrushed catalysts had an
average grain size of 12e60 mm, and signicant differences
can be observed between the distribution curves. By crushing
catalysts the grain sizes can be decreased to 1.5e1.8 mm, fur-
thermore the grain size distribution curves become similar.
2.3. Cracking apparatus and the analyses of products
Pyrolysis of HDPE and PS was performed in a Pyrex glass
reactor (volume: 500 cm
3
) under atmospheric pressure by
batch operation at isothermal temperatures (410, 430 and
450
C). The temperature of melted polymer was measured
with a thermometer. In each case 200 g of waste polymer
was fed into the reactor and in case of thermo-catalytic crack-
ing 2% catalyst by weight was added to the mixture of waste
polymers. The applied cracking apparatus is shown in Fig. 2.
For ensuring an inert atmosphere nitrogen was introduced into
the polymer with a ow rate of 7 dm
3
/h. The liquid products
obtained during the degradation were condensed using a water
condenser then collected and analyzed. The gaseous products,
which are not condensed as liquid products, were also mea-
sured and analyzed.
2.4. Analysis of products
Each cracking fraction was analyzed using the following
methods. The following standardized methods were used:
liquid density measurement (MSZ EN ISO 12185), determina-
tion of distillation curve (ASTM-D 1078), determination of
sulphur content of naphtha and diesel oil-like fractions
(ASTMD 6428 99), determination of nitrogen content of naph-
tha and diesel oil-like fractions (ASTMD 6366 99), determina-
tion of ash point (ISO 2719:2002 and MSZ 15967:1979),
determination of CFPP (MSZ EN 116:1999), corrosion test
(MSZ EN ISO2160:2000), determination of kinematic viscos-
ity (MSZ ISO 3105:1998).
Gases were analyzed using a Carlo-Erba Vega Series GC
6000 gas chromatograph with ame ionization detector pro-
vided with a 50 m!0.32 mm fused silica column with
Al
2
O
3
/KCl coating, at 40
C.
Liquid products were analyzed by gas chromatography
with a ame ionization detector using a TRACE GC gas chro-
matograph. It was provided with a 30 m x 0.32 mm Rtx
-1
(Crossbond
dW
dt
ZkW
n
1
The activation energies were calculated by using the Arrhe-
nius equation:
kZA
0
exp
E
RT
2
Fig. 5 represents the weight of volatile products as function
of cracking time. Integrating Eq. (1), the conversion (c) as
function of time (t) can be expressed by ln(1c) Zkt (Fig. 6).
The reaction rate coefcients were obtained from Fig. 6. It
was found that they increased with the cracking temperatures,
and were higher in the presence of catalysts. From the temper-
ature dependence of the reaction rate constants phenomeno-
logical activation energies were calculated (Table 4). In the
presence of catalysts the average activation energies were
lower than the activation energy of thermal reactions. The
activation energies of thermo-catalytic degradation could be
decreased also by decreasing the average grain size of the
catalysts. The lowest value was found with FCC catalyst.
3.5. Further application of products
One prospective possibility of the further utilization of
liquids formed in the cracking reactions is a fuel-like utiliza-
tion. Therefore liquids obtained in the cracking reactions
were measured and analyzed also as fuel-like products. For
the sake of investigation of this possibility, after thermal and
thermo-catalytic degradation the liquid products from the mix-
ture of waste polymers were separated with distillation into
naphtha-like (b.p. 35e210
C) and diesel oil-like (b.p. 85e
305
C) fractions. Fig. 7a and b shows the gas chromatograms
of naphtha- and diesel oil-like fractions in case of non-catalytic
cracking at 450
C. There are lots of peaks of alkenes and
Table 4
The apparent activation energies
Catalysts E
a
, kJ/mol
None 255
FCC 218
FCC
a
196
ZSM-5 217
ZSM-5
a
209
Clin. 224
Clin.
a
203
a
Crashed catalysts.
0,0
20,0
40,0
60,0
80,0
0 10 20 30 40 50 60 70
Time of degradation, min.
Y
i
e
l
d
s
o
f
v
o
l
a
t
i
l
e
p
r
o
d
u
c
t
s
,
%
Non-cat.
Clin.
FCC
ZSM-5
Fig. 5. The weight of volatile products as function of cracking time using
uncrushed catalysts (at 430
C).
Cracking time, min.
-1,50
-1,00
-0,50
0,00
0 10 20 30 40 50 60
l
n
(
m
/
m
0
)
Clin.
FCC
ZSM-5
Clin.*
FCC*
ZSM-5*
Fig. 6. The ln(1 c) as function of cracking time in case of thermo-catalytic
cracking (430
C).
523 N. Miskolczi et al. / Polymer Degradation and Stability 91 (2006) 517e526
alkanes, and aromatics in Fig. 7a, because the cracking reac-
tions of polyethylene resulted great number of hydrocarbons e
alkenes and alkanes e while polystyrene different light
aromatics at moderate conditions.
Table 5a and b presents the main properties of each distil-
late fraction. According to data in Table 5a the naphtha-
like fractions contained C
5
eC
17
hydrocarbons, but mainly
C
8
eC
10
compounds were in the highest concentration in
liquids. Each naphtha-like fraction contained about one third
of aromatics owing to cracking of polystyrene. Due to aro-
matics in naphtha-like fractions their octane numbers were
high. Liquid properties are considerably changed in the
presence of catalysts. Naphtha-like liquids obtained by
thermo-catalytic cracking of polymer wastes had more favour-
able properties for further application, than those obtained by
thermal cracking e.g. higher octane numbers, which can be
due to the greater branched hydrocarbon content. Branched
compounds have moderately high octane numbers and quite
small sensibility. However, neither the type of catalysts nor
their grain size signicantly affected the properties of
products.
Each raw polymer contained sulphur and nitrogen atoms
from different additives (e.g. ame retardant, antioxidants or
antifuming, etc.). The lighter liquid fractions also had sulphur
and nitrogen content, but in very low concentration. The con-
centration of the sulphur and the nitrogen were not more than
15 ppm. It is an important property for their further utilization,
because there is a great ambition to reduce the heteroatom
content (mainly sulphur) in reneries. Furthermore these
processes are quite expensive.
In contrast to the experimental results of naphtha-like frac-
tions, the heavier liquid fractions had considerably lower con-
centration of aromatics. As data show aromatics stayed in
naphtha-like fractions and their concentration was not more
Retention time, min.
Retention time, min.
5 10
C
5
H
10 C
6
H
12
CH
3
CH
3
CH
2
HC
CH
2
C
7
H
14
C
7
H
16
C
8
H
16
C
9
H
18
C
9
H
20
C
10
H
20
C
10
H
22
C
11
H
22
C
12
H
26
C
12
H
24
C
13
H
28
C
13
H
26
C
11
H
24
H
3
C CH
3
CH
2
CH
3
HC
HC
C
8
H
18
C
6
H
14
C
5
H
12
C
11
H
24
C
11
H
22
C
12
H
26
C
12
H
24
C
13
H
28
C
13
H
26
C
14
H
30
C
14
H
28
C
15
H
32
C
15
H
30
C
16
H
34
C
16
H
32
C
17
H
36
C
17
H
34
C
18
H
38
C
18
H
36
C
19
H
40
C
19
H
38
C
20
H
42
C
21
H
42
C
21
H
44
C
20
H
40
C
22
H
46
C
22
H
44
C
23
H
48
C
23
H
46
C
24
H
48
C
24
H
50
C
25
H
50
C
25
H
52
C
26
H
56
C
27
H
54
C
26
H
54
C
26
H
52
xylenes
U,mV
5 10 15 20
Trimer U, mV
(a)
(b)
Fig. 7. The gas chromatogram of (a) naphtha-like and (b) diesel oil-like fractions in case of non-catalytic cracking at 450
C.
524 N. Miskolczi et al. / Polymer Degradation and Stability 91 (2006) 517e526
Table 5
Composition and main properties
Non-catalytic FCC FCC
a
ZSM-5 ZSM-5
a
Clin. Clin.
a
a. Of naphtha-like fractions
Yield, % 48.8 59.4 61.6 62.4 63.1 59.7 60.5
Aliphatic content, % 54.39 61.93 64.37 57.44 58.23 62.50 62.82
C
5
eC
7
11.51 20.21 20.68 15.72 14.28 19.97 18.28
C
8
eC
10
26.34 29.60 30.59 28.09 28.24 29.41 29.37
C
11
eC
13
15.09 12.02 13.00 13.38 15.60 13.02 15.06
C
14
eC
16
0.89 0.11 0.11 0.25 0.12 0.11 0.11
C
16C
0.57 0.00 0.00 0.00 0.00 0.00 0.00
Aromatics content, % 45.61 38.07 35.63 42.56 41.77 37.50 37.18
Benzene 0.38 0.28 0.25 0.24 0.35 0.26 0.33
Toluene 3.90 2.34 3.05 4.11 3.60 3.15 3.34
Ethyl-benzene 3.25 2.62 2.70 3.82 3.05 3.84 2.10
Styrene 28.82 28.55 26.50 29.88 29.39 26.03 26.8
Xylenes 0.56 0.35 0.26 0.43 0.30 0.37 0.2
Isopropyl-benzene 0.74 0.60 0.42 0.37 1.15 0.59 056
a-Methylstyrene 2.01 1.64 1.36 1.71 1.70 1.63 0.02
C
10
eC
15
1.42 1.68 1.08 2.00 2.23 1.63 1.94
C
16C
4.53 0.00 0.00 0.00 0.00 0.00 0.00
Density, g/cm
3
0.752 0.730 0.729 0.731 0.734 0.728 0.730
ROM 78 76 75 77 78 76 76
MON 85 84 84 85 85 84 84
(ROMCMON)/2 82 80 80 81 82 80 80
Corrosion test Group 1 Group 1 Group 1 Group 1 Group 1 Group 1 Group 1
Distillation data,
C
IBP 38 35 34 37 33 34 35
20 63 64 67 64 65 63 66
50 135 133 132 137 134 133 134
70 145 149 147 144 146 143 142
FBP 209 207 206 205 201 204 208
Sulphur content, ppm 14 11 13 10 14 9 12
Nitrogen content, ppm 8 6 9 5 9 10 8
M, g/mol 119 102 98 105 96 104 103
C/H 6.0 5.8 5.9 5.9 5.8 5.9 5.9
Other impurities None None None None None None None
b. Of diesel oil-like fractions
Yield. % 51.2 40.6 38.4 37.6 36.9 40.3 39.5
Aliphatic content, % 98.48 99.02 99.97 99.48 99.71 99.47 99.82
C
11
eC
13
11.19 15.95 15.53 16.22 15.48 14.70 14.91
C
14
eC
16
35.59 39.06 40.50 41.24 40.95 39.88 40.01
C
17
eC
19
27.51 28.49 29.69 29.40 29.76 28.93 29.14
C
20
eC
22
13.52 11.00 10.85 10.69 10.06 10.17 10.09
C
23
eC
25
7.34 3.26 2.20 0.58 2.00 3.94 4.51
C
26C
3.33 1.26 1.20 1.35 1.46 1.85 1.16
Aromatics content, % 1.52 0.98 0.03 0.52 0.29 0.53 0.18
Density, g/cm
3
0.823 0.815 0.808 0.801 0.796 0.816 0.811
Cetane number 64 63 63 63 63 64 63
Diesel index 69 69 69 69 69 68 68
Viscosity, mm
2
/s 4.4 4.5 4.4 4.4 4.3 4.3 4.4
CFPP,
C 1 4 5 7 8 5 4
Flash point,
C 92 85 84 83 83 84 85
Corrosion test Group 1 Group 1 Group 1 Group 1 Group 1 Group 1 Group 1
Distillation data,
C
IBP 85 88 84 83 80 81 82
20 163 160 158 162 163 159 164
50 195 194 195 198 193 195 197
70 214 219 218 218 216 215 214
FBP 305 302 298 304 301 298 301
Sulphur content, ppm 15 14 12 11 14 13 10
Nitrogen content, ppm 10 9 11 8 9 10 12
M, g/mol 255 247 240 240 238 247 247
C/H 6.2 6.2 6.2 6.2 6.2 6.2 6.2
Other impurities None None None None None None None
a
Crashed catalysts.
525 N. Miskolczi et al. / Polymer Degradation and Stability 91 (2006) 517e526
than 1% in diesel oil due to the low boiling point of aromatics.
Similarly as it was mentioned in case of lighter liquid frac-
tions, only the presence of catalysts affected the properties
of diesel oil-like liquids and neither the type of catalysts nor
their grain size affected signicantly the properties of products
in case of thermo-catalytic cracking. Both cetane numbers and
diesel indices of products were high enough, while the CFPP
was rather moderately low.
4. Conclusions
Thermal and thermo-catalytic degradation of a mixture of
90% of high-density polyethylene (HDPE) and 10% of poly-
styrene (PS) wastes was investigated in a temperature range
of 410e450
C in Pyrex batch reactor under nitrogen atmo-
sphere. It was found that:
-the mixture of wastes could be converted into lighter frac-
tions with yields of 16e89% depending on temperature
and catalysts,
-the cracking temperature and catalyst grain size signi-
cantly affected the yields, but gas yields depended mainly
on the type of catalyst,
-the activation energy of the overall conversion could be
decreased by about 40 kJ/mol by using catalyst,
-both olen double bond and carbon-chain isomerisation
were observed in the presence of zeolite catalysts,
-liquid hydrocarbon products are of low sulphur content
therefore they may be favourable for fuel production.
Acknowledgement
The authors gratefully acknowledge the nancial support
for this work of the Chemical Engineering Institutes Cooper-
ative Research Centre (especially Ministry of Education of
Hungary and the Hungarian Oil and Gas (MOL) PLC).
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