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Int. J Sci. Emerging Tech Vol‐5 No 1 January, 2013 


 

Thermal and Catalytic Degradation of


Polystyrene with a Novel Catalyst
D. Houshmand1, B. Roozbehani* 1, A. Badakhshan2
1
HSE Department of Abadan Faculty of Technology, Petroleum University of Technology
North Bowardeh, Abadan, Iran
2
Department of Chemical and Petroleum Engineering, Faculty of Engineering University of Calgary
*1 1
1D.Houshmand@ymail.com
2Badakhshan.Amir@yahoo.com

Abstract— Waste polymer recycling has received a inorganic particles to polymers can enhance
great attention due to increasing amounts of waste conductivity. Until now four different methods has
polymers generate enormous environmental been developed which include: [1, 2, 8] Primary
problems. The pyrolysis of polystyrene was examined recycling, referring to ‘‘in plant’’ recycling of scrap
as an effective way to recycle this polymer and material [9]; Mechanical Recycling, in which
recover its monomer styrene. In this paper, thermal polymer separation is done by melt extrusion or
and catalytic degradation of polystyrene at the other techniques [10]; Chemical or feedstock
atmospheric pressure was investigated. Various recycling where depolymerization to the monomers
conditions of temperature and catalyst/Polystyrene is performed; Energy recovery, an effective way to
mass ratio were considered to determine the product reduce the volume of organic materials by
composition and effects of catalyst/ Polystyrene mass
incineration [8]. Solid acids and base are the most
ratio and temperature on conversion. The results
commonly used catalysts [11-14]. PS (polystyrene)
can be thermally depolymerized to monomer
showed that with increasing the temperature, the
styrene with a high selectivity in contrast to
conversion increased. The products of the
polyethylene and polypropylene [7].
degradation mostly consist of liquid, less gas and solid
residue. The AIT100s catalyst showed good catalytic In this field Zhang et al. reached a styrene yield
performance for the degradation of PS with selectivity of 70 wt. % at degradation temperature of 350 °C
to aromatics more than 99%. using a semi-batch reactor with a continuous flow
of nitrogen [15]. While, Audisio et al. used solid
Keywords—  Catalytic degradation, polystyrene, acids such as silica –alumina and HY or REY
monomer, AIT100s zeolites at 350 °C and showed a very low
selectivity (less than 5 wt.%) to the styrene in PS
1. Introduction [16]. Ukei et al. employed solid bases, especially
BaO and reported better selectivity of styrene
Nowadays, polymer composite productions are monomer in comparison to solid acids at 350 °C
used widely over the last few decades [1, 2]. It has [17].
been estimated that 100 million tonnes of plastics
The main objective of this work is to study the
are produced world-wide each year [3]. Polystyrene
production of liquid fuels by thermal and catalytic
is broadly used for many purposes such as
degradation of polystyrene using AIT100s as
packaging, consumer goods, etc., but this widely
catalysts. Also the effects of temperature and
use brings lots of wastes and causes environmental
catalyst on degradation are presented in this paper.
pollution because of their non-degradable nature.
Therefore, recycling, reuse and making them
biodegradable by various means will prevent this 2. Experimental
problem [4-7].
2.1. Material and catalysts
Among them polymers containing
semiconductor particles play a significant role,
especially for the manufacturing of electronic PS employed in this work, was granules form,
devices. Inorganic–organic polymer composites supplied by TAITA Chemical Company from
have attracted wide interest, because the addition of Taiwan. The properties of polystyrene are described
in Table 1.
_______________________________________________________________________
International Journal of Science & Emerging Technologies
IJSET, E‐ISSN: 2048‐8688
Copyright © ExcelingTech, Pub, UK (http://excelingtech.co.uk/)
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Int. J Sci. Emerging Tech Vol‐5 No 1 January, 2013 


 
Table 1. Polymer Properties. Table 2. Physical properties of the catalysts used in
the experiments

The catalytic and thermal degradation of PS was 3. Results and discussion


carried out in a semi-batch reactor. A mixture of PS
and catalyst was loaded inside a Pyrex vessel of Figure 2 shows the product yields obtained from
1000 ml. The reactor was pressurized and purged the pyrolysis of polystyrene. It illustrate the results
with nitrogen two times to ensure an oxygen-free for the absence of a catalyst, and in presence of
medium. The polymer and catalyst mixture was AIT100s catalyst in relation to catalyst temperature,
heated at a rate of 20 ºC/min to reach the desired respectively.
temperature. The reaction temperature was
measured by a thermocouple that was in direct
contact with the reaction mixture. The oil and gases
exiting the reactor were condensed in the condenser
system which consisted of a water-cooled
condenser illustrated in Figure 1, then volatile
hydrocarbons is separated into gases and liquids.
The condenser system was weighed before and
after the experiment to determine the total oil yield.

Figure 2. Effect of temperature on conversion.

According to the Figure 3 by increasing the


temperature, conversion was increased. It can be
seen from this table that adding AIT100s catalyst
led to an increase in pyrolysis conversion in lower
temperature. As it is clear from this Figure, an
  increase in catalytic reaction temperature caused
Figure 1. Schematic of experiment setup the conversion to increase from 65% from to
approximately 99%.
2.2. Characterization of catalyst

In this study a novel catalyst was used, named


AIT100s, which properties were shown in
Table 2.

 
Figure 3. Effect of temperature on catalytic
degradation of PS.
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Int. J Sci. Emerging Tech Vol‐5 No 1 January, 2013 


 
Figure 4 shows the influence of the wt. % for 350 and 370 °C, respectively. However,
catalyst/polystyrene ratio for the AIT100s catalyst. their amounts were very small at higher
Data presented in this table, showed the pyrolysis temperatures. This indicates that the competitive
of 100 (gr) of polystyrene in relation to the mass of cross-linking reactions take place first, especially at
the AIT100s. As the mass of catalyst increased, low temperatures; therefore, the cracking of the
reduction in the yield of conversion was observed. resulting cross-linked polymer becomes more
difficult.

1.1.1. Effect of catalyst: plastic ratio on


product yield
Figure 6 shows the effect of the catalyst:
polystyrene ratio on degradation product for the
AIT100s catalyst. As the mass of catalyst increased,
a reduction in liquid yield was observed. Increase
of this ratio also showed an increase in gas yield
and carbon formation on the catalyst surface.

Figure 4. Effect of catalyst on degradation of PS.

3.1. Product yield


PS with catalyst AIT100s in the reactor, was
degraded at various temperatures (350, 370, 390
and 410 ˚C) and different catalyst: plastic ratio.
Figure 5 illustrate the gases, liquids and residues on
the catalyst from the degradation experiment. The
amount of gases products was calculated by
subtracting the sum of weights for liquids and
residues, from the total weight of PS sample and Figure 6. Effect of catalyst ratio on product yield.
fresh catalyst initially loaded to the reactor.
Carbonaceous compounds adhering to the reactor After the catalytic cracking, the residue
wall were dissolved in n-hexane and were measured remaining within the reactor showed a black solid,
as degradation residues. In all cases, the liquid oils which completely covered the reaction zone.
were main products. However, this black residue was not observed in
thermal cracking experiments, which indicates that
the acid catalysts promoted the cross-linking
reactions. The main product of thermal and
catalytic degradation of polystyrene is liquid. By
increasing the temperature, the amount of liquid
product was increased. The reason is that at higher
temperature, more bonds will break. Styrene
monomer and dimer were the main components in
the oils obtained by solid acid. Since cracking of
hydrocarbons on solid acids has been explained in
terms of β-scission of C–C bonds [13], these were
probably produced by β-scission of C–C bonds in
the PS main chains as shown in Figure 7.

Figure 5. Product yield from the catalytic pyrolysis


of PS

It can be figured out from Figure 5 that the


amount of liquid products increased with
temperature, while the residues decrease with
temperature. At low temperatures, the amount of
residues for AIT100s catalyst was high, 31 and 18
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Int. J Sci. Emerging Tech Vol‐5 No 1 January, 2013 


 
catalyst in polymer degradation is to improve the
yield to more than 99%. In this work it was shown
that catalysis results conversion was more than
thermal pyrolysis. The effect of temperature and
catalyst: polymer ratio was examined in relation to
the gaseous and liquid pyrolysis products. Since the
oil product contained a high percentage of styrene
monomer, it is possible to use it directly for the
reproduction of the polymer. The AIT100s catalyst
showed good catalytic performance for the
degradation of PS with selectivity to aromatics
more than 99%. It was also observed that
temperature was the most effective parameter on
Figure 7. Cracking of hydrocarbons on solid acids pyrolysis, as by increasing temperature yield of
in terms of β-scission styrene and conversion increased. Our study
showed that the use of AIT100s catalyst leads to
The mechanism of acid catalyzed cracking is achieve more desired conversion of the waste
categorized as carbenium nature which is shown in polystyrene, while the harmful effects of these
Figure 8. The most likely reaction pathway waste was Severely decreased.
involves the attack of a proton associated with a
Brönsted acid site to the aromatic rings of PS, due References
to the reactivity of its side phenyl groups towards
[1] J. Scheirs, "Polymer Recycling," J. Wiley &
electrophilic reagents. The resulting carbocations
Sons, 1998.
may undergo β-scission followed by an inter/
intramolecular hydrogen transfer, leading to
different products (benzene, ethylbenzene, cumene, [2] G. P. Karayannidis D. S. Achilias, "The
etc.). Alternatively, the protonated polymer chemical recycling of PET in the framework of
backbone may proceed through cross-linking sustainable development," Water, Air & Soil
reactions among adjacent polymeric chains or even Pollution: Focus, vol. 4, p. 385, 2004.
inside the same polymer [13].
[3] Paul T. Williams and Ranbir Bagri,
"Hydrocarbon gases and oils from the
recycling of polystyrene waste by catalytic
pyrolysis," international journal of energy
research, pp. 31–44, 2004.

[4] T. Maharana, Y. S. Negi and B. Mohanty,


"Review Article: Recycling of Polystyrene,"
Polymer-Plastics Technology and Engineering,
pp. 729-736, 2007.

[5] W.Zhao, S. Hasegawa, J. Fugito, F. Yoshii, T.


  Sasaki, K. Makuuchi, J. Sun, S. Nishimoto,
"Effects of zeolites on the pyrolysis of
Figure 8 Mechanism of acid catalyzed cracking polypropylene," Polymer Degradation and
Stability, vol. 53, pp. 129-135, 1996.
The AIT100s catalyst showed good catalytic
performance for the catalytic degradation of PS, [6] W.C. McCaffrey, M.R. Kamal, D.G. Cooper,
without much formation of residues or cokes at 410 "Thermolysis of polyethylene," Polymer
˚C for 35min. All the runs produced aromatic liquid Degradation and Stability, vol. 47, pp. 133-
oils with high selectivity. While styrene is the 139, 1995.
major product in both thermal and catalytic
degradation over the solid acid catalysts, significant [7] Seung-Yup Lee, Jik-Hyun Yoon, Jong-Ryeul
differences are observed in the aromatic products Kim and Dae-Won Park, "Degradation of
distribution. polystyrene using clinoptilolite catalysts,"
Analytical and Applied Pyrolysis, vol. 64, pp.
4. Conclusion
71–83, 2002.
The pyrolysis of polystyrene was examined as an
effective way to recycle this polymer and recover [8] Dimitris S. Achilias, Iliana Kanellopoulou,
its monomer styrene. The main propose of using
238

Int. J Sci. Emerging Tech Vol‐5 No 1 January, 2013 


 
Panagiotis Megalokonomos, Eleni Antonakou Engineering, vol. 20, pp. 133-137, 2003.
and Angelos A. Lappas, "Chemical Recycling
of Polystyrene by Pyrolysis: Potential Use of
the Liquid Product for the Reproduction of 8
Polymer," Macromolecular, vol. 292, pp. 923–
934, 2007.

[9] S.M. Al-Salem, P. Lettieri, J. Baeyens,


"Recycling and recovery routes of plastic solid
waste (PSW): A review," Waste Management,
vol. 29, pp. 2625–2643, 2009.

[10] George P. Karayannidis and S. Dimitris,


"Chemical Recycling of Poly(ethylene
terephthalate)," Macromolecular Materials and
Engineering, vol. 292, pp. 128–146, 2007.

[11] G. Audisio, A. Silvani, "Catalytic thermal


degradation of polymers: Degradation of
polypropylene," Analytical and Applied
Pyrolysis, vol. 7, pp. 83–90, 1984.

[12] G. Manos, A. Garforth and J. Dwyer,


"Catalytic degradation of high-density
polyethylene over different zeolitic structures,"
Industrials & Engineering Chemistry Research,
vol. 39, pp. 1198-1202, 2000.

[13] H Ukei, T Hirose, S Horikawa, Y Takai, M


Taka, N Azuma and A Ueno, "Catalytic
degradation of polystyrene into styrene and a
design of recyclable polystyrene with dispersed
catalysts," Catalysis Today, vol. 62, pp. 67-75,
2000.

[14] J. Aguado, et al, "Catalytic conversion of


polyolefins into liquid fuels over MCM-41 :
Comparison with ZSM-5 and amorphous SiO2-
Al2O3," Energy & Fuels, pp. 1225-1231, 1997.

[15] Zhibo Zhang , Tamaki Hirose , Suehiro Nishio


, Yoshio Morioka , Naoto Azuma , Akifumi
Ueno , Hironobu Ohkita , Mitsunori Okada,
"Chemical Recycling of Waste Polystyrene into
Styrene over Solid Acids and Bases," Industrial
& Engineering Chemistry Research, vol. 34 ,
pp. 4514-4519, 1995.

[16] Sachin Kumara, Achyut K. Panda, R.K. Singh,


"A review on tertiary recycling of high-density
polyethylene to fuel," Resources, Conservation
and Recycling, vol. 55, pp. 893– 910, 2011.

[17] Chan-Gi Lee, Jun-Sik Kim, Pyung-Seob Song,


Gill-Soo Choi, Yong Kang and Myoung-Jae
Choi, "Decomposition Characteristics of
Residue from the Pyrolysis of Polystyrene
Waste in a Fluidized-Bed Reactor," Chemical

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