Journal of Analytical and Applied Pyrolysis

5859 (2001) 127 142

www.elsevier.com/locate/jaap

Thermal and catalytic cracking of polyethylene

under mild conditions
R. van Grieken a,*, D.P. Serrano a, J. Aguado a, R. Garca a,
C. Rojo b
a

Department of Experimental Sciences and Engineering, ESCET, Rey Juan Carlos Uni6ersity,
c/Tulipan s/n, 28933 Mostoles, Madrid, Spain
b
Repsol S.A., Technology Center, c/Embajadores 183, 28045 Madrid, Spain
Received 17 April 2000; accepted 14 August 2000

Abstract
Thermal and catalytic cracking of both high and low-density polyethylene (HDPE and
LDPE, respectively) under mild conditions have been investigated in order to study the
properties of the solid waxy product so obtained. The catalysts employed were n-HZSM-5
and HY zeolites, amorphous silicaalumina, activated carbon, Pd charcoal powder and
mesoporous aluminosilicate materials (MCM-41), with and without impregnated Pd. The
best results achieved in the LDPE degradation with regard to stability and homogeneity of
the waxy product were obtained using MCM-41 as catalyst. The high BET surface area,
uniform mesoporosity and medium acid strength of this catalyst promotes the polymer
cracking according to a random scission mechanism, as well as, the development of hydrogen
transfer reactions which reduce the olefinic character of the solid product. On the other
hand, the product obtained from HDPE has a higher homogeneity than that coming from
LDPE, leading to a waxy product with better quality for potential applications. 2001
Elsevier Science B.V. All rights reserved.
Keywords: LDPE; HDPE; Thermal degradation; Catalytic cracking; MCM-41

* Corresponding author. Tel.: + 34-91-4887007; fax: +34-91-6647490.

E-mail address: r.vangrieken@escet.urjc.es (R. van Grieken).
0165-2370/01/$ - see front matter 2001 Elsevier Science B.V. All rights reserved.
PII: S 0 1 6 5 - 2 3 7 0 ( 0 0 ) 0 0 1 4 5 - 5

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1. Introduction
Huge amounts of plastic wastes are currently generated due to the wide applications of polymeric materials. Plastic wastes account for about 8 wt.% of the
municipal solid wastes (MSW), whereas this proportion increases up to 20% in
volume due to their low density [1,2]. At present, plastic wastes are mainly disposed
of in landfills or incinerated with energy recovery [3,4]. Among plastic materials,
polyethylene world production in 1997 reached 33 million metric tons, accounting
for 70% of polyolefins consumption and 44% among all thermoplastic materials.
An emerging alternative for the treatment of plastic wastes is feedstock recycling,
which allows the plastic residues to be transformed into chemicals and fuels [1]. In
this way, thermal and catalytic degradations have been used to convert different
polyolefins into hydrocarbon mixtures. Recent works on the degradation of plastics
have revealed that catalytic processes allow the quality of degradation products to
be improved. Solid acid catalysts have mostly been used for the catalytic degradation of polyolefinic plastic wastes. Thus, Uemichi et al. reported that a valuable fuel
oil, like gasoline, was obtained from the degradation of polyethylene over a
silica alumina catalyst at about 500C [5,6]. Recently, results on the use of
catalysts, such as ZSM-5 zeolite and mesoporous MCM-41 for polyolefin cracking
have been reported [7 10]. Mertinkat et al. reported about the polystyrene and
polyethylene cracking over a spent commercial FCC catalyst, to obtain mainly
basic chemicals [11]. Aguado et al. have investigated the catalytic conversion of
polyolefins into liquid fuels at 400C, higher activities being obtained over MCM41 compared with amorphous silica alumina and ZSM-5 zeolite catalysts [12 14].
Most of the previous works about the thermal and catalytic cracking of polyolefins have been aimed at the production of gaseous and liquid hydrocarbons
[15 19]. In contrast, the present work deals with the thermal and catalytic
degradation of both, high and low-density polyethylene (HDPE and LDPE, respectively) under mild conditions in order to study the properties of the solid product
remaining in the reactor. Thereby, a variety of catalysts have been used for
promoting the polyethylene degradation: zeolites such as n-HZSM-5 and USY, a
commercial amorphous silica alumina, activated carbon, Pd charcoal powder and
mesoporous aluminosilicate materials (MCM-41), with and without impregnated
Pd.

2. Experimental

2.1. Materials
High and low density polyethylene, supplied by Repsol S.A., were used as raw
materials. Zeolite USY (Grace Division), amorphous silica alumina (Sudchemie,
KA-3), activated carbon (Chemviron Carbon) and Pd charcoal powder (Alpha)
were commercial catalyst samples.

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129

The synthesis of ZSM-5 with crystal size in the nanometer range (n-HZSM-5)
was carried out according to a procedure recently reported using tetrapropylammonium hydroxide (TPAOH) as template [20]. Tetraethyl orthosilicate (Aldrich, 98
wt.%) and aluminum isopropoxide (Aldrich, 98 wt.%) were used as silica and
aluminum sources, respectively. The crystallization took place under autogenous
pressure at 170C for 72 h. The zeolite obtained was separated by centrifugation,
washed with deionized water, dried at 110C for 12 h, and finally calcined under
static air for 7 h.
The MCM-41 sample was prepared according to a method previously described
[21], using hexadecyltrimethylammonium chloride as surfactant, and aluminum
isopropoxide and tetraethyl orthosilicate as aluminum and silica sources, respectively. Initially two solutions were prepared under stirring, one formed by the
surfactant and hydrochloric acid and the second one including the sources of silica
and aluminum. Once these solutions were homogenized, they were mixed and
stirred for 75 min at room conditions. In a second step, condensation reactions
were promoted by dropwise addition of a 2 wt.% aqueous ammonia solution under
stirring. The solid phase so obtained was washed with deionized water in a Buchner
funnel, dried at 110C for 12 h, and finally calcined at 550C in static air for 12 h.
Following this method, the acid form of MCM-41 was directly obtained, ion-exchange treatments being not necessary. Pd MCM-41 was prepared by wetness
impregnation of the MCM-41 sample with a tetraaminepalladium(II)-chloride
aqueous solution. The wetness-impregnated solid was dried at 110C for 12 h and
finally calcined under static air for 7 h. Thereafter, a reduction in hydrogen
atmosphere at 400C was carried out in order to obtain Pd0.

2.2. Catalyst characterization

Si/Al atomic ratios of the different samples were determined by X-ray fluorescence (XRF) with a Philips PW 1404 spectrometer. Measurements of the crystallinity of the samples were carried out by X-ray diffraction (XRD) using a Philips
XPERT MPD diffractometer with Cu Ka radiation.
N2 adsorption isotherms at 77 K were obtained using a Micromeritics ASAP
2010 apparatus, measuring both adsorption and desorption curves. Previously, the
samples were outgassed at 200C under vacuum for 5 h. Surface areas were
obtained by application of the Brunauer Emmet Teller (BET) procedure, while
the pore size distribution were determined by the BJH method applied to the
adsorption branch of the isotherm. In these calculations, cylindrical pore geometry
was assumed and the Harkins Jura equation was used to obtain the thickness of
the adsorbed layer. The micropore volume was calculated by application of the
t-plot method to a selected zone of the isotherm.

2.3. Reaction setup

The experiments for thermal and catalytic degradation of polyethylene were
carried out in a batch reactor provided with a helicoidal stirrer at 120 rpm (Fig. 1).

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In a standard experiment, 50 g of plastic was loaded into the reactor. Three

temperatures (380, 400 and 420C) and different reaction times (0360 min) under
nitrogen flow were studied. The effluent from the reactor was connected to a
water-cooled trap in order to condense the liquid products, whereas the effluent gas
was finally collected in a teflon bag. The gaseous products were analyzed in a
Hewlett Packard 5880A GC using a Porapak Q column. Liquid products were
analyzed in a Varian 3800 GC equipped with a flame ionization detector (FID) and
using a MXT 2881 semicapillary column.
Both the effluent liquid and the waxy product remaining in the reactor were also
characterized by nuclear magnetic resonance (NMR) using a Varian 300 MHz
spectrometer. The analysis were carried out at 120C, using a pulse width of 7 ms
(45) and 4.3 ms (45) with 3 and 5 s of delay time between accumulations for 1H
and 13C NMR, respectively. Deuterated tetrachloroethane was used as solvent to
identify the aromatic protons of the sample. Likewise, the waxy product was
analyzed by differential scanning calorimetry (DSC) with a Seiko DSC 620 instrument. Previously, in order to remove the thermal history of the sample, it was
heated at 10C min 1 from room temperature up to 150C, and thereafter cooled
at a rate of 20C min 1 up to 0C. The analysis was finally carried out heating up
to 150C at a rate of 10C min 1. A Waters model 150-C GPC equipped with a
differential refractometer detector and a Viscotek 110 differential viscometer was
used to determine the molecular weight averages and molecular weight distribution
of the raw polymer and the waxy products. Two PL-GEL mixed bed columns
connected in series were employed as GPC analytical columns. Each sample was
dissolved in 1,2,4-trichlorobenzene (TCB) with a concentration of 5 mg ml 1. The
eluent TCB was pumped at a constant flow of 0.7 ml min 1. Both, column and
detector temperatures were maintained at 145C.

Fig. 1. Scheme of the experimental cracking reaction system.

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131

3. Results and discussion

3.1. Catalysts properties

The main physicochemical properties of the catalysts used for the polyethylene
degradation are summarized in Table 1. A wide variety of catalysts have been
selected taking into account the previous experience of our research group and the
bibliography. Some of these catalysts have acid character with a wide range of Si/Al
atomic ratio: crystalline samples (n-HZSM-5 and HY zeolites), amorphous samples
(SiO2 Al2O3), and pseudocrystalline materials (MCM-41 and PdMCM-41). Nonacid catalysts are carbon-based materials: activated carbon and Pd charcoal
powder.
With regard to the textural properties of the catalysts shown in Table 1, the high
BET surface areas of MCM-41, Pd MCM-41 and activated carbon samples are
noteworthy, compared with the other catalysts. With regard to the pore volume, it
is interesting to emphasize that neither MCM-41 nor Pd MCM-41 nor SiO2 Al2O3
show micropores, while this range of pore sizes are present in the other samples.

3.2. LDPE degradation

Fig. 2 shows the results obtained in the thermal and catalytic cracking of LDPE
at different temperatures, where the yield of gases, liquids and solid products of the
different experiments have been plotted versus temperature.
The formation of both gaseous and liquid products is enhanced for catalysts with
the increase of temperature. The highest conversion of LDPE into gaseous products
is observed over the n-HZSM-5 zeolite, with a gas yield of 65 wt.% at 380C (Fig.
2a). Likewise, this catalyst leads to the production of large amounts of liquids at
temperatures as low as 340C. The maximum liquid yield is obtained over MCM-41
catalyst with a yield close to 50 wt.% for a reaction temperature of 420C (Fig. 2b).
According to the previous analysis of gaseous and liquid products, the solid yield
follows a decreasing trend with the reaction temperature (Fig. 2c), the highest yields
being obtained in the thermal cracking experiments. A slightly lower solid yield is
observed when the reaction is carried out over silica alumina, activated carbon and
HY zeolite, while a sharp decrease is observed when MCM-41 is used as catalyst.
The high cracking activity of n-HZSM-5 zeolite leads to the lack of solid product
for temperatures above 380C.
The activity found for the different catalysts can be related to their corresponding
physicochemical properties. Thus, the MCM-41 sample shows a high activity,
which can be due to the right combination of BET surface area, mesoporosity and
acid strength. The product distribution obtained with this catalyst suggests a
random scission mechanism as the main contribution to the overall cracking
process that takes place inside the pore structure of the solid.
Also a high activity is observed for the n-HZSM-5 zeolite reaching 100%
conversion to gaseous and liquids products at 380C and 30 min, although this
sample exhibits a lower BET surface area compared with MCM-41. Having in mind

n-HZSM-5
30
430
0.48
0.15

Catalyst
Si/Al
BET surface (m2 g1)
Pore volume (cm3 g1)
Micropore volume (cm3 g1)

Table 1
Physicochemical properties of the catalysts

3
583
0.26
0.23

HY

1070
0.48
0.48

Activated carbon

800
0.68
0.27

Pd charcoal powder

2
261
0.97

SiO2Al2O3

76
1275
0.79

MCM-41

85
934
0.54

PdMCM-41

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133

the micropore nature of this catalyst, which avoids the primary cracking reactions
to take place in the internal surface of the material, these results could be assigned
to its large external surface area, caused by the low crystal size of this sample ( 50
nm). Besides, the high acid strength of the zeolite active sites favors the LDPE
degradation according to an end-chain cracking mechanism, leading mainly to
gaseous hydrocarbons.
Regarding the results obtained over the amorphous silica alumina and activated
carbon samples the activity shown by these catalysts is lower than that of MCM-41,
although both materials possess pore sizes in the range of mesoporous, and even
certain macroporosity is present in the activated carbon sample.
The low activity obtained over HY zeolite can be explained having in mind its
microporous channels (0.74 nm) connecting the large cavities of 1.3 nm size
(supercages) present in this molecular sieve, which may allow the formation of
bulky coke precursors. Besides, the high aluminum content of HY zeolite (Si/Al =
3) may enhance coke formation reactions within its pore structure, which results in
a low activity for the LDPE cracking.
The product yield plots are useful to compare different activities but do not offer
the possibility of measuring the nature of the waxy product obtained by LDPE
degradation, which is the main goal of this work. Thereby, the solid product has
been investigated by 1H NMR, 13C NMR, DSC and GPC analysis.
From 1H NMR measurements, it has been possible to determine the olefinic
character of the waxy product obtained in the cracking experiments, which is
related to the stability of this product. Fig. 3 illustrates the 1H NMR spectra of the
raw LDPE and the waxy products coming from thermal cracking and catalytic
cracking over MCM-41. Two main peaks at 0.95 and 1.33 ppm can be observed,
which correspond to protons on methyl and methylene groups, respectively. The
plot in the range from 4 to 8 ppm shows other minor peaks corresponding to
different olefinic (4 6 ppm) and aromatic protons (7 ppm).
It is remarkable the significant differences between the solid products when
MCM-41 is used as catalyst, not only with regard to the decrease of the olefinic
protons contribution but also the selective removal of certain type of double bonds
present in the waxy product coming from thermal cracking. Also a higher aromatic
character is observed when the cracking process is carried out over MCM-41. In the
spectrum of the raw LDPE neither aromatic nor olefinic carbons are detected.
The relative number of protons in methyl groups can be regarded as a measurement of the cracking extension, hence a correlation between the latter and the
stability of the waxy product can be established, assuming that the stability is
related to the presence of olefinic bonds. Fig. 4 shows olefinic protons versus methyl
protons from 1H NMR analysis of the waxy product obtained over the different
catalysts investigated.
The product coming from the catalytic cracking of LDPE over MCM-41, shows
a quite different nature with a lower olefinic character compared with the products
obtained by thermal cracking and over the other catalysts. Most of the solid
products show a linear trend increasing the olefinic character with the cracking
extension up to an asymptotic limit value.

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Fig. 2. Thermal and catalytic cracking of LDPE at different temperatures (340, 380, 400 and 420C) and
at 30 min, (a) gas yield; (b) liquid yield; (c) solid yield.

R. 6an Grieken et al. / J. Anal. Appl. Pyrolysis 5859 (2001) 127142

135

Fig. 3. 1H NMR spectra, (a) raw LDPE; (b) waxy product from thermal cracking (420C, 120 min); (c)
waxy product from catalytic cracking over MCM-41 (420C, 120 min).

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Fig. 4. Olefinic protons vs. methyl protons in the waxy products.

DSC analysis provides information about the homogeneity and melting properties of the waxy products. Fig. 5 shows the DSC analysis corresponding to the raw
LDPE, and the solid products formed in the thermal degradation and catalytic
cracking over MCM-41. The product from thermal cracking shows a shift of the
main peak towards lower temperatures when it is compared with LDPE, as well as
shoulder at temperatures below 90C, probably due to the presence of lighter
hydrocarbons. The solid obtained in the LDPE catalytic conversion over MCM-41
presents a higher homogeneity than the one coming from thermal cracking, since a
narrower peak is observed in the DSC analysis, whereas the shoulder is less
accentuated. However, the solid product from the catalytic cracking exhibits two
main peaks one located at temperatures similar to the one corresponding to
LDPE, whereas the second one is in the temperature range of the solid product
obtained by just thermal treatment.
Additional information about the cracking degree and homogeneity of the waxy
product have been obtained by GPC analysis, through the measurement of the
weight-average molecular weight (Mw), the number-average molecular weight (Mn)
and the polydispersity (PD= Mw/Mn). The results obtained are as follows:
Raw LDPE: Mw =249016, Mn =31276, Pd= 7.96.
Waxy product from thermal cracking at 420C and 30 min: Mw = 3230, Mn =
810, PD= 4.00.

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137

Fig. 5. DSC analysis corresponding to raw LDPE, and waxy products from thermal and catalytic
cracking over MCM-41 (420C, 30 min).

Waxy product from catalytic cracking at 420C and 30 min: Mw = 4240,

Mn =2360, PD=1.98.
It is interesting to note that under the same reaction conditions the solid product
coming from the thermal cracking presents lower Mw and Mn compared with the
catalytic cracking. This result may indicate that in the earlier stages of the catalytic
LDPE conversion, crosslinking reactions take place beside the cracking process
[22]. Regarding the homogeneity, the polydispersity is lower in the case of catalytic
cracking, which indicates that the solid in this case is more homogeneous, which
agrees well with the results of the DSC analysis previously mentioned.
On the other hand, Table 2 summarizes the results of the 13C NMR measurements, for the raw LDPE, and the solid products coming from thermal degradation
and catalytic cracking over MCM-41. As it was expected, the raw LDPE shows

Table 2
Results from 13C NMR analysis of the raw LDPE and the solid product coming from thermal and
catalytic cracking over MCM-41 at 420C and 30 min
Product

Raw LDPE
Thermal
cracking
Catalytic
cracking

Number and type of branches in the

main chain per 1000 C atoms

Terminal methyl groups per 1000 C

atoms

C1

C2

C4

C6+

0.63

0.69
3.05

0.89
3.18

1.26

0.34

0.58

4.18

2.94

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butyl and higher hydrocarbon branches, the former being removed in the solid
obtained by thermal cracking. The reactivity of the tertiary carbon atoms in the
polymer chains promotes the scission of the branches as result of the primary stages
of the cracking process. However, the increase observed for C6 + branches in both
thermal and catalytic cracking is probably related to crosslinking reactions between
long hydrocarbon chains. These crosslinking reactions are promoted when MCM41 is used as catalyst, since the solid product is in this case more branched than that
obtained by thermal degradation.
Table 3 shows the results obtained in the 1H NMR analysis of the liquid and
solid products obtained in several of the thermal and catalytic cracking experiments. The comparison between thermal and catalytic cracking using MCM-41 at
420C shows a slightly higher cracking extension for the latter with a higher
contribution of protons in methyl groups. The olefinic character of the liquid and
solid products is clearly decreased when using MCM-41 as catalyst, whereas the
aromatic content of the liquid product is five-fold the one obtained in the liquid
from thermal cracking. These results indicate that hydrogen transfer reactions
leading to paraffinic and aromatic hydrocarbons are strongly promoted over the
MCM-41 catalyst.
From the point of view of the possible commercial applications of the waxy solid,
it would be interesting to obtain a product with low olefinic character, which would
provide it stability against oxidation. For this reason, it was considered interesting
to promote further the hydrogen transfer reactions by incorporation of group VIII
elements (Pd, Pt) into catalysts, which are known to promote hydrogen transfer
reactions. Thus, a commercial Pd charcoal powder and mesoporous material
MCM-41 impregnated with Pd were tested as catalysts in the LDPE cracking.
The results obtained over the Pd charcoal powder are also shown in Fig. 2,
leading to similar values to those obtained when activated carbon is used as the
catalyst. Likewise, from Fig. 4, where olefinic protons versus methyl protons are
plotted, it can be observed that this catalyst follows a similar trend to that
corresponding to thermal degradation and catalytic cracking over most of the
catalysts tested, with the exception of MCM-41. However, the results of 1H NMR
analysis of the waxy and liquid products obtained with Pd charcoal powder and
PdMCM-41 (Table 3), show that the aromatization and hydrogen transfer
reactions are not really improved in the Pd-containing catalysts compared with
MCM-41.
On the other hand, the solid and liquid products obtained with Pd MCM-41
show a lower number of methyl protons if compared with MCM-41, which is
related to a decrease in the cracking activity. The introduction of the Pd phase
through the aqueous impregnation solution may lead to ion exchange with protons
in Bronsted acid sites, which results in a decrease of the MCM-41 acidity.

3.3. HDPE degradation

Once selected, MCM-41 as the best catalyst for the production of a waxy solid
with low olefinic character, this material was also checked for the degradation of

T (C)

420
380
400
420
420
420

Experiment

Thermal cracking
MCM-41
MCM-41
MCM-41
Pd charcoal powder
PdMCM-41

30
30
30
30
30
30

t (min)

0.154
0.012
0.034
0.111
0.065
0.097

0.069
1.36
0.63
0.35
0.44
0.15

0.571
0.106
0.152
0.263
0.484
0.242

4.60
4.26
4.50
3.65
5.60
5.15

Liquid

Solid

Solid

Liquid

Olefinic protons (%)

Aromatic protons (%)

Table 3
Results from 1H NMR analysis of the waxy and liquid products

7.41
5.60
6.90
11.1
5.30
10.00

Solid

20.63
39.54
38.18
37.10
42.70
36.00

Liquid

Methyl protons (%)

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139

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Table 4
Results of LDPE and HDPE thermal and catalytic cracking
Catalyst

Thermal cracking
Catalytic cracking over MCM-41
Thermal cracking
Catalytic cracking over MCM-41

Plastic

LDPE
LDPE
HDPE
HDPE

T (C)

380
380
380
380

t (min)

360
360
360
360

Yield (%)
Gases

Liquids

Solids

7.3
37.3
2.5
35.9

2.5
23.2
0.0
22.9

90.2
39.5
97.5
41.2

HDPE. The results obtained are shown in Table 4. It can be seen that HDPE
thermal degradation requires higher reaction temperatures compared with LDPE to
obtain the waxy product, which is due to the lower reactivity of the linear polymer,
as it lacks in reactive tertiary carbon atoms. However, the use of MCM-41 as
catalyst leads to similar degradation degrees for both polyolefins. Higher proportions of gaseous and liquid hydrocarbons are produced in the catalytic cracking
compared with thermal degradation. Moreover, from the 1H NMR analysis, the
waxy product obtained in the HDPE catalytic treatments over MCM-41 presents a
significant lower content of olefins, which would confer it a higher stability, as it
was observed in the LDPE degradation.
Fig. 6 shows a comparison between the DSC analysis of the solids obtained from
LDPE and HDPE under the same reaction conditions. The DSC curve corresponding to the product of the HDPE cracking at 380C presents a Gaussian shape with
no formation of any type of shoulder, in contrast to the DSC analysis of the
product from LDPE cracking where the shoulder increases with the intensity of

Fig. 6. DSC analysis of waxy products from catalytic cracking of LDPE and HDPE with MCM-41
(380C, 360 min).

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141

cracking. This result indicates the lower homogeneity of the waxy product from
LDPE cracking, due to the formation of a more branched product, as it was
previously described for the LDPE cracking solid product.

4. Conclusions
LDPE cracking under mild conditions yields, in appropriate reaction conditions,
a solid waxy product with potential applications as alternative to hydrocarbon
mixtures obtained from petroleum fractionation.
Although thermal cracking between 360 and 420C leads to the highest solid
yields, its high olefin content makes it unsuitable for commercial uses due to
reactivity by oxidation. LDPE cracking is enhanced when catalysts are used,
lowering the solid yield although in the case of MCM-41, a clear improvement in
the stability of the solid product is achieved. The product distribution obtained for
the latter suggests a random scission mechanism governing the overall cracking
process.
The medium acid strength of MCM-41 avoids an intensive LDPE cracking,
whereas the large pore and low Al content of this material prevents its rapid
deactivation by coke formation. These properties are also responsible for crosslinking reactions between long hydrocarbon chains, as well as hydrogen transfer
reactions that lead to a decrease in the olefinic character of the solid product.
The use of HDPE instead of LDPE as starting material yields a solid with a
higher homogeneity, improving the properties of the waxy product for potential
applications.

Acknowledgements
Financial support from Comunidad Autonoma de Madrid (Project no: 07M/
0420/1997) is gratefully acknowledged. We are also grateful to REPSOL-YPF S.A.
for supplying the polyolefin samples and to CEPSA Research Center for the XRF
measurements of catalysts.

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