Pt/ITQ-6 zeolite as a bifunctional catalyst for hydrocracking of waste plastics

E. Fuentes, A. Salbidegoitia, M.P. Gonzlez-Marcos and J.R. Gonzlez-Velasco

Dept. Chemical Engineering, Fac. Science and Engineering, The University of the Basque Country, UPV/EHU,
P.O. Box, 644, E-49940 Bilbao, Spain
edwingustavo.fuentes@ehu.es

Abstract
Delaminated ITQ-6 and ferrierite have been synthetized from the same precursor (PREFER). These supports were used
for the preparation of bifunctional catalysts based on platinum, for hydrocracking of waste plastics. The catalysts were
tested in polystyrene hydrocracking under optimized conditions. It has been found that delaminated, Pt/ITQ-6 material,
with higher BET and external surface, although with less acidity, both total and Brnsted, is more effective for polystyrene
degradation than Pt/Ferrierite. Differences in selectivity can also be observed, the low microporosity of the Pt/ITQ-6
yielding to hydrocarbons with intermediate molecular weight, whereas Pt/Ferrierite yields more gas products, due to its
microporosity and acidity, which causes shape selectivity and cracking of the intermediate hydrocarbons to gas.
Keywords: Polystyrene, Hydrocracking, ITQ-6, Delaminated, Zeolites

1. Introduction
Nowadays, catalysis represents both a huge opportunity
and a challenge for the conversion of waste plastics, as
catalytic processes ensure lower operating temperature
and pressure and higher conversion and selectivity to the
target products [1]. Specifically, zeolites had
demonstrated to be effective in waste plastics
degradation [2], and are materials whose properties can
be configured according to reaction requirements.
Among alternative catalytic processes for waste plastic
conversion, hydrocracking is very attractive because it
can degrade the plastic and transform it into more
valuable products at the same time. Bifunctional catalysts
based in zeolites and precious metals can promote
plastic degradation through transformation reactions
such as: hydrogenation, dehydrogenation, ring opening,
isomerization, dehydrohalogenation, cracking and others.
Acidic and external surface of zeolites are known to be
the most determining properties in polyolefin
hydrocracking reactions [3]. In this study, delamination of
zeolites for catalyst synthesis of high external surface
materials is explored.

tetrapropylammonium hydroxide (TPAOH) and refluxed

for 36 h at 368 K. Delamination was performed by
ultrasound treatment for 1 h. Finally, the solid phase was
separated by centrifugation and washed, dried at 373 K,
and calcined at 853 K for 7 h, yielding ITQ-6. XRD
patterns in Figure 1 confirm the structure of the
synthesized zeolites.
Bifunctional catalyst: Pt/Zeolite catalysts were
prepared by ionic exchange, with 0.5% wt. of metal,
using tetraammine-platinum(II) nitrate (Pt(NH3)4](NO3)2)
as metallic source. The exchange was carried out under
mix and reflux at 353 K for 24 h and pH of 7. Afterwards,
the solid was separated, washed, dried at 383 K,
calcined at 823 K for 2 h and reduced in hydrogen flow at
800 K. Characteristics of catalysts such as: BET surface,
external surface, acidity (FTIR of absorbed pyridine),
metallic content (ICP) and dispersion of Pt (H 2
chemisorption) were evaluated.

2. Materials and Methods

Delaminated zeolite: Delaminated ITQ-6 material was
synthesized following indications of Corma and
coworkers [4]: 10 g of silica, 2.3 g of alumina, 9.2 g of
NH4F, 3.1 g of HF 49.8% concentration, 26 g of 4-amino2,2,6,6-tetramethylpiperidine, and 27.9 g of deionized
water were mixed in an autoclave at 448 K for 5 days.
The resulting product was afterwards filtered, washed
and dried at 333 K (PREFER). The PREFER material
was
swollen
in
a
water
solution
of
cetyltrimethylammonium
bromide
(CTABr)
and

Figure 1. XRD patterns of zeolites and precursor

7th International Symposium on Feedstock Recycling of Polymeric Materials (7 th ISFR 2013)

New Delhi, India, 23-26 October 2013

Table 1. Catalyst characterization

Catalyst

SBET

SEXT

Brnsted

Lewis

Pt

m2/g

m2/g

molpyridine/g 523 K

Pt/Ferr

261

81

6.8

61

0.5

Pt/ITQ-6

580

500

10.6

41

0.5

wt.
%

Catalytic activity: Reactions of polystyrene (PS)

hydrocracking, in the liquid phase, were performed as
model plastic reactions and the optimized operational
conditions were: 5% PS solved in decahydronapthalene,
623 K, 180 bar of H 2, 1800 rpm, 2.36 gl1 of catalyst in
slurry, with an stirred autoclave reactor.

3. Results and Discussion

In Table 1, the main characteristic of microporous and
their respective mesoporous materials are shown. There,
it can be observed that delamination produces material
with two times higher surface BET than the microporous
ferrierite. Additionally, the external surface increases in
ITQ-6 due to the formation of small layers. Unfortunately,
the acidic properties of the zeolites change during the
delamination process. The ITQ-6, as a consequence of
delamination, lost acidity, especially Brnsted type, which
is important in the cracking process.
The catalytic activity of zeolites was tested and
compared to the thermal process in the hydrocracking of
polystyrene The operational conditions of the reactions
were optimized in order to avoid gas-liquid and liquidsolid mass transport diffusional controls. The differences
in the reaction behavior are then completely associated
to activity and internal diffusion control.
The conversion of polystyrene degradation is plotted in
Figure 2 as function of reaction temperature. The results
clearly show that the catalytic process improves
polystyrene hydrocracking, increasing the conversion

and reducing the operation temperature, with respect to

the thermal process.
When the performance of both catalysts is compared,
ITQ-6 gives a higher conversion than ferrierite, indicating
that the gain in accessibility due to delamination is more
important than the loss of acidity.
With respect to selectivity, differences in products can be
observed. Pt/Ferrierite yields more gas products, due to
secondary reactions of cracking inside microporous
surfaces, whereas Pt/ITQ-6, due to its lower acidity and
microporosity, does not present shape selectivity, what
prevents formation of higher amount of gases. The
intermediate molecular weight products are more
valuable than gas for uses as liquid fuels.
Time of swollen is the most important variable in
delamination process, and the acidic properties of ITQ-6
depend on this variable. The optimization of acidic and
textural properties for hydrocracking of polystyrene and
other plastics will be interesting.

4. Conclusions
The process of delamination of zeolites has been found
to drastically increase the external surface of the catalyst.
With these materials, it is possible to prepare bifunctional
acid/metallic catalysts in which the active centers are
more easily accessible for polymer macromolecules, so
that selectivity to the intended products can be tuned.

Acknowledgements
The authors want to thank the Basque Government (GICIT-450-07 and IT-657-13) and the Spanish Ministry for
Science and Innovation (CTQ2010-17277) for their
economical support.

References
[1] T. Bhaskar. Feedstock Recycling and Valorization of
Polymeric Materials, (2011) 9-11.
[2] J. Y. Lee, S. M. Park, S. K. Saha, S.J. Cho, and G.
Seo. App. Cat. B., 108-109 (2008) 61-71.
[3] J.A. Salbidegoitia, E.G. Fuentes, J.L. Ayastuy, M:A..
Gutirrez-Ortiz, M.P. Gonzlez-Marcos and J.R.
Gonzlez-Velasco. Internacional Congresos of Chemical
Engineering. (2012) 47.
[4] A. Corma, U. Daz, M. E. Domine, and V. Forns. J.
Am. Chem. Soc. 122-12 (2000) 28042809.

Figure 2. Conversion of polystyrene in hydrocracking

reactions. 5 % PS in decaline, 180 bar H2, 1800 rpm and
2.36 gcatl-1.
7th International Symposium on Feedstock Recycling of Polymeric Materials (7 th ISFR 2013)
New Delhi, India, 23-26 October 2013