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ELSEVIER Polymer Degradation and Stability 91 (2006) 3330e3338
www.elsevier.com/locate/polydegstab

Catalytic degradation of high density polyethylene over

nanocrystalline HZSM-5 zeolite
J.F. Mastral, C. Berrueco, M. Gea, J. Ceamanos*
Department of Chemical and Environmental Engineering, C.P.S, University of Zaragoza, Mara de Luna 3, 50018 Zaragoza, Spain
Received 20 December 2005; received in revised form 31 May 2006; accepted 16 June 2006
Available online 15 September 2006

Abstract

High density polyethylene (HDPE) was catalytically degraded using a laboratory fluidised bed reactor in order to obtain high yield of gas
fractions at mild temperatures, between 350 and 550  C. The catalyst used was nanocrystalline HZSM-5 zeolite. High yields of butenes (25%)
were found in the gas fractions, which were composed mainly of olefins. Waxes were wholly composed of linear and branched paraffins, with
components between C10 and C20. The effects of both temperature and polymer to catalyst ratio on the product yield were studied. Gas con-
version was dramatically decreased when the operation temperature was low (below 450  C) or when the polymer to catalyst ratio was greatly
increased (9.2). Gas and wax compositions significantly altered over 500  C, showing that a part of the HDPE was degraded thermally, increas-
ing the olefin concentration in the waxes. The same variation was observed in the experiments carried out at high polymer to catalyst ratios,
obtaining a 50% olefinic concentration in the waxes. The differences observed in product distributions can be attributed to both thermal and
catalytic degradations.
2006 Elsevier Ltd. All rights reserved.

Keywords: High density polyethylene; Zeolite; Catalyst; Pyrolysis; Product distribution

1. Introduction 6%, resulting in a 5% increase in plastic residues which

Huge amounts of plastic wastes are generated every year
due to the increasing variety of uses of plastics. Consumption
of polymers in Europe between 2000 and 2002 increased by
Abbreviations: ATOS, pillared clay derivative of a saponite (particle
size < 160 mm); AZA, pillared clay derivative of a montmorillonite (Zenith-
N) (particle size < 160 mm); FID, flame ionization detector; GC/MS, gas chro-
matograph/mass spectrum detector; HDPE, high density polyethylene; HDPE/
Cat, ratio of grams of HDPE fed per gram of catalyst in the reactor; HUSY,
ultrastable zeolite Y (H, acid form), or Faujasite, structure FAU; HZSM-5,
zeolite Socony Mobil e five (H, acid form), structure MFI; LDPE, low
density polyethylene; LLDPE, linear low density polyethylene; MCM-41,
mesoporous aluminosilicate in the hexagonal phase; MOR, mordenite (H,
acid form), structure MOR; NZ, natural zeolite, clinoptilolite type; SAHA,
silicaealumina, commercial name Synclyst 25; TCD, thermal conductivity
detector; TPD, temperature programmed desorption.
* Corresponding author. Tel.: 34 976762160; fax: 34 976761879.
E-mail address: ceamanos@unizar.es (J. Ceamanos).
were mainly eliminated by landfill and incineration. This
causes severe environmental problems because of chemical
inertness and pollutants [1]. The tertiary or chemical recycling
of plastics has become the most attractive method for the
environmentally friendly recovery of these solid residues.
Polyethylene, considering all types, is the most widely
generated plastic residue. Being an addition polymer, it cannot
be recycled by solvolysis. Consequently the processes studied
in previous work have been directed towards gasification and
pyrolysis. Due to the gaseous, oil and solid contaminants
generation during gasification and the partial consumption of
the polymer treated, pyrolysis is the most common method
tested by previous authors. However, thermal pyrolysis of
polyethylene requires high temperatures (above 650  C) to
generate considerable gaseous fractions [2]. Moreover, the
product distribution is very wide. Because of the energy and
the separation required, pyrolysis cannot be considered
economically viable.

0141-3910/$ - see front matter 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.polymdegradstab.2006.06.009
 J.F. Mastral et al. / Polymer Degradation and Stability 91 (2006) 3330e3338
In the last 10 years, researchers have been testing the use
of different catalysts in the pyrolysis of HDPE and low density
polyethylene (LDPE) [3e9]. Previous works show that there are
many solids that can reduce the temperature and increase the
selectivity of the process, obtaining similar yields of the gas
fraction than those obtained in pure thermal pyrolysis. These
can be grouped into zeolitic, mesoporous and clay catalysts.
Zeolitic materials are often used in the catalytic degrada-
tion of polyethylene and other addition polymers. Their acidity
and structure are suitable for obtaining high gas conversions
at relatively low temperatures, between 350 and 500  C.
Seo et al. [10] tested different types of zeolites such as
HZSM-5, ultrastable zeolite (HUSY) and mordenite (MOR)
for HDPE pyrolysis at 450  C, obtaining higher gas yields
over HZSM-5(powder) (63.5%) than over HUSY(powder) (27.0%)
and MOR(pellet) (18.5%).
This extraordinary yield can be explained by the properties
of HZSM-5. Most zeolites, including HZSM-5, show an excel-
lent catalytic efficiency on cracking, isomerization and aroma-
tization due to a strong acidity and a crystalline microporous
structure. HZSM-5 catalyst has an MFI structure with inter-
secting 5.4  5.6 and 5.1  5.5 A channels. Therefore, the ini-
tially cracked fragments can diffuse through its pores and react
further in the cavities created at the intersection of the two
channels, yielding more gaseous products. HZSM-5 presents
an excellent stability due to its particular structure, which pre-
vents the formation of coke. Furthermore, the opportunity of
pore blocking is low due to the intersecting connection of
the channels [11]. On the other hand, HUSY presents larger
pore size (7.4 A) than HZSM-5 and large supercages in the
channel systems. This structure leads to lower gas yields and
easy deactivation by coke deposition. Mordenite has a bottle-
neck pore structure consisting of a parallel two-dimensional
structure with intersecting channels of two different sizes,
which result in rapid deactivation. These results show that deg-
radation activity of zeolites depends not only on pore size and
acidity, but also on their shape [12].
Park et al. [13] tested many more zeolites (Beta, natural ze-
olite (NZ(clinoptilolite type)), HUSY and HZSM-5), also obtaining
the greatest gas yield from degradation over HZSM-5. How-
ever, their activity and selectivity depend on other factors,
the most important being the acidity, due to the role of acid
sites in the degradation mechanism. Bronsted acidity can be
increased by substituting the Na counter-ion by H protons.
The acid form is thus frequently used in the cracking pro-
cesses. TPD analysis showed that HZSM-5 and Beta zeolites
had the highest acidity, unlike HUSY and natural zeolite which
had medium and low acidities, respectively [14,15]. Lewis
acidity can be increased by changing the Si:Al ratio. In fact,
Park et al. [13] proved that the smaller the Si:Al ratio, the
higher the production of gases. The distribution of Si and Al
atoms in the structure can also affect the acidity, but only
the strength of the acid sites [16].
The pore size of zeolites works as a molecular sieve ob-
structing the free diffusion of large or wide molecules into
the internal surface of the catalyst. This can be a problem in
HDPE pyrolysis if the crystal size is not very small. Serrano
3331
et al. [15] carried out experiments of pyrolysis of a polyolefin
mixture (46.5% LDPE, 25% HDPE, 28.5% PP) over two dif-
ferent types of HZSM-5, one with a 75 nm crystal size and the
other with 3 mm. The results showed 85% and 10% gas con-
version, respectively. HZSM-5 with a crystal size in the nano-
meter range has enough external cracking activity to generate
molecules small enough to pass through the pores and over-
crack leading to higher gas yields.
The last factor to consider is deactivation. Both pore size
and acidity accelerate or inhibit coke deposition, which is
the main cause of deactivation [17,18]. Although HZSM-5
has strong acidity, and therefore a high degree of activity, its
pore size inhibits coke formation, making it highly resistant
to deactivation [19]. The large pores of HUSY and MOR
make deactivation easy in these cracking processes [20,21].
Mesoporous materials such as aluminiumesilicate MCM-
41 and silicaealumina SAHA, studied by different authors
[19,22e24], did not give adequate results due to their lower
acidity and wide pore size distribution.
The most recently studied catalysts are clays and pillared
clays. Gobin and Manos [20] tested linear low density polyeth-
ylene (LLDPE) degradation over saponite, montmorillonite
and their pillared derivatives (ATOS, AZA). Despite the high
liquid conversion, they showed a strong regenerability after
coke deposition during the experiments. Due to their wide dis-
tribution of pore size and their weak acid sites, they could not
produce higher gaseous fractions than other zeolites such as
HUSY and HZSM-5.
In the work presented here nanocrystalline HZSM-5 was se-
lected in order to study the catalytic pyrolysis of polyethylene.
One problem identified in the previous works [19,21,25] is the
poor contact between the catalyst and the polymer, so this study
has been carried out in a fluidised bed reactor which favours
isothermal control and mass transfer. The influence of temper-
ature and polymer to catalyst ratio on the yields to the different
fractions and on the product distribution has been analysed.
2. Materials
High density polyethylene was obtained from HOECHST
(HOSTALEN GH 4765), with a density of 0.958 g/cm3, a soft-
ening point of 80  C and a mean particle size of 3 mm. The cat-
alyst used in the experiments was zeolite HZSM-5 with crystal
size in the nanometer range; provided in powder form by Sud
Chemie Corporation. The physical properties were as follows:
MFI structure (5.3  5.6/5.1  5.5 A pore size), Si:Al ra-
tio 35, crystal size 100 nm, BET surface 397 m2/g and
hydrogen is used as the cation in the structure. The material
was sieved to obtain the adequate particle size, and was previ-
ously activated by calcination at 550  C under static air.
The composition of the reaction bed was 90% (by weight)
silica sand and 10% catalyst. Several fluidisation runs were
performed at ambient temperature and pressure to select the
suitable particle size range and to optimise the fluidising N2
flow rates to be used during the experiments. The particle sizes
were 75e150 mm for silica and 150e350 mm for HZSM-5 in
order to avoid segregation.
3332 J.F. Mastral et al. / Polymer Degradation and Stability 91 (2006) 3330e3338

3. Laboratory scale pyrolysis Table 1

Series A: experimental conditions and product yields (wt% of feed) for pyrol-
ysis experiments at different temperatures
The experimental system used in this work is shown in
Fig. 1. The study was carried out using a stainless steel, flui- Experiment A1 A2 A3 A4 A5
dised bed reactor 4.8 cm in diameter and 23 cm in height. Temperature ( C) 350 400 450 500 550
The reactor was externally heated using an electrical ring fur- Number of 3 5 5 5 5
batches
nace. The bed temperature was measured by a K type thermo- gBATCH (g) 4 4 4 4 4
couple inside the bed. Catalytic pyrolysis of HDPE was tested HDPE/Cat 0.60 1.33 1.23 1.41 1.33
at different temperatures (350, 400, 450, 500 and 550  C) and Qfluidization 30 30 30 35 30
with different polymer to catalyst ratios (HDPE/Cat 0.93, (ml N/s)
1.41, 9.20 and N(Thermal)). tTOTAL (min) 100 115 42 35 90
Gas yield (%) 16.77 60.46 77.88 78.48 69.12
High density polyethylene was gravity fed, via a gate valve, Wax yield (%) 10.90 13.08 22.12 21.52 30.88
to the fluidised bed. HDPE was dropped directly into the bed Solid residue (%) 72.33 26.46 0.00 0.00 0.00
in five batches of 4 g every 10 min, the time required for the
complete degradation of the polymer [20]. For experiments
in which the HDPE degradation rate was too slow (HDPE/ HPPlot/Al2O3, 50 m  0.53 mm  15 mm, with a flame ioniza-
Cat ratio 0.93 or 350  C), it was necessary to vary the quan- tion detector (FID). The concentration of H2 was determined
tity of every batch or the number of batches (Tables 1 and 2). by the TCD detector whilst the rest of the hydrocarbons
Complete fluidisation of the bed was secured with a contin- from C1 to C7 were detected by the FID.
uous N2 flow of 30 ml N/min which entered at the bottom of the Waxes were collected and analysed by GC/MS. They were first
reactor. The product stream was passed through a cyclone to dissolved in tetrahydrofuran (THF). The equipment included an
remove any particulate matter. The resulting vapours were HT-5 aluminium clad column, 25 m  0.32 mm  0.1 mm (non
passed through a cool water heat exchanger at 20  C, where polar), with a Tmax of 450  C. Helium was used as a carrier gas
some heavy hydrocarbons were condensed. The remaining with a flow rate of 1 ml N/min. Samples of 1 ml were injected
components were condensed using an iceeNaCl bath at in splitless mode in order to increase the quantity of dissolved
10  C. The exit flow was divided into two fractions. One wax injected. The high temperature column enabled oven temper-
fraction was made to pass through silica gel in order to retain atures of 400  C to be reached ensuring that hydrocarbons up to
waxy products carried by the gas in aerosol form, and subse- C60 could be analysed. The temperature programme was as
quently emitted to the atmosphere. The other was collected follows: 40  C initial temperature followed by a heating rate of
online in 3 l Tedlar bags for analysis during the experiment, 5  C/min up to 180  C, then an increase up to 350  C at a heating
one being used in every batch charged in the reactor. rate of 10  C/min, and finally 10 min at 350  C. The ion trap
detector had a mass range from 32 to 800 amu and was linked
to a computer with a WILEY library.
4. Analysis

The gas fraction was analysed by gas chromatography us- 5. Results

ing two HP 5890 series II. One of them was equipped with
a Porapack N column, 2.8 m  3 mm packed with 80/ 5.1. Product yields
100 mesh, and a molecular sieve 0.9 m  3 mm packed with
45/60 mesh, using a thermal conductivity detector (TCD). HDPE catalytic pyrolysis was carried out at five different
The second chromatograph included a semi-capillary column temperatures (350, 400, 450, 500, and 550  C) in order to study
HDPE
Hopper

Thermocouple K
v'V Gate Valve
Flow Controller I Fluidized Bed Reactor Gas Sampling Bag

rirspa
I ? <!
o
o
o
0 Water
Condenser
X Produced Gas

N,
Gas
Q ....
Temperature
Control
LV
Electrical
Furnace
isrmnr
1
-
Ice NaCI
Condenser
1
-
Ice NaCI
Condenser
^
Silica Gel and
Cotton Filter
to Atmosphere

TT
=
Data Acquisition
Cooling Water

Fig. 1. Scheme of the experimental cracking installation.

 J.F. Mastral et al. / Polymer Degradation and Stability 91 (2006) 3330e3338 3333

Table 2 A high increase in gas production was observed between

Series B: experimental conditions and product yields (wt% of feed) for pyrol- 340 and 400  C, and the solid residue disappeared at over
ysis experiments at 500  C and at different polymer to catalyst (PE/Cat) ratios
380  C. According to these results, it seems that the catalytic
Experiment B1 B2 B3 B4 effect is reduced at the highest temperatures. This fact can be
HDPE/Cat 0.93 1.41 9.2 N(Thermal) explained by considering the deactivation of the catalyst.
Number of batches 7 5 5 3 Studies of deactivation of zeolites by TGA showed that the
gBATCH (g) 2 4 4 4
%ZeolyteBED 10 10 1.35 0
activity of HZSM-5 is affected by temperature due to struc-
Qfluidization 35 35 30 30 tural changes. Apparently, high temperature affects the strong
(ml N/s) acid centres, mainly due to a dealumination process, although
tTOTAL (min) 76 35 56 100 this effect appears at higher temperatures (around 600  C)
Gas yield (%) 80.13 78.48 46.86 33.16 [26]. Miskolczi et al. [27] observed that the difference be-
Wax yield (%) 19.87 21.52 53.14 66.84
Solid residue (%) 0.00 0.00 0.00 0.00
tween non-catalytic and thermo-catalytic crackings became
less significant with increasing temperature. They indicated
that it could be a consequence of the coking of the catalyst
surfaces at higher temperature, which may block the active
the effect of the temperature on the yields of the pyrolysis prod- sites of the catalyst. There could therefore be an interaction
ucts. Table 1 shows the yields to the different fractions obtained between catalytic and thermal processes, and this is dis-
and the experimental conditions in every test. At lower temper- cussed below.
atures, polymer cracking is not able to form lighter molecules, Table 2 and Fig. 3 show the results of the experiments
thus little gaseous product is yielded. Moreover, a solid residue carried out with different polymer to catalyst ratios. No solid
is produced, corresponding to the partially pyrolysed HDPE, residue was produced due to the operation temperature
too heavy to escape from the catalytic bed. This residue tends (500  C). The lowest production of gas corresponds to
to react with wax compounds while the temperature is in- HDPE thermal cracking (HDPE/Cat N(Thermal)). Increasing
creased, and finally disappears in the experiment at 450  C the catalyst content favours gas generation and minimizes
(Fig. 2). The higher the temperature, the greater the amount wax yield. However, when the ratio is decreased from 1.41
of gases collected. The most outstanding growth in gas yield to 0.93, a very small gas fraction variation, from 78.48%
is observed when the experimental temperature increases to 80.13%, is observed. This was demonstrated by thermog-
from 350 to 400  C. The gaseous fraction increases in the range ravimetric studies made in a cycled spheres reactor. Schirmer
from 17% to 60%, dramatically reducing solid residue conver- et al. [25] reported that small variations in zeolite to HDPE
sion. At the higher temperatures studied (over 500  C), the gas ratios when the ratio was small (around 1) could not signif-
yield suddenly decreases while waxy products increase. icantly reduce the degradation temperature of HDPE. How-
Although HDPE catalytic cracking conversion depends on ever, ratios greater than 7 produced a strong decrease in
the physical properties of HZSM-5 (BET surface, crystal gas production.
size, acidity.), similar results were obtained in previous
works. Hernandez et al. [26] degraded HDPE at different
temperatures in a fluidised bed reactor using HZSM-5 zeo- 5.2. Gas composition
lite. The highest increase in gas yield was obtained between
300 and 400  C. They reported a decrease in gas production As is shown in Table 3, the gas yield is composed mainly
at higher temperatures, over 600  C. Van Grieken et al. [19] of olefins. Catalytic cracking of HDPE over nanocrystaline
used a stirred batch reactor and obtained similar results. HZSM-5 samples proceeds with high activity and very

100 Gas Yield (%) 100

Wax Yield (%) GasYield (%)
Solid Residue (%) Wax Yield (%)
80 80
Yield (%wt.)

Yield (%wt.)

60 60

40 40
'
A.
20 20

0 A- A- A 0
350 400 450 500 550 0.93 1.41 9.20 GO (Thermal)
Temperature (C) ratio PE/Cat

Fig. 2. Influence of the pyrolysis temperature on product distribution (Series A, Fig. 3. Influence of the catalyst ratios on product distribution (Series B,
HDPE/Cat z 1.3). T 500  C).
3334 J.F. Mastral et al. / Polymer Degradation and Stability 91 (2006) 3330e3338

Table 3 high generation rates (9.27 g/gHDPE) at the lowest temperature

Series A: gas composition (wt% of feed) for HDPE catalytic pyrolysis (HDPE/ tested (350  C).
Cat z 1.3) at different temperatures
These results are in agreement with those of other authors.
Experiment A1 A2 A3 A4 A5 Garforth et al. [22] studied the degradation of HDPE over
Temperature ( C) 350 400 450 500 550 HZSM-5 in a fluidised bed reactor and obtained olefins at
CH4 0.00 0.00 0.00 0.00 0.00 different temperatures (290e430  C). Propylene, cis/trans-
C2H6 0.00 0.00 0.00 0.00 0.10 butene and iso-butene were the compounds produced in the
C2H4 0.00 0.18 0.79 0.78 0.91 greatest quantities at each temperature in that interval. In
C2H2 0.00 0.00 0.00 0.00 0.00
C3H8 0.00 1.59 0.44 0.26 0.47
the formation of C5eC7 fraction, similar trends were ob-
C3H6 3.22 9.80 18.30 18.17 16.59 served, their yields being reduced by increasing the temper-
C4 5.27 18.31 24.88 23.85 22.46 ature and leading to lighter fractions (C1eC4). Bagri and
C4H10 0.19 0.39 0.36 0.21 0.20 Williams [4] described a great variation in ethane production
cis-C4H8/trans-C4H8 2.09 7.68 10.19 10.30 9.37 when the temperature was near 550  C. They confirmed
i-C4H8 2.35 7.98 10.63 9.64 8.84 a significant methane production at that temperature and an
C4H8 (1-butene) 0.49 2.28 3.74 3.84 3.95 increase at 600  C.
C4H6 (1,3-butadiene) 0.15 0.36 0.32 0.07 0.31
The gas distribution is clearly influenced by the HDPE/
C5eC7 9.27 30.3 35.17 35.99 28.68
Cat ratio (Table 4). Although high HDPE to zeolite propor-
tions (HDPE/Cat 9.2/N(Thermal)) increase the production
high selectivity towards olefinic gases [2]. Some fractions are of the heaviest fractions (C5eC7), the lightest hydrocarbons
influenced by temperature. Although propylene is the most (methane and ethane) are detected in that conditions. These
important product whatever be the temperature, its yield de- compounds are not produced in experiments with low
creases over 500  C. The same phenomenon is observed in HDPE/Cat ratios, where substantial amounts of butenes and
butene production, which shows an important concentration propylene are formed. Small variations in the HDPE/Cat ra-
of iso-butene compared to 1-butene production (Fig. 4). Nei- tio can change the gas composition. Butene production in-
ther methane nor hydrogen is detected in this range of tem- creases from 23.8 g/gHDPE to 44.5 g/gHDPE by reducing this
peratures. Small amounts of other products such as ethene ratio from 1.41 to 0.93. On the other hand, the C5eC7 frac-
appear and show an increase in their yield when the temper- tion decreases from 36.0 g/gHDPE to 25.6 g/gHDPE. As the ra-
ature changes from 400 to 450  C (0.18 g/gHDPE at 400  C tio is increased, the gas distribution becomes similar to that
and 0.79 g/gHDPE at 450  C). Another remarkable fact is of the gaseous products produced by thermal pyrolysis (infin-
the production of ethane which starts at the highest temper- ite ratio). Methane and ethane, which are produced in ther-
atures (550  C). mal pyrolysis experiment, are not detected at low ratios
Lower temperatures produce gases rich in heavy (C5eC7) (0.93 and 1.41), but they are produced at a ratio of 9.2.
compounds. The higher the temperature, the lighter the com- The zeolite effect is again shown in the production of all bu-
pounds produced. Temperatures between 450 and 550  C pro- tenes. Thermal pyrolysis produces the same quantity of cis/
duce high concentrations of C1eC4 fractions, which are trans-butene, iso-butene and 1-butene while cis/trans-butene
mainly represented by propylene and butenes. On the other and iso-butene reach twice the level of production of 1-
hand, the fraction of heavier compounds (C5eC7) shows butene when HZSM-5 is added (Fig. 5).

Alkane (C10-C20) Alkane (C21-C40) D Branched Alkane

Alkene Branched Alkene Cycled and aromatic
Table 4
Series B: gas composition (wt% of feed) for HDPE catalytic pyrolysis at
100 500  C and at different polymer to catalyst ratios (HDPE/Cat)
Experiment B1 B2 B3 B4
80
PE/Cat 0.93 1.41 9.2 N(Thermal)
CH4 0.00 0.00 0.05 0.26
60
C2H6 0.00 0.00 0.13 0.29
% Area

C2H4 0.93 0.78 0.30 0.40

40 C2H2 0.00 0.00 0.00 0.09
C3H8 0.35 0.26 0.25 0.24
20
C3H6 9.72 18.17 5.85 2.58
C4 44.54 23.85 8.60 4.24

0 C4H10 0.06 0.21 0.23 0.31

350 400 450 500 550 cis-C4H8/trans-C4H8 18.16 10.30 3.71 1.73
Temperature (C) i-C4H8 17.54 9.64 3.20 1.06
C4H8 (1-butene) 8.84 3.84 1.68 1.07
Fig. 4. Area percentage of compound types detected in wax analysis from Se- C4H6 (1,3-butadiene) 0.00 0.07 0.00 0.06
ries A experiments carried out at HDPE/Cat z 1.3 and at different
C5eC7 25.64 35.99 34.08 25.72
temperatures.
 J.F. Mastral et al. / Polymer Degradation and Stability 91 (2006) 3330e3338 3335

Alkane (C10-C20) Alkane (C21-C40) ED Branched Alkane -hr Propene Butane cis/trans Butene
Alkene Branched Alkene Cycled and aromatic i- Butene 1-Butene 1,3-Butadiene
100 20
18
80 16
14

Yield (% wt.)
60 12
% Area

10

40 8
6
4
20
2

0
0.93 1.41
Ratio HDPE/Cat
Fig. 5. Area percentage of compound types detected in wax analysis from Se-
ries B experiments carried out at 500  C and at different polymer to catalyst
ratios.
5.3. Wax composition
Waxy products are composed of linear hydrocarbons (high
molecular weight paraffins) between decane and eicosene. As
is shown in Fig. 6, this composition is invariant at middle-
range temperatures (350e500  C). An important change in
the composition is observed when the temperature is raised
to 550  C. The waxes produced are then composed of a mixture
of heavy and light linear hydrocarbons (C10eC20 and C21e
C40). Some olefins, branched paraffins and aromatics are
also detected.
Varying the HDPE/Cat ratio determines the wax composi-
tion greatly (Fig. 7). Low ratios (HDPE/Cat 0.93, 1.41) pro-
duce light and linear hydrocarbons (between decane and
eicosene). Increasing the ratio (HDPE/Cat 9.2) generates
waxes richer in olefinic hydrocarbons, branched paraffins
and aromatics. This composition is quite similar to that
obtained in the absence of catalysts (thermal degradation).
Waxes rich in olefins and aromatics were produced in the
experiment carried out at 500  C and HDPE/Cat N(Thermal).
-hr Propene cis/trans Butene
1-Butene C5-C7
40
0 * =&
0.93 1.41 9.2 CO (Thermal)
9.20 00 (Thermal)
Ratio (HDPE/Cat)
Fig. 7. Evolution of main gases obtained with polyethylene/catalyst ratio (Se-
ries B, T 500  C).
Some typical chromatograms are presented in Fig. 8. Cata-
lytic pyrolysis waxes (experiments at ratios of 0.93 and 1.41)
show wide peaks which represent linear alkanes. Little
branched alkane content is quantified and no alkene is de-
tected. Many differences are shown in the waxes from the
runs carried out with a ratio of 9.2. Peaks representing alkenes
appear near the wide linear alkane peaks. This chromatogram
is quite similar to those obtained from the thermal pyrolysis
experiments previously carried out by other authors.
6. Discussion
It is generally believed that thermal degradation occurs by
a radical mechanism, generating many oligomers by hydrogen
transfer from the tertiary carbon atom along the polymer
chain. However, catalytic degradation of HDPE is known to
proceed by a carbenium ion mechanism [13,28e30]. The ini-
tial step is considered to occur either by the abstraction of the
hybrid ion (by Lewis acid sites) from the HDPE molecule or
by the addition of a proton (by Bronsted acid sites) to the
CeC bonds of the HDPE molecule or thermally degraded ole-
fins. The cracking of polymer carbocation proceeds there after
iso-butilene step-by-step into lower molecular weight hydrocarbons.

35
__
-G- -a.
These carbenium and carbonium mechanisms require the
presence of strong acid sites. However, a direct relationship
between the acid strength and the measured activities is not
30 /
B- "
'
'

f]
observed. On the contrary, a direct relationship is clearly ob-
Yield (% wt.)

/
25 /
/ served between the activity, the external surface area/crystal
20 /
/
size of the zeolite samples and the pore shape, which confirms
/
/
/ A- that steric and/or internal diffusion hindrances are present for
15 /
/ the catalytic cracking of the bulky polymer molecules [12,15].
10 i f
/
^ As expected, the catalysts having small crystals present high
5 external surface area. The external acid sites are not limited
0 + by steric or diffusion problems. Thus, they are essential to pro-
350 400 450 500 550 mote the initial steps of the polyolefin cracking.
Temperature (C) Accordingly, bulky molecules which are not able to enter
Fig. 6. Evolution of main gases obtained with pyrolysis temperature (Series A, the zeolite micropores can be cracked on the external surface.
HDPE/Cat z 1.3). Moreover, given the small crystal size the primary products of
3336 J.F. Mastral et al. / Polymer Degradation and Stability 91 (2006) 3330e3338

(a)
Tridecane Tetradecane
Dodecane Pentadecane

Hexadecane
Abundance
Undecane Heptadecane

Hexadecane

Octadecane
Nonadecane

n.d n.d n.d n.d n.d.

n.d
n.d

C11 C12 C13 C14 C15 C16 C17 C18 C19 C20
n.d.: not determined.

(b)
Dodecane

Abundance
Dodecene
Abundance

C12

if V m
i [
C10 C15 C20

Fig. 8. Chromatogram of waxes obtained in the experiments carried out at: (a) 500  C and PE/Cat 1.41; (b) 500  C and PE/Cat 9.2.

degradation are favoured in nanocrystalline HZSM-5, like the
one used in this study.
Some researchers indicate that the main reaction pathway is
end-chain scission, which yields light hydrocarbons as primary
products. Other reactions that may take place are oligomeriza-
tion, cyclization and aromatization leading to the formation of
a wider variety of hydrocarbons, although limited and con-
trolled by the HZSM-5 shape-selectivity [30]. In the case of
nanocrystalline HZSM-5, it is expected that the presence of
a high external surface affects negatively its shape-selectivity.
However, the obtained results indicate that, in spite of their
high external surface, the end-chain cracking is the predomi-
nant mechanism. Only when the catalyst activity is very
high, oligomerization, cyclization and aromatization reactions
are important enough to promote the formation of heavier
products.
Catalytic cracking of high density polyethylene that starts
at the active sites on the external surface of the zeolite con-
tinues on the strong acid sites inside the pores [26,30]. The
cracking could occur in the channels, due to the strong inter-
action existing between the adsorbed carbenium ions and the
zeolite surface, though the reaction is less energetically
favourable due to the formation of primary carbenium ions.
The stability of these chemical species increases as alkyl-sub-
stitutes are added to the carbon atom. Thus, carbenium ions
formed on acid sites will isomerize in order to stabilize, ex-
plaining the low selectivity to terminal alkenes (1-butene).
The porous structure of zeolites makes a restrictive selection
of molecules by size. Big molecules formed at the external
surface cannot enter the pores and crack on the external acid
sites. Moreover, the small pores prevent bimolecular reactions
such as protolytic cracking or oligomerization from taking
place. The smaller the pore diameter, the stronger the interac-
tion between the adsorbed carbenium ions and the zeolite sur-
faces, resulting in a more direct cracking. The smaller the pore
size, the greater the extent of suppression of the hydrogen
transfer reaction of alkenes. The hydrogen transfer reactions,
which involve the formation of bulky bimolecular reaction in-
termediates, are mainly controlled by steric constraints, by the
space available inside the micropores of the zeolites [11].
The most important mechanism in the pores is b-scission
producing light olefinic compounds. Gases composed of
light olefins result from catalytic cracking taking place in
the internal pores. The stability of terminal carbenium ions
 J.F. Mastral et al. / Polymer Degradation and Stability 91 (2006) 3330e3338
and the b-scission mechanism are the two factors that obstruct
ethylene formation and favour propylene and butene yields.
On the other hand, acid sites on the external surface are not
restrictive. Paraffin producing reactions such as hydrogen
transfer or alkylation can take place. Waxes composed of
heavier and paraffin hydrocarbons are mainly produced in
the acid sites of the external surface. Branched and linear par-
affins are the result of bimolecular reactions which are not hin-
dered by the structure.
6.1. Temperature effect
Temperature has a direct effect on gas, wax and solid
yields. The higher the temperature, the more important are
the b-scission reactions. In these conditions, light molecules
are formed that can enter the pores and overcrack. As a result
of this phenomenon a very sharp increase of the gas yield be-
tween 350 and 450  C is observed. This is not, however, a con-
stant tendency. When the temperature is too high, thermal
cracking can take place and polyethylene degrades in both
ways: thermally and catalytically. The gas yield decreases at
550  C due to the higher production of wax by thermal degra-
dation at this temperature.
It is well known that thermal degradation of HDPE is
a chain reaction mechanism in which free radicals are con-
sumed and produced [2,31]. Typical reactions of these species
are b-scission, isomerization, hydrogen transfer, oligomeriza-
tion and DielseAlder addition. There are no pore restrictions
in thermal cracking, so temperature is the only parameter that
determines all the thermodynamic equilibria leading to the
final conversion of each compound produced. Aromatics,
olefins and branched olefins are significant components of
the wax.
Various previous works report the influence of catalyst de-
activation on product yields at high temperatures. Hernandez
et al. [26] attributed the decrease in gas yield operating at
an HDPE/Cat ratio of 5 and at 600  C to temperature deactiva-
tion. High temperatures can distort the structure of the zeolite,
favouring dealumination and sintering inside the crystal which
would directly alter the acidity and consequently its activity.
Other researchers [27] indicate that the different activities ob-
served at different temperatures could be a consequence of the
coking of the surfaces at higher temperatures, which may
block the active sites. In these conditions, HDPE would be
mainly thermally degraded. Nevertheless, the temperatures
tested are not too high. Products obtained at 550  C show an
influence of thermal cracking which is clearly seen in the com-
position of olefin waxes. It is thus possible that the effect of
the thermal pyrolysis process is more significant than zeolite
deactivation by dealumination, which is not reported by
some authors at 550  C [4,29]. Gas and wax compositions
do not vary over a wide range of temperatures (350e
500  C). However, the influence of thermal cracking at
550  C changes both distributions. Aromatics and olefins are
formed in the wax fraction, and gases contain light paraffins.
Cracking activity decreases producing heavier gaseous frac-
tions (C5eC7) and waxy linear paraffins (C21eC40).
3337
6.2. HDPE/Cat ratio effect
The ratio of polymer to catalyst has a very important effect
on the composition and yield of every fraction produced. Low
ratios result in a high concentration of acid sites per gram of
polymer fed, and thus high gas conversion [24]. Waxes ob-
tained in the experiments at ratios of 0.27 and 1.41 are com-
posed of linear paraffins, typical of the catalytic pyrolysis
over HZSM-5.
Increasing the ratio directly affects the way in which the
polymer degrades. The higher the HDPE/Cat proportion, the
greater the HDPE being thermally degraded. Gas products
from the experiments carried out at an HDPE/Cat ratio of
9.2 and N(Thermal) contain methane, which is not formed by
catalytic pyrolysis (b-scission mechanism). Moreover, the
gas fraction generated is relatively low whilst the wax fraction
is important due to the low temperature (500  C).
It is generally accepted that the thermal pyrolysis mecha-
nism begins to dominate HDPE cracking at 500  C. The com-
position of waxes at a 9.2 ratio is rich in olefins. In any case,
increasing the catalyst content can reduce the thermal effect,
and this shows that the temperature is not so high as to have
any influence over the predominance of the catalytic pathway.
However, as has been explained above, experiments under-
taken at 550  C show the influence of thermal cracking in spite
of the high polymer to catalyst ratio (1.14).
7. Conclusions
Catalytic pyrolysis of HDPE is a possible lower cost alter-
native to other polymer recycling technologies. The use of
nanocrystalline HZSM-5 allows greater yields of gas fractions
at mild temperatures and a higher selectivity to the products
obtained than those achieved by thermal cracking. First, poly-
ethylene is cracked over the acid sites on the external surface
of the zeolite. A part of the compounds produced can then dif-
fuse into the internal active surface through the zig-zag pores
and overcrack giving lighter compounds. Due to the size re-
striction of the pores, gases are produced mainly in the pores
while waxes are the result of external cracking. The tempera-
ture affects the gas and wax yields. Gas production increases
as the temperature rises. However, when the temperature ex-
ceeds 500  C, some HDPE is cracked thermally, increasing
the wax yield and varying the wax and gas compositions. If the
catalytic pyrolysis temperature is too low (350e400  C), the
polymer is not fully cracked and a solid residue is produced
in the reaction bed.
The gases are mainly composed of olefins. Cracking reac-
tions (b-scission) control the reaction mechanism inside the
pores. Due to their small dimensions, HZSM-5 pores inhibit
bimolecular reactions, which are a source for paraffin produc-
tion. Terminal olefins are not produced in significant quantities
because of the strong effect of isomerization reactions.
The waxes obtained have very high concentrations of com-
pounds between C10 and C20. This composition does not change
over a wide temperature range (350e500  C). The paraffin pro-
duction mechanism controls the process (b-scission hydrogen
3338 J.F. Mastral et al. / Polymer Degradation and Stability 91 (2006) 3330e3338
transfer). As with the gas distribution, the wax composition
changes at temperatures exceeding 500  C. Typical thermal
pyrolysis products such as heavy olefins, cycles and aromatics
are detected at 550  C.
The polymer to catalyst ratio also affects the product yields.
This influence is especially noticeable when the ratio is high.
In these cases, the number of acid sites per gram of polyethyl-
ene is not sufficient to degrade all the polymer, resulting in
a lower gas production and altering the product distribution.
It has been demonstrated that thermal pyrolysis (HDPE/
Cat N(Thermal)) produces lower gas yields than catalytic py-
rolysis, and that this fraction is largely composed of heavier
compounds (C5eC7). The chain reaction mechanism and rad-
ical species involving the thermal degradation of polyethylene
produce olefinic gases, as in the catalytic mechanism, but they
also allow methane formation which had not previously been
produced. The most important compositional change is ob-
served in the waxes which increase their olefinic and cycle
contents as the HDPE/Cat ratio increases.
The results obtained show that the most suitable tempera-
ture and HDPE/Cat ratio for the process are 450  C and
1.41, respectively. In these conditions no solid residue is
formed and the wax obtained does not contain olefins and cy-
clics which are environmentally and operationally dangerous.
Acknowledgements
The authors express their gratitude to C.I.C.Y.T. (Project
PPQ2002-01625) for providing financial support for this work.
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