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ANALYTICAL and
Journal of Analytical and Applied Pyrolysis APPLIED PYROLYSIS
ELSEVIER 43 (1997) 15 25
Abstract
The thermal degradation of plastic polymers into fuel oil over mesoporous silica (KFS-16)
catalyst has been investigated. The product yields, composition and degradation rate of
polyethylene over KFS-16 were compared with those over solid acid catalyst (silica alumina
and zeolite) and non-catalytic thermal degradation. The initial rate of degradation of PE
over KFS-16, which possesses no acid sites was as fast as that over silica alumina (SA-1)
and the yield of liquid products was higher. The composition of the liquid products of
degradation over KFS-16 was different from that over SA-1 and similar to that of
non-catalytic thermal degradation. SA-1 catalyst deactivated very rapidly due to coke
deposition, whereas KFS-16 deactivated much more slowly. These findings over mesoporous
silica suggest that the mesopores surrounded by the silica sheet may act as a flask for storing
radical species for a long time and then long-lived radicals accelerate the degradation of
plastics. 1997 Elsevier Science B.V.
1. Introduction
The discovery of the mesoporous folded silicate materials M-41S [1] and FSM [2]
family having an array of hexagonal pores of \ 20 A opened up new possibilities
in the field of catalysis involving larger molecules. Some attempts have been made
to utilize mesoporous silica and mesoporous aluminosilicate in acid catalyzed
reactions such as the cracking of hydrocarbons [3]. However, due to the absence of
strong acid sites, these mesoporous materials displayed very low catalytic activity
compared to the conventional solid acid catalysts such as silicaalumina and
zeolites. These mesoporous materials may find application in the catalysis of
reactions requiring weak acidity and involving bulk size molecules. Recently, the
catalytic degradation of plastic polymers into liquid hydrocarbons has become very
important from view point of the utilization of waste plastics as an energy resource
and environmental issues. In particular, the degradation of polyethylene, the most
widely used plastic, has been investigated extensively [47]. We have already
reported the catalytic processes for the degradation of polypropylene (PP) [8] and
polyethylene (PE) [9] into fuel oil over solid acid catalyst, silicaalumina. The
objective of this work is to explore the potential of mesoporous silica KFS-16B
(Kanemite-derived folded silica) as a catalyst for the degradation of polyolefinic
polymers (such as polyethylene, polypropylene) into liquid hydrocarbons. The rate
of degradation, composition and yields of products from degradation of polymers
catalyzed by the use of KFS-16B was investigated.
2. Experimental
The polyethylene studied was high density polyethylene (HDPE) obtained from
Mitsui Petrochemical Co. Ltd. Thermal and catalytic degradation of polyethylene
was performed in a glass reactor under semi-batch conditions. Experimental
details and product analyses were described previously [12]. In brief, 10 g of
HDPE for thermal degradation and, 10 g of HDPE mixed with 1 g of the
catalyst for the catalytic degradation was loaded into the reactor, and then
temperature of the reactor was raised to the predetermined degradation tempera-
ture, 430C, by an electric furnace. The products of degradation were classified
into three groups viz., liquid products, which are condensable at room tempera-
ture; gaseous products; and residues, which refers to both carbonaceous species
and waxy compounds. The liquid and gaseous products were analyzed by two
gas chromatographs with a thermal conductivity detector and a flame ionized
detector, respectively.
The product yields for thermal and catalytic degradation of HDPE performed
at 430C are shown in Table 1. In catalytic degradation, two types of silicaalu-
mina, SA-1 and SA-2 having different SiO2/Al2O3 mole ratios, zeolite ZSM-5 and
mesoporous silica KFS-16B were used as catalysts. Acidity (strength) of these
catalysts was investigated by NH3 temperature programmed desorption (TPD)
method. NH3 TPD results shown in Fig. 1 revealed that the acidity of these
catalysts are in the following order: SA-1\ ZSM-5\ SA-2 KFS-16B= 0. Thus,
mesoporous silica (KFS-16B) possesses virtually no acidity. In Table 1 (left half),
silicaalumina catalyst SA-2 with moderate acidity produced the greatest amount
of liquid products. ZSM-5 possessing strong acid sites produced less liquid prod-
ucts and more gaseous products than the other acid catalysts (SA-1, SA-2). These
results are in agreement with the fact that strong acid catalysts catalyze the
degradation/cracking of heavier hydrocarbons into more lighter or gaseous hy-
drocarbons than the weak acid catalysts. In thermal degradation, the yield of
liquid products was ca. 69 wt% and residue, 21 wt%. On the other hand KFS-
16B, having no acid sites, produced liquid hydrocarbons with a yield more than
71 wt% and the yield of residues was much less than that of non-catalytic
thermal degradation.
18
Table 1
Product yields (%) for thermal and catalytic degradation of polyethylene (HDPE) at 430C, and life test of KFS-16B catalyst by repeated batch operation
a
HDPE sample (10 g)+catalyst (1 g).
b
Average carbon number on NP-gram of the liquid.
c
BN [g (Br2)/100 g (liquid)].
d
The catalyst used at 4th run was calcined with air at 600C for 3 h.
Y. Sakata et al. / J. Anal. Appl. Pyrolysis 43 (1997) 1525
Y. Sakata et al. / J. Anal. Appl. Pyrolysis 43 (1997) 1525 19
Fig. 2 shows the cumulative volume of liquid products and the temperature in the
reactor as a function of lapsed time. Lapsed time was counted from when the
heating of the sample from 120C to the degradation temperature commenced. The
initial slope of the cumulative volume vs. lapsed time curve represents the initial
rates of degradation of HDPE into liquid products. As can be seen, the rate of
degradation of HDPE over solid acid catalysts is much faster than the thermal
degradation. Surprisingly, over mesoporous silica (KFS-16B) which contains no
acid sites, the rate of HDPE degradation was also faster than non-catalytic thermal
degradation and comparable to that over solid acid catalysts (SA-1, SA-2). These
results suggest that mesoporous silica KFS-16B having a uniform hexagonal pore
of 3.6 nm accelerated the degradation of HDPE, even though the KFS-16B catalyst
does not contain any significant acid sites.
The yields of gaseous products for HDPE degradation are shown in the Table 1.
Fig. 3 shows the composition of gaseous products. For thermal degradation, the
gaseous products were mainly C3 (propane, propylene), C2 (ethane, ethylene) and a
u
o
W)
o
0>
L .
C
.O
Cu
L
O -
t /1
-or QJ
*i
X
z,
Temperature / C
Fig. 1. TPD spectra of the catalysts.
20 Y. Sakata et al. / J. Anal. Appl. Pyrolysis 43 (1997) 1525
12
10
S
H
J
I
3
8 <x>
3
o Xi
fD
> n
6 DS
c-
ft
03 "1
3
3 4 o
3 n
u
2
0
0 100 200 300 400 500 600
Lapse time / min
Fig. 2. Cumulative volume of liquid products from thermal and catalytic degradation of HDPE at
430C.
liquid products from catalytic degradation over SA-1 was very similar to commer-
cial auto gasoline fraction hydrocarbons. The quantitative analysis of the oil
fraction for aliphatic, olefins, diolefins and aromatics were not carried out. How-
ever, the qualitative analysis of the liquid products by infrared spectroscopy
revealed the following: Oil obtained from thermal degradation contained both
paraffins and olefins but no aromatics. Degradation oil from catalytic degradation
over SA-1 contained more olefins than the thermal degradation oil and much less
aromatics than the catalytic degradation over ZSM-5. The liquid products from
degradation over KFS-16B were much lighter than the thermal degradation prod-
ucts but heavier than the solid acid catalytic degradation products as shown in Fig.
4, and also indicated in Table 1 by the average carbon number (Cnp) of the liquid
products. For KFS-16B, the bromine number of the liquid products was also
similar to that for thermal degradation. From a comparison of the composition of
kerosene and diesel oil by NP-gram, the liquid products from degradation over
KFS-16B contain mainly kerosene and diesel fraction oil. As fuel for boiler or oil
fired furnace, kerosene and diesel fraction hydrocarbons are more desirable than
the gasoline fraction hydrocarbons as they are easy to handle. Compared to
non-catalytic thermal degradation , KFS-16B not only accelerates the rate of
degradation of HDPE but also degrades the heavier waxy compounds into kerosene
or diesel fraction hydrocarbons.
60
Thermal
KFS - 16 B
SA - 1
40
H
E3
SA -2
ZSM -5
I: %
i|
I
c 4 17/. \
o i v; \
V
u
Cu
m
m-*V
\
\
s
i
ig
wy
v,
% y.
\
Ip \
JS
b
5 20 iis p ii #
gg
\
* x
I ISI
Ip1
/
x
Ilf
\
2
x
11I
x
iii 2
2
X
X
X
Jj?3 IS 3 |g i \
111 X
0
1 2 3 4 5
Carbon Number
Fig. 3. Composition of the gaseous products from thermal and catalytic degradation of HDPE at 430C.
22 Y. Sakata et al. / J. Anal. Appl. Pyrolysis 43 (1997) 1525
30
O
Thermal
A
4
-- A
SA - 1
c 20 r F * SA -2
: < .
*
a ZSM -5
u \ i
0
%
V : KFS - 16B
* i
XL ) M-
61
a> I \
\
10 , 9 4*
\
\
\
A \9
.O
b -S-v .\
- o
...O - O" o. .N
D..
\
o.
\
a.
A' a.
.
o.
0
' ~ ~A --- A
"O . .
5 10 15 20 25
Carbon Number
Fig. 4. NP-grams of liquid product from catalytic degradation of HDPE at 430C.
Life test or stability test of KFS-16B for HDPE degradation was performed by
repeating batch operation using the same catalysts in four consecutive runs. The
yields of products are shown in Table 1 (right hand side). Results of the 1st run
with the fresh catalyst were mentioned earlier. In the 2nd through 4th run, the yield
of liquid products were more than 80%. It is interesting to note that after the 1st
run, the colour of the catalyst remained almost white, i.e. no coke formation was
observed. Whereas, with solid acid catalysts SA-1, SA-2 and ZSM-5, the catalysts
turned black after the 1st run due to the formation of coke on the catalysts surface.
With KFS-16B, even after four consecutive runs, the colour of the catalyst was off
white or light brown. Fig. 5 shows the cumulative volume of liquid products over
KFS-16B for repeated runs compared with that of non-catalytic thermal degrada-
tion. The rate of degradation of HDPE decreased slowly after repeated use of the
catalysts, indicating slow deactivation of the catalysts. However, the rate of
degradation even in the 4th run was faster than the thermal degradation. After the
4th run, the catalyst was regenerated by burning off the coke in air (calcination) at
600C for 3 h. The rate of degradation of HDPE over the regenerated catalyst was
the same as in the 2nd run. We performed similar life test experiments with SA-1
Y. Sakata et al. / J. Anal. Appl. Pyrolysis 43 (1997) 1525 23
3.6. Mechanistic aspects of the polymer degradation o6er mesoporous silica catalyst
12
10
E
a 8
E
3
o
6
v
>
fl
3 4
E
3
u 2
ric reactor vessels where the radicals are longer-lived than the conventionally used
solution medium, resulting in the production of polymers with high molecular
weight. Similarly, the acceleration of degradation of PP and PE polymers over
mesoporous silica (KFS-16B) of this study can be explained thus: the radicals
produced by thermal degradation of polymers are long-lived in the pores of
KFS-16B which accelerates the degradation reaction. This radical flask concept
explains explicitly all of our findings on plastic degradation with KFS-16B: rate
acceleration of degradation; and a product components distribution similar to the
thermal degradation.
4. Conclusions
This study has revealed that the mesoporous silica (KFS-16), which possess no
acid sites accelerate the rate of degradation of plastic polymers into liquid hydro-
carbons. It seems likely that the degradation mechanism of polymers over KFS is
related to its hexagonal pore structure. The mesopores surrounded by the silica
sheet act as a radical-flask. The radical species in the so-called radical-flask remain
active for long time and accelerate the degradation of plastics. These findings
provides new insight into the degradation of plastic polymers over non-acidic
mesoporous silica catalyst.
Acknowledgements
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