Polymer Degradation and Stability 110 (2014) 482e491

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Polymer Degradation and Stability

journal homepage: www.elsevier.com/locate/polydegstab

Catalytic and thermal pyrolysis of polycarbonate in a fixed-bed

reactor: The effect of catalysts on products yields and composition
E.V. Antonakou a, K.G. Kalogiannis b, S.D. Stefanidis b, c, S.A. Karakoulia b,
K.S. Triantafyllidis a, b, A.A. Lappas b, D.S. Achilias a, *
a
Department of Chemistry, Aristotle University of Thessaloniki, 54124, Thessaloniki, Greece
b
Chemical Process and Energy Resources Institute, Centre for Research and Technology Hellas, 57001, Thermi, Thessaloniki, Greece
c
Department of Mechanical Engineering, University of Western Macedonia, 50100, Kozani, Greece

a r t i c l e i n f o a b s t r a c t

Article history: A meaningful and advanced method concerning the management of waste electrical and electronic
Received 9 July 2014 equipment (WEEE) becomes a necessity, mainly due to their increased production, applications and their
Received in revised form short life. Thermal methods have been an attractive option and for this reason the investigation of py-
1 October 2014
rolysis and catalytic pyrolysis as a potential method for the recycling of polycarbonate (PC) based plastics
Accepted 7 October 2014
Available online 29 October 2014
has been the aim of the current study. Nine different catalysts with variations in properties (such as
porosity and acidity/basicity) were introduced in a bench scale pyrolysis system together with the
polycarbonate polymeric material and the pyrolysis fractions were collected and analyzed. The liquid
Keywords:
Polycarbonate
product consisted mainly of phenols and substituted phenols as well as the original monomer and, due to
Pyrolysis the commercial value of these products in the chemical industry, it is expected to enhance the economic
Zeolites viability of the process. Results showed a reduction in the degradation temperature in the presence of all
Catalysts catalytic materials, depending on the pore characteristics and the acidic nature of the solid. It seems that
Phenols in the presence of the basic catalysts, PC degradation leads to lower molecular weight compounds and
high phenolic fractions in the liquid produced. In terms of reduction in the production of the monomer,
pore size rather than acidity appears to be the determining factor.
© 2014 Elsevier Ltd. All rights reserved.

1. Introduction A typical WEEE contains 20e30% [2] plastics. The composition

The evolution in the technology of waste electrical and elec-
tronic equipment (WEEE) combined with a short life for most of the
products, is posing an increasing problem of the management of
the specific waste stream. The numbers are representative: in the
EU, 9.5 million tons of WEEE were disposed in 2008, and this is
expected to rise to 12.3 million tons by 2020 [1,2]. EU, in an attempt
to deal with the problem and at the same time maintain the oil and
fossil fuel reserves, has introduced the 2002/96/EC directive, which
demands 70e80% of the WEEE generated to be recovered in terms
of energy and materials [2]. The directive clearly aims to minimize
the percentage of solid wastes that will be landfilled or combusted
and states that by 2020, all solid waste streams (including plastics)
should be diverted towards thermal and/or mechanical treatment
and energy recovery.
* Corresponding author. Tel.: þ30 2310997822.
E-mail address: axilias@chem.auth.gr (D.S. Achilias).
can vary, but an example of the breakdown from actually collected
WEEE is acrylonitrileebutadieneestyrene (ABS) 30%, high impact
polystyrene (HIPS) 25%, polycarbonate (PC) 10%, PC/ABS 9%, poly-
propylene (PP) 8%, poly(phenylene ether) (PPE)/HIPS 7%, poly(vinyl
chloride) (PVC) 3%, polystyrene (PS) 3%, polyamide (PA) 3%, poly(-
butylene terephthalate) (PBT) 2% [3].
Poly(bisphenol A carbonate), PC, one of most significant frac-
tions of the WEEEs, is a polymer with a variety of optical and
technical applications and an advancing production technology. It
is widely used in optical data storage devices, such as CD, CDeR and
DVD discs [4]. Its global production is steadily increasing from
2.3 Mt in 2004, to 3.3 Mt in 2008 [5,6]. Because of its optical clarity,
excellent thermal resistance and high impact strength, poly-
carbonate (PC), is used in a wide range of industrial applications,
such as automotive and transportation, building and construction,
packaging, medical, optical and ophthalmic, and also finds use in
the audio, video and interactive software media [7]. Because of its
resistance at high temperatures, it is also used as a water container
and in baby milk bottles. Finally, polycarbonate as well as its blends

http://dx.doi.org/10.1016/j.polymdegradstab.2014.10.007
0141-3910/© 2014 Elsevier Ltd. All rights reserved.
 E.V. Antonakou et al. / Polymer Degradation and Stability 110 (2014) 482e491
with other polymers found in WEEEs (such as acryloni-
trileebutadieneestyrene (ABS)), exhibits effective flame retardant
properties, which again opens a new area of applications [8].
A meaningful recycling method will make full use of the prod-
ucts embodied energy and will not contribute to environmental
pollution. Concerning PC, the traditional methods of disposal, such
as landfilling and incineration which are still in use, apart from the
obvious social, economic and environmental limitations that apply
to all disposed polymers, are also related to the leaching of the
monomer bis-phenol A (BPA) and BPA based oligomers. BPA is an
endocrine disruptor and exhibits a series of harmful effects to both
humans and the environment. Most of the PC recycling methods
result in a large amount of the actual polymer or the monomer in
the solid waste stream, which make it difficult to handle, since it is
not biodegradable, has a high melting point [7], requires a
complicated product separation scheme and it is related to a series
of environmental problems [9]. Thermochemical degradation
methods appear to be a promising alternative for polymers treat-
ment since they provide energy and materials recovery, while their
disadvantages are related to the low selectivity in terms of the
monomer and variety in the products composition, both of which
could be overcome with the introduction of a suitable catalyst in
the pyrolysis process.
The main pyrolysis products of PC are expected to be its
monomer (BPA) and also a series of organic compounds of phenolic
origin, which add an additional interest in these degradation
studies by the fact that phenols could potentially add a commercial
value to the pyrolysis products. Phenols can be used as colorants,
antioxidants in the food industry to increase shelf-life and in
medicine specifically in the protection against a number of patho-
logical disturbances, such as atherosclerosis, brain dysfunction and
cancer. Additionally, polyphenols may be used for the production of
paint, paper and cosmetics, as well as in wood adhesives (resins)
applications.
Most of the published studies on polycarbonate pyrolysis focus
on the investigation of its mechanism and, although they originate
in 1964 [10,11], there still seem to be different scientific opinions
about its decomposition reactions. Early studies [10,11] suggested
that the degradation process follows a random chain scission
mechanism with the formation of free radicals, while other works
proposed that the initial step is the oxidative hydrogen cleavage
from isopropylidene linkage [12].
Montaudo et al. proposed that the degradation of PC is mainly
an ionic process and that the major degradation pathways for PC
are the rearrangement of carbonate linkage by intramolecular ester
exchange and disproportionation of isopropylidene linkages
[13,14]. Puglishi et al [12] later suggested a meaningful reaction
scheme to describe the thermal degradation pathways of PC, which
include cyclic oligomers generation by an intramolecular exchange
reaction at 400e500  C and also hydrolysis reactions producing
phenolic end groups and CO2 in this temperature range. He also
suggested the formation of ether bridges by decarboxylation of the
carbonate groups, which is also responsible for the evolution of
CO2. At higher temperature (500e700  C) other decomposition
reactions involving molecular rearrangements or decomposition of
the polycarbonate's structural unit to yield phenyl and isopropenyl
end groups, dibenzofuran units and compounds containing
xanthone and fluorenone units have been discussed [12].
In a more recent study, Nam Jang et al. [15], reported a more
extended identification of products by applying TGA/FTIR tech-
niques. They also suggested that the main degradation pathways of
polycarbonate follow the chain scission mechanism and the main
reactions were classified into two categories: chain scission of
isopropylidene linkages and hydrolysis/alcoholysis of carbonate
linkages [8].
483
It becomes clear from the above that although different research
groups agree on the nature of most of the compounds produced
through polycarbonate pyrolysis (e.g. phenol, substituted phenols,
the monomer), there are still controversial arguments regarding
the pathway followed in the reaction mechanism: random chain
scission versus ionic reaction mechanisms, which makes it still an
open area for further investigation.
One of the main drawbacks of pyrolysis is the wide range of the
products, which can be explained by the random character of the
free radical mechanism of the thermal decomposition. Catalytic
pyrolysis seems to be able to overcome this and also other disad-
vantages of the method, since the introduction of a suitable cata-
lytic material will favor the pyrolysis process both by tailoring the
composition of the products and by reducing the energy needs
since the reaction's activation energy is lowered. Some of the ad-
vantages of a catalyst in the degradation process are: lowering the
degradation temperature, shortening the degradation time,
increasing the extent of degradation, reducing the proportion of
solid residue in final products, and/or narrowing the product dis-
tribution [7,15] and more specifically in the case of PC, increasing
the percentage of liquid product and subsequently increasing the
amount of the desirable phenolic fraction.
Despite these advantages of the introduction of the catalyst in
the pyrolysis system, the literature on catalytic pyrolysis of PC is
very limited [6,16], while most of the research on PC degradation
focuses on thermal treatment under different atmospheres (pres-
ence or absence of oxygen) and different types of reactors and
products analysis. Grause et al. [5] have studied a series of basic
catalytic materials in the pyrolytic hydrolysis of PC, and they re-
ported that BPA was obtained as the main product at 300  C with a
yield of 78% with MgO [5]. Chiu et al. [7] performed an extensive
report on pyrolysis of PC in the presence of ten different metal
chlorides. The four more active metal chlorides were SnCl2, ZnCl2,
FeCl3, and MgCl2, and they have been reported to enhance the
degradation of PC and to increase the conversion from 8.5% to more
than 70%. They have suggested that the catalytic activity of the
metal chlorides could be due to the redox properties of the tran-
sitions metals involved. Li et al. [17] studied the effect of a metal
complex catalyst (zinc glutarate) on the thermal decomposition of
the poly(propylene carbonate) PPC. Only minor effects in reducing
the activation energy were reported. Day et al. [18], in a study of
pyrolysis of polymers used by the electronics industry, reported the
pyrolysis of PC in the presence of copper (Cu) and the results sug-
gested that Cu can significantly affect the degradation reaction
pathways and the pyrolysis product distribution, since most of the
products were increased by the use of Cu. Blazso [19] used copper
chlorides as catalysts at 600  C and observed an increase of BPA
among the pyrolysis products. On the other hand, Sala et al. [20]
reported that thermal treatment in the presence of CuCl2, in ni-
trogen atmosphere, substantially reduced the BPA production.
Although in most of the above studies the selection of a catalyst
was related to its redox properties, it was also decided on the basis
of the experience on pyrolysis of other polymeric materials [21e26]
to also consider the porosity and acidic characteristics of the
catalyst. Tuning of the acid sites (number, type and strength) is an
important step in designing the catalyst, as it significantly affects
the activity and product selectivity. Acidic zeolites exhibit excellent
properties as catalysts for the pyrolysis of plastic wastes; they have
been reported to decrease the decomposition temperature, pro-
mote deoxygenation and gasoline type compound (aromatic and
branched) formation and allow more valuable gaseous products to
be obtained [21,27]. HZSM-5 zeolites have proved to be efficient
catalysts for catalytic degradation of polymers because of their
strong acidity for the carbonecarbon bond scission and unique
pore structure to favor formation of small aromatics and to reduce
484 E.V. Antonakou et al. / Polymer Degradation and Stability 110 (2014) 482e491

Table 1
Porosity characteristics of the catalysts.

Catalysts Surface area (m2/g)a Total pore Micropore Meso/macropore Average pore diameter (nm)e
volume (cm3/g)b volume (cm3/g)c volume (cm3/g)d

ZSM-5 450 0.273 0.133 0.140 microporous

ZSM-5 eq/dil. 138 0.108 0.037 0.071 microporous,~4.0f
Silicalite 390 0.227 0.111 0.116 microporous
USY 746 0.482 0.244 0.238 microporous
Al-MCM-41 882 1.123 e 1.123 2.7
g-Al2O3 195 0.632 e 0.632 13e15
MgO-HP 63 0.362 e 0.362 28.7
MgO-MP 62 0.366 e 0.366 29.2
CaO 10 0.034 e 0.034 e
a
From multi-point BET method.
b
Calculated at P/Po ¼ 0.99.
c
From Vet plot analysis.
d
From the difference of total pore volume at P/Po ¼ 0.99 minus the micropore volume.
e
BJH analysis of adsorption data.
f
Average mesopore size of the silicaealumina matrix, estimated by BJH pore size distribution analysis.

coke production [21]. Mesoporous materials of the MCM-41 type 2. Materials and methods
appear to have the advantage of facilitating the access of more
bulky polymeric molecules, which is of great importance, since the 2.1. Materials and catalysts
catalytic activity and selectivity is enhanced if the reactant mole-
cules are able to access the active sites located in the interior of the Commercial poly(bisphenol A carbonate) (Aldrich) was used for
pores [21]. Base catalyzed depolymerization of polycarbonate has the experiments (Tg (DSC, onset) 149.0  C and melt index 7.00 g/
not been reported in literature. A recent study in the area of lignin 10 min). A mill was used to grind the PC pellets and particles to a
degradation in the presence of NaOH suggests that the basic cata- size of less than 2 mm that was used for the pyrolysis experiments.
lyst enhances the cleavage of the most common bond in lignin, the The catalysts that were studied in the pyrolysis of PC comprised
ether bond and produces phenolic compounds such as aldehydes, of both acidic and basic materials. The acidic catalysts were
acids, and alcohols [28]. representative zeolites (ZSM-5, silicalite, USY), a mesoporous
The investigation of thermal and catalytic pyrolysis as potential MCM-41 alumino-silicate and g-alumina (g-Аl2O3), while the basic
methods for the recycling of PC based plastics has been the aim of catalysts were magnesium oxides (MgO) and calcium oxide (CaO)
the current study. Pyrolysis has been performed in a fixed bed derived from calcination of calcium hydroxide (Ca(OH)2). In addi-
reactor and nine different catalytic systems, comprising acidic and tion to the different acid-base nature, the above catalytic materials
basic materials, with different properties have been introduced in exhibited varying textural and morphological characteristics. A
the pyrolysis system together with the polymeric material in order pure crystalline ZSM-5 zeolite with Si/Al ¼ 40 was tested (CBV
to identify any systematic correlation between the catalyst prop- 8014, provided by Zeolyst); this zeolite was initially in NHþ 4 -form
erties and the selectivity towards desirable fractions. The liquid and was converted to Hþ-form by calcination at 500  C for 3 h in air
product consisted, as expected, mainly of phenols and substituted flow (denoted as “ZSM-5”). The second ZSM-5 catalyst used was a
phenols, which remain intact under these conditions and can commercial equilibrium formulation of ZSM-5 zeolite (denoted as
potentially be used as source to the chemical industry. The corre- “ZSM-5 eq/dil.”) diluted with silica-alumina (containing ~ 30 wt.%
lation of catalytic activity and product selectivity with the physi- crystalline zeolite). In addition, a silicalite zeolite with the MFI
cochemical characteristics of the different catalysts will facilitate structure (provided by Union Carbide) with Si/Al > 1000 was also
the understanding of the reaction mechanisms in catalytic pyrolysis used (denoted as “Silicalite”). The last zeolitic catalyst was an ultra-
of PC and will eventually lead to the enhanced production of stable Y (faujasite) zeolite (CBV 712, provided by Zeolyst) with Si/
desirable products. Al ¼ 6; CBV 712 was received in NHþ 4 -form and was converted to
Hþ-form by calcination at 500  C for 3 h in air flow (denoted as
Table 2 “USY”). The two basic magnesium oxides (MgO) used were pro-
Chemical composition, acidic and basic characteristics of the catalysts. duced industrially via calcination of natural magnesite at temper-
Catalysts Chemical Total acidity B/Ld Total basicity atures between 700 and 1100  C (Grecian Magnesite S.A.). The
composition (wt.%) (mmol NH3/g)c (mmol CO2/g)e difference between these two MgO was in their purity; the “MgO-
ZSM-5 0.85/0.01a 270 6.6 e HP” sample was of high purity regarding the MgO content, while
ZSM-5 eq/dil. 14.6/0.23a 153 2.0 e the sample “MgO-MP” had a moderate purity (see Table 2). The
USY 5.9/0.03a 680 1.6 e calcium hydroxide (Ca(OH)2) used was provided by Biochimica S.A.
0.26/~ 0a
Silicalite 120 1.7 e
and was thermally treated at 600  C in order to convert it to CaO.
Al-MCM-41 1.52/0.05a 225 0.65 e
g-Al2O3 e 279 Lewis e
MgO-HP 92.6b ~0 e 244
MgO-MP 86.7b ~0 e 133 2.2. Catalyst characterization
CaO e ~0 e 104
a
Where x/y is the wt.% of Al and Na respectively. The chemical composition of the catalytic materials was deter-
b
wt.% of MgO; the impurities comprise mainly SiO2 and CaO, and for MgO-HP are mined by inductive coupled plasma e atomic emission spectros-
1.21% and 1.06% respectively, while for the MgO-MP are 5.93% and 2.44% respec- copy (ICP-AES) using a Plasma 400 (Perkin Elmer) spectrometer,
tively. The volatiles upon ignition at 1000  C for both samples are ~4.5%. equipped with Cetac6000AT þ ultrasonic nebulizer.
c
Total number of acid sites determined by TPD-NH3 experiments.
d
Ratio of Bro € nsted acid sites/Lewis acid sites from in-situ pyr-FTIR Powder X-ray diffraction (XRD) was applied for the determi-
measurements. nation of the crystalline structures of the catalysts using a Rigaku
e
Total number of basic sites determined by TPD-CO2 experiments. Rotaflex 200B diffractometer equipped with Cu Ka X-ray radiation
 E.V. Antonakou et al. / Polymer Degradation and Stability 110 (2014) 482e491
and a curved crystal graphite monochromator operating at 45 kV
and 100 mA; counts were accumulated in the range of 5e75 2q
every 0.02 (2q), with counting time 2 s per step.
Nitrogen adsorption/desorption experiments at 196  C were
performed for the determination of specific surface area (multi-
point BET method), total pore volume (at P/Po ¼ 0.99), micropore
volume (t-plot method) and average mesopore size (BJH analysis of
adsorption data) of the samples, which were previously outgassed
at 150e350  C for 16 h under 5  109 Torr vacuum, using an
Automatic Volumetric Sorption Analyzer (Autosorb-1MP,
Quantachrome).
The total number of acid sites of the catalysts was determined by
temperature programmed desorption (TPD) of ammonia, using a
home-made apparatus consisting of a fixed bed vertical quartz
reactor (I.D. 10 mm), a vertical high temperature furnace equipped
with a programmable controller, feeding system with mass flow
controllers with back-pressure regulator and an on-line quadrupole
mass spectrometer (Baltzers, Omnistar). The samples were out-
gassed at 550  C for 1 h prior to NH3 (5% NH3 in He) adsorption at
100  C for 1 h. Flushing with pure He was then applied overnight at
100  C in order to remove any physically adsorbed NH3, followed by
heating of the sample from 100 to 800  C at a heating rate of 10  C/
min under 50 cc/min He flow. The desorbed NH3 was quantitatively
determined based on the m/z ¼ 15 fragment.
The determination of the amount and strength of Bro €nsted and
Lewis acid sites of the catalysts was performed by Fourier transform
e infrared (FT-IR) spectroscopy combined with in situ adsorption of
pyridine [29,30]. The FT-IR spectra were recorded on a Nicolet 5700
FTIR spectrometer (resolution 4 cm1) using the OMNIC software
and a specially designed heated, high-vacuum IR cell with CaF2
windows. Data processing was carried out with the GRAMS soft-
ware. All samples were finely ground in a mortar and pressed in
self-supported wafers (15 mg/cm2). The wafers were outgassed in
situ at 450  C for 1 h under high vacuum (106 mbar) and a back-
ground spectrum was recorded at 150  C. Adsorption/equilibration
with pyridine vapors was then conducted at 150  C, by adding
pulses of pyridine for 1 h at a total cell pressure of 1 mbar. Spectra
Fig. 1. Nitrogen adsorptionedesorption isotherms of the catalysts.
485
were recorded at 150  C, after equilibration with pyridine at that
temperature and after outgassing for 30 min at higher tempera-
tures, i.e. 250, 350 and 450  C, in order to evaluate the strength of
the acid sites. The bands at 1545 cm1 (pyridinium ions) and
1450 cm1 (coordinated pyridine) were used to identify and
quantify the Bro € nsted and Lewis acid sites, respectively, by adopt-
ing the molar extinction coefficients provided by Emeis [31].
The basic properties of the МgO and CaO catalysts were studied
with temperature programmed desorption of CO2 (TPD-CO2), using
the apparatus described above for the TPD-NH3 experiments. In a
typical TPD-CO2 experiment, 0.2 g of the sample were loaded in the
fixed bed quartz reactor and pre-treated at 500e600  C in He for
1 h. After cooling the catalyst to 80  C under He flow, adsorption of
CO2 was performed by passing a flow of 40% CO2/He over the
catalyst bed for 1 h at 80  C. Flushing with pure helium at 80  C for
3 h was then applied to remove the physisorbed CO2. TPD analysis
was carried out from 70 to 600  C at a heating rate of 10  C/min and
a helium flow rate of 50 ml/min. The composition of the exit gas
was on line monitored by a quadrupole mass analyzer (Omnistar,
Balzer). The m/z fragments registered were as follows: CO2 ¼ 44, 45,
28, Н2Ο ¼ 18, N2 ¼ 28, O2 ¼ 32, 16. Quantitative analysis of the
desorbed CO2 was based on m/z ¼ 44.
2.3. Bench-scale studies
The bench-scale pyrolysis experiments were performed on a
fixed bed tubular reactor (ID 1.4 cm, height 36 cm), made of
stainless steel 316 and heated by a 3-zone furnace. A specially
designed piston system was used to introduce polycarbonate
feedstock into the reactor. The amount of polycarbonate used in all
experiments was 1 g and the amount of silica sand (in non-catalytic
experiments) or of catalyst (in catalytic experiments) was 0.5 g.
In a typical pyrolysis experiment, the solid feedstock was
inserted from the top of the reactor and was pushed down
instantaneously with the aid of a piston in the hot reactor zone (at
600  C). The produced pyrolysis vapors were driven through the
catalyst's bed with the aid of flowing N2 (100 cm3/min) for 15 min,
while additional purging with N2 (50 cm3/min) was performed for
another 10 min. The above described catalytic pyrolysis experi-
ments can be referred to as in situ upgrading of pyrolysis vapors and
are of the “ex-bed” type (i.e. there was no mixing of solid feedstock
with the solid catalyst). It should be emphasized that, the operation
of the reactor concerning the pyrolized material (i.e. polymer) was
in a batch mode, meaning that a specified amount of the solid
feedstock was initially added into the reactor and not continuously.
Moreover, the pyrolysis products were collected and analyzed only
after the pre-specified degradation time of 15 min.
The liquid products were collected and quantitatively deter-
mined using a pre-weighted glass receiver submerged in a liquid
bath (17  C). The water/aqueous phase present in the liquid
product was separated from the organic phase using an organic
solvent (dichloromethane). The organic phase of the bio-oil was
analyzed by GCeMS using an Agilent 7890A/5975C gas
chromatograph-mass spectrometer (Electron energy 70 eV; Emis-
sion 300 V; Helium flow rate: 0.7 cm3/min; Column: HP-5MS
30 m  0.25 mm ID  0.25 mm). Internal libraries were used for
the identification of the compounds found in the liquid product and
their categorization into main functional groups. The gaseous
products were collected and measured by the water displacement
method. The gaseous products were analyzed in a HP 5890 Series II
gas chromatograph, equipped with four columns (Precolumn: OV-
101; Columns: Porapak N, Molecular Sieve 5A and Rt-Qplot
30 m  0.53 mm ID) and two detectors (TCD and FID). The
amount of the solid residue left in the reactor consisted mainly of
486 E.V. Antonakou et al. / Polymer Degradation and Stability 110 (2014) 482e491
charcoal and coke-on-catalyst formed by thermal and/or catalytic
cracking and was determined by direct weighting.
2.4. Thermogravimetric experiments
TGA was performed on a Pyris 1 TGA (Perkin Elmer) thermal
analyzer. Samples of about 10 mg were used. They were heated
from ambient temperature to 700  C under a 20 ml/min nitrogen
flow. TGA measurements of each sample were performed a heating
rate of 10  C min1 and sample mass versus temperature was
continuously recorded.
3. Results and discussion
3.1. Physicochemical characteristics of the catalytic materials
The nitrogen adsorptionedesorption isotherms of the catalysts
studied are shown in Fig. 1 while the surface area, total pore vol-
ume, micropore and meso/macropore volume and pore size data
are presented in Table 1. The adsorption isotherms of ZSM-5 and
ZSM-5 eq/dil. zeolites are typical for microporous materials (type I
in the IUPAC classification [32]). Zeolite ZSM-5 comprises a 2-D
channel-like pore system with perpendicularly intersecting chan-
nels of ~0.55 nm in diameter and possesses mainly microporous
characteristics while structural and textural defects as well as the
relatively small size of the crystals generate the observed meso/
macroporosity (Table 1). The porous characteristics of the silicalite
zeolite, which possesses the MFI structure as ZSM-5 but is almost
aluminum-free, are similar to those of ZSM-5 (Table 1). As expected,
the surface area of the equilibrium ZSM-5 diluted with silica-
alumina was much lower (~140 m2/g, Table 1), originating from
the micropores of the crystalline ZSM-5 (30 wt.%) and the meso-
pores (~4 nm) of the silicaealumina matrix. Thus, the micropore
volume of this catalyst was significantly lower compared to that of
the pure ZSM-5 zeolite, while the relative fraction of its meso/
macropore volume was significantly higher due to the presence of
silica-alumina. The adsorption isotherm of USY zeolite exhibits a
gradual increase of nitrogen uptake from ca. P/Po > 0.5 and higher
due to the presence of secondary mesopores and macropores that
have been generated by the partial breakdown of the crystalline
structure due to the intense hydrothermal treatment of this catalyst
Fig. 2. TPD-NH3 curves of representative catalysts.
[29]. Despite the severe steaming, the surface area of USY zeolite
remains as high as ~750 m2/g, mainly due to the presence of
micropores.
Concerning the Al-MCM-41 mesoporous aluminosilicate mate-
rial the adsorption isotherm is of type IV, exhibiting the typical
steep nitrogen uptake step due to capillary condensation inside the
uniform tubular mesopores (~2.8 nm) that occurs at P/Po values of
~0.3e0.4. The surface area of this type of ordered mesoporous
materials is high and in this case is ~880 m2/g. The Al-MCM-41
catalyst also exhibits high textural porosity, as can be realized by
the increase in N2 sorption at P/Po > 0.9, due to the aggregated
morphology of its particles. The nitrogen adsorption isotherm of
the commercial g-Al2O3 catalyst is of type IV but the nitrogen up-
take step is at higher P/Po and not so steep as compared to that of
the ordered mesoporous Al-MCM-41, thus resulting in larger size
pores with relatively broader distribution (average pore size of
13e15 nm). The g-Al2O3 catalyst exhibits also relatively low surface
area (~195 m2/g), as can be seen in Table 1.
The adsorption isotherms of the MgO catalysts (Fig. 1) are of
type II showing relatively narrow hysteresis loops, typical of non-
porous materials or materials with high textural porosity origi-
nating from inter-particle voids at the meso/macroporous scale
(average pore sizes of 29 nm, Table 1). The calcination conditions
(temperature and duration) of the industrial magnesite are of vital
importance for the final textural and porosity characteristics of the
MgO catalysts. More specifically, the higher temperature and
duration of the calcination results in enhanced sintering of the
crystals and consequently lower surface area. On the other hand,
the impurities of the initial magnesite do not seem to have an
important effect on the porosity characteristics for samples sub-
jected to the same calcination procedures, as can be seen in Table 1
for the high (MgO-HP) and moderate (MgO-MP) purity samples of
the present study. The adsorptionedesorption isotherm of CaO
catalyst, derived after calcination of Ca(OH)2 at 600  C, was typical
of a non-porous material with very low surface area (~10 m2/g,
Table 1 and Fig. 1).
The chemical composition, the total number of acid sites
(expressed as mmoles NH3 per g catalyst determined by TPD-NH3),
the mole ratio of Bro € nsted to Lewis acid sites (B/L ratio determined
by FT-IR measurements coupled with in situ sorption of pyridine),
as well as the total number of basic sites (expressed as mmoles CO2
per g catalyst determined by TPD-CO2) of the basic catalysts are
shown in Table 2. In addition, the TPD-NH3 curves of representative
catalyst samples are shown in Fig. 2.
It is well known that the highly crystalline ZSM-5 and Y zeolites
possess Bro €nsted acid sites (attributed to bridging framework hy-
droxyls) [33]. According to the results shown in Table 2, USY zeolite
has higher total number of acid sites than pure ZSM-5 due to the
higher aluminum content of the former catalyst. However, due to
the presence of extra-framework SieAl species in USY (generated
from the steaming process during its preparation) it possesses
significant portion of Lewis acid sites in contrast to the pure ZSM-5
zeolite, which has mainly Bro €nsted acid sites, as evidenced by the
FT-IR/pyridine experiments (B/L ratio in Table 2). As expected, the
equilibrium/diluted ZSM-5 has lower acidity compared to the pure
ZSM-5 zeolite, while the Bro €nsted to Lewis acid sites ratio was also
much lower (2 compared to 6.6 for the pure ZSM-5) due to the
nature of acid sites in the silica-alumina matrix and the presence of
extra-framework SieAl species in the equilibrium ZSM-5 catalyst.
The acidity of the amorphous Al-MCM-41 mesoporous alumino-
silicate is attributed to both Bro€ nsted and Lewis type acid sites but
with higher portion of Lewis sites compared to the above crystal-
line zeolites (Table 2). The acidity of silicalite can be attributed to
the presence of very small amounts of tetrahedral aluminum atoms
in its zeolitic framework, which generate relatively strong Bro €nsted
 E.V. Antonakou et al. / Polymer Degradation and Stability 110 (2014) 482e491 487

acidity, similar to that of the isostructural ZSM-5 zeolite [34]. The

acidic characteristics of g-Al2O3 are attributed to Lewis acid sites
generated after dehydroxylation of the surface and formation of
coordinatively unsaturated aluminum ions [35].
As expected [36], the MgO catalysts exhibited negligible acidity
(i.e. <2.5 mmoles NH3/g) probably attributed to the presence of
impurities, all of which was assigned to Lewis sites as verified by
FTIR-pyridine sorption measurements. CaO catalyst showed similar
behavior in acidity with MgO catalysts (Table 2).
The basicity of MgO catalysts was measured with TPD-CO2 ex-
periments. Both MgO catalysts exhibited relatively high number of
basic sites (133e244 mmol CO2/g) compared to other conventional
MgOs [37,38]. The high purity material (MgO-HP) showed the
highest basicity due to the larger content of the MgO phase
(Table 2). The larger portion of basic sites (80%) had medium
strength generated from the Mg2þeO2 ion pairs (TPD-CO2 peak at
70e400  C) while the rest of the basic sites had strong basicity
generated from the isolated O2 anions (TPD-CO2 peak at
400e600  C) [39]. On the other hand, the moderate purity material
(MgO-MP) had larger portion of both strong Lewis and Bro € nsted
basic sites [40], due to the higher amount of impurities and espe-
cially CaO (2.4 wt.% in MgO-MP and 1.1 wt.% in MgO-HP) which can
generate strong basic sites [41]. CaO catalyst, derived from Ca(OH)2
after calcination at 600  C, provided less basicity in comparison to
MgO catalysts (Table 2), which was ascribed exclusively to strong
bas sites (Fig. 3).

3.2. Thermogravimetric studies

In Fig. 4a and b, thermogravimetric studies are shown in the

presence of all nine catalytic materials. These experiments served
as preliminary screening tests for the selection of the most prom-
ising catalysts.
It can be seen that most of the catalysts seem to favor the
degradation process by decreasing both the initial and the final
degradation temperatures. It also became clear that the most
important parameter are the surface properties (acidity, basicity) of
the catalysts, while porosity could also have an additional effect Fig. 4. a, b: PC TGA catalytic experiments(acidic and basic catalysts).

since large molecules are involved [23,24,27]. From the data in

Fig. 4, it can be seen that the basic materials, as well as the acidic
zeolitic or mesoporous aluminosilicate catalysts which exhibit
silicalite and g-Al2O3, which however contains only Lewis acid sites, € nsted or both Bro€ nsted and Lewis acidity. However, the basic
Bro
are more reactive in the decomposition of PC, compared to the
catalysts seem to initiate the decomposition at lower temperatures.
Another important observation among the acidic catalysts is that
neither the porous characteristics nor their differences in the
number, type and strength of their acid sites seem to affect strongly
their performance in the decomposition of PC, at least on the basis
of the above TGA data.
Still, there can be another explanation for this behavior; the
microporous structure of zeolites could inhibit the diffusion of the
large polymeric molecules into its internal strong acid sites, thus
resulting in an apparent activity similar with that of the meso-
porous Al-MCM-41, which may allow facile diffusion of reactants/
products but its intrinsic reactivity will be low due to its mild acid
character.

3.3. Thermal and catalytic pyrolysis of polycarbonate

The pyrolysis and catalytic pyrolysis experiments were per-

Fig. 3. TPD-CO2 curves of the basic catalysts.
formed in a laboratory-scale fixed bed reactor, in the facilities of the
Laboratory of Environmental Fuels and Hydrocarbons (LEFH), at the
Chemical Process and Energy Resources Institute (CPERI) in The-
ssaloniki. The bench scale pyrolysis unit is being used mainly for the
study of pyrolysis and catalytic pyrolysis of biomass samples. A
series of experiments, aiming at the selection of the optimum
488 E.V. Antonakou et al. / Polymer Degradation and Stability 110 (2014) 482e491

catalyst for the pyrolysis of polycarbonate (PC) as a model com-
pound but also aiming at future thermal treatment of a variety of
model and waste polymers, have been performed in the fixed-bed
reactor. The nine catalytic materials under study here exhibit sig-
nificant differences in their properties, namely acidic, basic and
porosity characteristics, as it has already been mentioned in para-
graph 3.1 and the following discussion will attempt to correlate
these properties with the pyrolysis products distribution.
3.3.1. Effect on product yield and composition
As already explained in the introduction, the PC degradation
products (as in all pyrolysis experiments) fall under three main
categories: total liquid product (TLP), gas and solid and their dis-
tribution in all thermal and catalytic experiments, expressed in
wt.% on PC, is shown in Table 3.
From the data in Table 3 it can be seen that, among acidic cat-
alysts, USY decrease the yield of liquid product towards gas and
solids (coke) formation possibly due to the co-presence of Lewis
acid sites as well as due to the relatively larger micropores
compared to those of ZSM-5 (7.4 vs. 5.5 Å). The higher number of
acid sites of USY (Table 2) could also contribute to its higher activity.
The ZSM-5 and the silicalite are less active compared to the above
two zeolites. The mildly acidic Al-MCM-41 exhibits similar reac-
tivity with the mildly acidic equilibrium/diluted ZSM-5 zeolite (in
terms of gas production) and this comes to support our hypothesis
described above in the analysis of the TGA data, which proposed a
compensation effect between the accessibility to the acid/active
sites and the intrinsic reactivity of the acid sites. It should be
emphasized here that in the bench-scale experiments, the products
of the non-catalytic pyrolysis were further converted on the cata-
lyst (in-situ upgrading), while in TGA the catalyst(s) contribute to
initial polymer decomposition too. From the TGA experiments it
was clear that acidic catalysts only slightly reduce the decomposi-
tion temperature while basic catalysts significantly reduced it. Even
more elucidating, is the performance of g-Al2O3 which seems to be
the more reactive amongst all catalysts tested, and could further
support the hypothesis of the high reactivity of the Lewis acid sites,
as was also suggested for USY above. The larger mesopores of g-
Al2O3 could offer additional advantages to this catalyst. An inter-
esting and rather no expected result is the lower reactivity of the
acidic ZSM-5 zeolite compared to equilibrium/diluted ZSM-5
mainly in terms of lowering the liquid yield production. As it has
already been mentioned the activity of the ZSM-5 zeolite is related
€nsted acid sites, which have been reported to
to the existence of Bro
favor mainly cracking reactions, while the thermal decomposition
of PC, as it will become more clear later, appears to follow a free
radical mechanism consisting a and b scission reactions.
With respect to the basic catalysts, CaO seems to be the most
reactive, comparable to the reactivity of Al-MCM-41. The CaO
catalyst seems to produce less gases compared to the thermal py-
rolysis case, which is counter intuitive since both TLP and the solid
product are reduced and increased respectively, suggesting a very
active catalyst. This can be explained by the fact that CaO reacts
with the CO2 in the pyrolysis vapors to form CaCO3, which also
explains the high solid yield. The high purity and more basic MgO-
HP catalyst is the next most active basic catalyst, while the less
basic MgO-MP catalyst of moderate purity shows very low activity.
MgO does not react at 600  C (pyrolysis temperature used) with
CO2 and even the MgO-MP catalyst that has a low CaO content did
not seem to affect the pyrolysis products in the way the CaO catalyst
did.
Results from the catalytic pyrolysis of PC in the literature are
very limited, but the liquid yields are reported to be between 38.80
and 80.36% on the initial polymer [5,7,42e44], depending on
reactor configuration and conditions, as well as the presence or
absence of a catalyst.
The main gaseous products were CO2, CO, H2 and CH4 in all
catalytic and non-catalytic runs. Only the amounts of CO2 were
significant (about 11e13 wt.% on PC) and the catalysts that promote
its production (i.e. decarboxylation reactions) were the g-Al2O3 and
USY. Although the differences are not that significant it seems that
the presence of Lewis acid sites as well the large micropores/
mesopores, which are characteristics of the two catalysts, favor
decarboxylation reactions. Relatively high levels of CO2 were also
produced in the presence of silicalite and Al-MCM-41, both mild
acidic catalysts but with large pores and Lewis sides, which also
verifies the trend. The levels of CO production seem comparable in
all catalytic experiments, while the production of CH4 seems to be
also favored by the g-Al2O3 and USY. Low levels of all gases and
especially CO2 were detected in the presence of CaO, for the reasons
explained above.
It becomes clear from the results in Table 4 that CO2 and all the
recorded gases can be easily separated from the monomer's
molecule in these temperatures. Decarboxylation and CH3.
abstraction are reported to be the main reaction pathways, even at
temperatures lower than 500  C. Mc Neill, at an early study [11], has
suggested that fragmentation in order to produce CO and direct
scission of methyl groups from the isopropylidene group in order to
produce CH4 might also take place at elevated degradation tem-
peratures. During pyrolysis, CO2 production is generally preferable
to CO, as more oxygen (two oxygen atoms) is removed from the
pyrolysis vapors for every carbon atom that is lost to the gas
product and in this way, higher yield of liquid product is obtained
with less oxygen content and higher calorific value.
The solid product obtained in all catalytic experiments, con-
tained mainly coke on catalyst together with some unreacted
polymer, while that from the non-catalytic one mainly carbonized
polymer.
The discussion upon the desirable catalyst should be based
mainly on the analysis of the liquid and the gaseous fractions,
which are presented in Tables 4, 5 and also in Fig. 5. As expected,

Table 4
Table 3 Main gases composition (wt.% on PC).
Product yields from the pyrolysis of PC (wt% on polymer).
Analysis of gaseous products CO2 CO H2 CH4
Analysis of products (%wt on polymer) Liquid yield Gas yield Solid yield (wt.% on polymer)

Non-catalytic 57.03 18.46 24.50 Non-Catalytic 11.93 3.53 0.16 2.48

ZSM-5 57.47 19.06 23.47 ZSM-5 12.83 2.98 0.18 2.26
ZSM-5 eq/dil. 47.25 20.80 31.95 ZSM-5 eq/dil. 12.27 3.62 0.21 2.79
Silicalite 58.32 20.32 21.36 Silicalite 13.24 3.40 0.19 2.70
USY 40.80 22.82 36.39 USY 13.91 3.29 0.27 2.95
Al-MCM-41 48.75 20.29 30.96 Al-MCM-41 13.15 2.72 0.19 2.48
g-Al2O3 38.49 22.07 39.45 g-Al2O3 13.56 3.83 0.40 3.02
MgO-HP 51.01 18.37 30.61 MgO-HP 11.82 3.50 0.15 2.47
MgO-MP 52.32 17.75 29.93 MgO-MP 11.92 2.79 0.22 2.39
CaO 49.70 12.49 37.80 CaO 4.79 3.96 0.36 2.93
 E.V. Antonakou et al. / Polymer Degradation and Stability 110 (2014) 482e491 489

Table 5
Liquid pyrolysis fraction composition of PC (chromatogram area%).

Analysis of products Aromatics PAHs Carbonyls Phenols Others Unidentified

(% wt on organic)

Non-catalytic 2.31 0.72 0.32 70.77 3.27 22.60

ZSM-5 4.71 0.58 0.00 66.73 4.78 23.20
ZSM-5 eq/dil. 8.20 5.96 0.00 71.32 3.57 10.94
Silicalite 3.11 0.00 0.24 78.46 4.15 14.05
USY 11.36 13.93 0.00 68.47 2.53 3.71
Al-MCM-41 8.12 3.16 0.29 73.97 6.82 7.64
g-Al2O3 12.54 2.45 0.27 78.77 3.08 2.88
MgO-HP 5.49 0.00 0.23 87.58 5.68 1.02
MgO-MP 5.41 0.00 0.00 88.36 1.47 4.76
CaO 6.55 0.52 0.56 81.80 5.07 5.64

the phenolic fraction is dominant in the liquid produced (more than
70 wt.% on organic) even in the non-catalytic runs, which indicates
that pyrolysis, and even thermal pyrolysis, is a promising process
for the production of phenolic compounds and the recovery of the
original monomer. Almost all catalysts (with an exception of the
ZSM-5 and the USY which exhibit a minor decrease) seem to pro-
mote the production of phenols in the liquid fraction. It can be
deduced that the increase of phenols could be related with a
decrease of Brӧnsted acidic sites of the zeolitic catalysts, while
catalysts of moderate acidity and Lewis acid sites (silicalite and
alumina) as well as the mesoporous structure (Al-MCM-41) seem to
favor this desirable fraction. The most promising catalysts seem to
be the ones with basic properties, which indicate a correlation
between lack of total acidity and selectivity towards phenols pro-
duction. The highest production of phenols was observed in the
presence of CaO and the two natural MgOs. Among the three basic
catalysts, the less basic MgO-MP catalyst with moderate purity
produces a slightly higher fraction of phenols compared to the
more basic MgO-HP catalyst with higher purity, while the CaO
catalyst follows.
It is worth mentioning at this point that, from the area of
biomass pyrolysis it has been reported that the very active crys-
talline ZSM-5 zeolite induced a small decrease of phenols
compared to the non-catalytic pyrolysis oil, while the equilibrium/
diluted ZSM-5 catalyst increased phenols, which also indicates a
correlation between decreased acidity and increase of the phenolic
fraction [27].
Other classes of compounds detected in the liquid fraction are
also of aromatic origin (aromatics and PAHs). The presence of ar-
omatic and aliphatic hydrocarbons is desirable if the liquid fraction
produced is to be used for fuels production. Aromatics are high in
the presence of silicalite and MgO-HP, while PAHs are high in the
presence of USY. The latter could be explained by the high CO2
production in the presence of the USY catalyst, which could lead to
the production or polyaromatic compounds without oxygen in
their molecule. Essentially the mesoporous acidic materials, ZSM-5
eq/dil., USY Al-MCM-41 and Al2O3, favor the production of aro-
matics, while their large pores allow condensation reactions that
leads to PAHs, an undesirable product. The mesoporous basic MgO-
HP on the other hand does produce aromatic hydrocarbons, how-
ever the lack of acidity also results in the lack of PAHs since no
condensation reactions take place, hence the bulk of the oil is either
aromatic or phenolic. In addition, a small fraction of carbonyl
compounds is found, especially in the presence of the more basic
catalysts.
3.3.2. Phenols breakdown
As it has already been stated, the fraction of phenols is of major
importance for the specific set of experiments, since it constitutes
the main fraction in the liquid products. This fraction consists of
one ring and two rings phenolic compounds, some of them
substituted and/or branched and also the PC monomer: phenol,
4,4(1-methyl-ethylidene) bis or bisphenol A and some of its pre-
cursors. Each one of these categories has a different role in the
reaction mechanism and also different end uses. For this reason, a
breakdown of the phenolic products is presented in Table 6.
Some useful observations can be made from Table 6; first of all,
single ring phenolic compounds and more specifically phenol/4-
methylphenol, 4-ethylphenol/4-isopropyl and isopropenyl phe-
nols seem to be more abundant than two ring compounds, present
in considerable amounts, even in the non-catalytic runs. Most of
the catalysts seem to favor the production of specific single ring
compounds, and even more interesting is the fact that they do it at
the expense of the production of the monomer.
More specifically:

phenol production was significantly increased in all catalytic

Fig. 5. Phenols relative abundance (chromatogram area%).
experiments. The increase was so significant in the presence of
the mesoporous material Al-MCM-41, the USY and the g-Al2O3
(up to a 6-fold increase compared to the non-catalytic runs),
which makes this catalytic process very attractive for phenol
production. Phenol is produced by a scission reaction at the a
bond of the original polycarbonate structure and it becomes
clear that the increased pore size of the mesoporous materials
and the mild acidity will facilitate this reaction. More specif-
ically, it seems that the mesoporous structure will allow the
diffusion of the bulky products of the thermal pyrolysis and
facilitate more scission reactions.
4-methylphenol and 4-ethylphenol also seem to be favored by
the presence of all the catalytic materials under study and the
most significant upgrade towards their production was
490 E.V. Antonakou et al. / Polymer Degradation and Stability 110 (2014) 482e491

Table 6
Phenols relative abundance (chromatogram area%).

Non-catalytic ZSM-5 ZSM-5 eq/dil. Silicalite USY Al-MCM-41 g-Al2O3 MgO-HP MgO-MP CaO

Phenol 5.74 14.57 21.36 9.90 30.05 32.34 35.31 17.53 15.94 23.03
Phenol, 4-methyl- 14.37 13.84 15.51 15.11 17.65 15.43 22.31 18.61 20.57 21.71
Phenol, 2-methyl- 0.00 2.18 5.71 1.86 2.45 2.07 2.44 0.00 0.00 1.07
Phenol, 4-ethyl- 8.17 4.02 1.74 6.90 4.80 5.32 10.43 10.85 10.96 11.94
Phenol, 4-(1-methylethyl)- 2.01 1.77 1.62 2.10 2.37 3.40 3.52 5.16 4.88 5.80
Phenol, 4-isopropenyl 1.09 2.21 2.26 0.00 3.40 1.17 0.00 12.79 10.50 5.05
Phenol, 4-(1-methyl-1-phenylethyl) 6.79 4.80 4.29 5.84 1.39 1.20 1.45 4.90 5.22 3.10
Phenol,4,4'-(1-ethylidene)bis 2.67 2.12 2.15 2.07 0.00 1.12 0.00 1.37 1.78 1.06
Phenol,4,4'-(1-methylethylidene)bis 27.44 16.01 14.93 27.28 3.00 3.61 3.59 15.38 15.69 7.43

performed in the presence of g-Al2O3 and the basic catalysts. For
the formation of these substituted phenols, a two-step mecha-
nism is suggested; a scission at a bond followed by CH3 migra-
tion and H abstraction. This leads to the scission at b, b' and
leads to CO2 production, formation of 4-methyl and 4-
ethylphenol respectively
4-isopropyl and isopropenyl phenols were generally produced
in lower concentrations. Again, they are favored by the presence
of most catalysts and even more favored by basic catalysts. They
are formed by homolytic fission at the isopropylidene group
followed by H abstraction. This was found to be the first step in
the pyrolysis process and thus the reaction with the lower
activation energy
As expected, the monomer bisphenol A was generally detected
in significant amount in the liquid fraction. The observed levels
of the recovered monomer are in agreement with other litera-
ture findings [42e44]. Its concentration, as well as the concen-
tration of the other phenolic compounds with two benzene
rings that have been detected, was decreased in the presence of
all catalysts under study, which was expected, as it indicates
extended degradation in the presence of catalysts. Whether this
is a desirable or undesirable effect depends on the potential use
of the liquid pyrolysis product and whether the aim is to pro-
duce fractions enriched in high added-value single ring phenols
or rather to recover a significant amount of the original mono-
mer. What can be deduced is that conventional, rather than
catalytic, pyrolysis is suggested as a suitable thermal process for
the monomer recovery and that the role of acidity does not
seem to follow a pattern here. The catalysts producing the
lowest percentage of the monomer were USY, Al-MCM-41 and
g-Al2O3. The high reactivity of these three catalysts and more
specifically of the USY catalyst (due to its significant acidity) in
terms of the reduction of the monomer, indicates that acidity is
a determining factor in the degradation of PC, but only when it is
combined with the appropriate pore size so that the polymer/
oligomer molecules can access the catalysts sites. The surface
area does not appear to be a determining factor since the g-
Al2O3 seems to be equally efficient in the decomposition of the
PC monomer (surface area of the g-Al2O3 is 195 m2/g, compared
to 750 m2/g for the USY and 882 m2/g for the Al-MCM-41). Sil-
icalite exhibited similar behavior to the non-catalytic runs and
the ones producing the highest amounts were ZSM-5 and the
two natural MgOs. The last observation should be taken into
account when selecting an appropriate catalyst, since the last
two basic catalysts do not seem to produce a fraction of lighter
phenols.
4. Conclusion
A series of screening experiments in the presence of nine cata-
lytic materials was performed in a bench scale reactor for the
pyrolysis of commercial polycarbonate in order to investigate po-
tential correlation(s) between the catalyst structural characteristics
and the selectivity towards desirable pyrolysis products. The type
and availability of acid sites, as well as the pore size seem to have a
significant effect on the products yields and composition. More
specifically, a combination of Lewis acidity and high microporous/
mesoporous structure (which is the case for the USY, the Al-MCM-
41 and the g-Al2O3 catalysts) seems to have a positive correlation
towards the production of desirable products such as light phenols.
Basic catalysts also appear to favor PC degradation at lower tem-
peratures compared to both the non-catalytic experiments and the
acidic catalysts and produce significantly high phenolic fractions.
Acknowledgments
This research has been partially financed by the European Union
(European Social Fund e ESF) and Greek national funds through the
Operational Program “Education and Lifelong Learning” of the
National Strategic Reference Framework (NSRF) e Research Fund-
ing Program: Heracleitus II. Investing in knowledge society through
the European Social Fund.
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