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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
128
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.
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.
130
131
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
132
R. 6an Grieken et al. / J. Anal. Appl. Pyrolysis 5859 (2001) 127142
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.
134
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.
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).
136
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.
137
Fig. 5. DSC analysis corresponding to raw LDPE, and waxy products from thermal and catalytic
cracking over MCM-41 (420C, 30 min).
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
C1
C2
C4
C6+
0.63
0.69
3.05
0.89
3.18
1.26
0.34
0.58
4.18
2.94
138
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.
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
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
140
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).
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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