J Mater Cycles Waste Manag (2001) 3:88–92
SPECIAL FEATURE: ORIGINAL ARTICLE
Eiko Obuchi · Masaki Suyama · Katsuyuki Nakano
Decomposition of mixed plastics consisting of polypropylene and
polyethylene terephthalate into oils over titania/silica catalysts
Received: July 19, 2000 / Accepted: October 20, 2000
Abstract
The catalytic decomposition of mixed plastics consisting of
polypropylene (PP) and polyethylene terephthalate (PET)
has been investigated over titania/silica catalysts at 698 K.
The yield of oil produced was about 70%, and the large
amounts of C18+ hydrocarbons this contained was from the
aromatics in PET. Gas was also produced, including C3–C5
hydrocarbons. The carbon-number fractions in the oil was
influenced by the PET/(PP + PET) ratios and the catalyst
weight. The titania/silica catalysts could be used repeatedly,
and after they had been fouled, could be regenerated. From
the Fourier Transform Infrared (FT–IR) spectroscopic data
of adsorbed pyridine on the catalyst surface, most of the
acid sites of the titania/silica catalysts were found to be
Lewis sites where the hydride abstracted from PP pyroly-
sates react with PET pyrolysates to form oil and gas.
Key words Polypropylene · Polyethylene terephthalate
(PET) · Oil production · TiO2/SiO2 catalyst · Lewis acid site
Introduction
Since plastics are convenient materials and indispensable to
daily life, the amount of plastics produced increases yearly,
and the total reached about 14 million tons in Japan in 1998.
Consequently, the increase in waste plastics has given rise
to numerous environmental problems. In 1998, the total
amount of waste plastics was about 10 million tons, with
municipal waste and industrial waste in a 50 : 50 ratio. To
reduce the amount of waste plastics, new waste treatment
laws and changes in the infrastructure have been intro-
duced, so that 44.2% of waste plastics are now recycled. Of
this 44.2%, 12.7% is being regenerated, 0.7% is being used
E. Obuchi · M. Suyama · K. Nakano (*)
Department of Chemical Engineering, Fukuoka University, 8-19-1
Nanakuma, Johnan-ku, Fukuoka 814-0180, Japan
Tel. +81-92-871-6631; Fax +81-92-865-6031
e-mail: knakano@fukuoka-u.ac.jp
© Springer-Verlag 2001
Chemical Feedstock Recycling (2)
as solid fuel, 0.4% is used as liquefaction and/or blast
furnace feed stock, 16.7% is used as fuel for power genera-
tion, and 14.0% is being incinerated for thermal utilization.
Of the remaining 55.8% of waste plastics, 22.5% is in-
cinerated and 33.3% is sent to landfill disposal sites.
Homogeneous plastics in industrial wastes can be used
after regeneration and easily converted into monomers.
However, because of the heterogeneity and dirtiness of
waste plastics in municipal waste, the cost involved in sep-
arating, collecting, transforming, and washing it is very high,
and so the proportion which is recycled is low. Although in
1997, the Japanese government decided on guidelines to
convert thermoplastic resin into fuel oils, only 10 000 tons
of waste plastics have been converted into fuel or blast
furnace fuels to date (all the statistics given above were
obtained from the Plastic Waste Management Institute’s
homepage.) At present, there are a few operational plants
that treat polyolefin resin, but the process is far from
perfect. It is very complicated, and the catalyst used is deac-
tivated owing to the deposition of coke-like substances on
the catalyst surface. In addition, since chlorine in polyvinyl
chloride (PVC) forms hydrogen chloride, which causes cor-
rosion of the reactors, an intermediate treatment is required
for PVC. All municipal plastic waste also contains PET
resin, which must be removed at the inlet stage of the
system because pyrolysates of PET form large amounts of
carbon and/or phthalic acids, which choke up the reactor
and prevent continuous operation. The amount of PET
consumption and waste continues to rise, and it would be
impossible to remove PET completely from municipal
plastic waste. Consequently, it is necessary to develop a
system that can treat all types of plastic without any sepa-
ration process.
In a previous paper,1 we reported that polyethylene
(PE), polypropylene (PP), and polystyrene (PS) were con-
verted into oils over a TiO2 catalyst supported on silica
beads which had macropores.The pyrolysates of plastics can
diffuse into the inner pores of the beads, be adsorbed on the
active sites, and then be decomposed to lower molecular
weight hydrocarbons. In this system, the process is simpli-
fied because it has the advantage that the pyrolysis and

catalysis of the plastics can proceed in the same reactor. The
purpose of the present work is to study the decomposition
of mixed plastics consisting of PP and PET over TiO2/SiO2
catalysts, and to investigate which operating conditions
influence product composition and the mechanism of oil
production. In addition, we tried to regenerate the catalysts
in order to use them repeatedly.
Experimental
Preparation of catalyst2,3
Silica beads with a mean pore diameter of about 50 nm (Fuji
Silysia Chemical, Kasugai, Japan; 5–10 mesh and 86 m2/g
Brunauer Emmett Teller (BET) surface area) were im-
mersed in an isopropanol (IPA, C3H7OH) solution contain-
ing titanium tetraisopropoxide (TIP, Ti(OC3H7)4) (molar
ratio, TIP : IPA = 1 : 2) and left overnight. After the hydroly-
sis of TIP in humidified air, the treated beads were calcined
at 773 K for 2 h. Thus, a 20 wt. % TiO2/SiO2 catalyst was
obtained.
The characterization of the catalyst was made using
FT–IR (1600 series, Perkin Elmer, USA) spectroscopic data
of pyridine adsorbed in the catalyst.
Experimental operation
The apparatus consisted of a vertical tubular Pyrex reactor
(26 mm diameter and 900 mm length) in an electric furnace
with temperature controller, as shown in Fig. 1. The TiO2/
SiO2 catalysts were packed in the reactor below the sample
holder, which was packed with a mixture of PP and PET. A
nitrogen stream was set at a flow rate of 40 ml min-1. At 698
K, pyrolysis gas from mixed plastics passed through the cat-
Fig. 1. Schematic diagram of the apparatus. 1 N2 gas bomb; 2 needle
valve; 3 silica gel dryer; 4 reactor; 5 sample holder; 6 catalyst; 7
electric furnace; 8 temperature controller; 9 thermocouple; 0 sam-
pling tee; - condenser; = ice bath; q soap-film flow meter
89
alyst bed and was liquefied and stored in a condenser cooled
in an ice bath. For the preliminary experiment, we under-
took a study to investigate whether different packing styles
for the PP and PET would produce different amounts of oil
and different oil compositions. The first sample was a sand-
wich of PET between two layers of PP. The other was a
sample of PP and PET which had been homogeneously
fused. A comparison of the oils produced indicated that
both samples could be decomposed into similar oils over a
TiO2/SiO2 catalyst. As the sandwich-type sample is easier
to set up, it was decided to use this type for the following
experiments. The product gas and oil (liquid) were analyzed
using gas chromatographs equipped with an Flame Ioniza-
tion Detector (FID) (Autosystem, Perkin-Elmer, Norwalk,
CT, USA) and a thermal conductivity detector (TCD) (G-
2800, Yanaco, Bunseki Kogyo, Kyoto, Japan). We measured
the weight of the oil produced and the volume of the gas
produced. We estimated the weight of the gas by measuring
the distribution of hydrocarbons produced. The “sample
holder residue,” i.e., the residue that was left in the sample
holder, and the “adsorbed substance,” i.e. the substance that
was adsorbed on the catalyst, were both estimated by
measuring their mass before and after the reaction.
Regeneration of the used catalyst
The used catalyst was regenerated as follows. The catalyst
was packed in the reactor and heated to between 673 and
773 K at an air-flow rate of 150 ml min-1. As CO2 was pro-
duced by combustion of the “adsorbed substance” on the
catalyst surface, the amount of CO2 was measured by gas
chromatography (GC) (TCD). When no further CO2 could
be detected other than the amount of CO2 in the air, we con-
sidered that the catalyst had been regenerated completely.
The regenerated catalyst was then used in the experimen-
tal operations.
Results and discussion
PET itself did not convert into oils over a TiO2/SiO2 cata-
lyst and formed a milk-white solid which was probably a
kind of phthalic acid. The reason for this may be the fact
that pyrolysates of PET contain aromatic compounds
and oxygen, but lack hydrogen. We hoped that PET would
decompose when the PP pyrolysates, which have a higher
hydrogen content, were mixed with them over macroporous
TiO2/SiO2. We expected that PET could be completely
decomposed into oils under the conditions indicated by the
shaded area in Fig. 2. Outside this area, solid material was
produced in the oils. A comparison of the carbon-number
fractions in the oils produced from the PP and the mixture
of PP and PET at a catalyst weight of 7.5 g, when the
PET/(PP + PET) ratios were 0 and 0.15, respectively, can
be seen in Fig. 3. It was found that oil produced from the
mixture of PP and PET contained smaller amounts of
C5–C17 hydrocarbons (except for C8) and larger amounts of
90
Fig. 2. Operating conditions that produce oil with no solids
Fig. 3. Changes in carbon-number fractions due to the changes in
PET/(PP + PET) ratios (0 and 0.15) and reaction temperatures (723 K
and 698 K, respectively)
C18+ hydrocarbons compared with the oil from PP. As the
PET ratio increased, this tendency became stronger, as
shown in Fig. 4. This is because C18+ hydrocarbons are found
in the aromatics in PET. If the PET/(PP + PET) ratio is
greater, the oil produced contains some solids as mentioned
above.
The comparison between the product distributions and
the carbon-number fractions in the oil produced over dif-
ferent weights of catalyst can be seen in Figs. 5 and 6, respec-
tively. Figure 5 shows the weight percentage of oil produced,
gas produced, sample holder residue, and adsorbed sub-
stance on the catalyst. Not all examples reach 100% of the
total weight, and this is attributed to the residue left on the
reactor wall. At PET/(PP + PET) = 0.15 and a catalyst
weight of 2.5 g, the oil yield was about 70%, but this
decreased with increasing catalyst weight. The greater the
catalyst weight, the lighter the oil fraction and the larger
Fig. 4. Changes in carbon-number fraction due to the changes in
PET/(PP + PET) ratios
Fig. 5. Comparison of the product distributions from a mixture of PP
and PET over different weights of catalyst at 698 K
the amount of gas, because the heavier components were
decomposed on the surface of the catalyst. The gas pro-
duced consisted mainly of C3–C5 hydrocarbons, and this is
potentially useful as a fuel. PET molecules contain oxygen
which may be converted into CO, CO2, and other oxy-
genated compounds. CO and CO2 were detected in the gas
produced, and from the composition of these gases, the mass
balance of oxygen was about 60% over the TiO2/SiO2 cata-
lyst. Since other oxygenated compounds did not appear in
the gas and oil produced, we assume that the oxygen is con-
verted into water and oxygen gas, which is difficult to detect
using gas chromatographic analysis, as in this experiment.
The TiO2/SiO2 catalyst was used repeatedly, as shown in
Fig. 7. A mixture of PP and PET (PET/(PP + PET) = 0.15)
was converted into oils without the formation of solids up

Fig. 6. Comparison of carbon-number fractions of oils produced from
a mixture of PP and PET over different weights of catalyst
Fig. 7. Yields of oil produced with repeated uses of fresh and regen-
erated TiO2/SiO2 catalysts
to the 8th run in fresh catalyst. It was found that the yield
of oil produced increased gradually, and this oil included
heavier components with repeated use of the catalyst. In the
9th run, the mixture of PP and PET could not be completely
converted into oils owing to the formation of the solids
derived from PET pyrolysates, and therefore the catalyst
was then regenerated as described above. The yield of oil
for the regenerated catalyst was almost the same as for the
fresh catalyst until the 7th run. We had discovered that we
could use the TiO2/SiO2 catalyst repeatedly and regenerate
it successfully. However, the fact that the number of
repeated uses of the catalyst decreased was assumed to be
because the regeneration was incomplete, or because sub-
stances which were not removed were adsorbed strongly
on the catalyst. In general, coke consists of both “hard”
(nonvolatile) and “soft” (volatile) coke. Whereas soft coke
is easily burned off at a relatively low temperature in air,
91
Fig. 8. FT–IR spectra of adsorbed pyridine on the TiO2/SiO2 catalyst:
(a) before the adsorption of pyridine; (b) after the adsorption of pyri-
dine; (c) the differential spectrum
Table 1. Assignment of infrared absorption bands of adsorbed pyri-
dine in the range 1700–1400 cm-1
Vibration mode PyB (cm-1) PyL (cm-1)
8a 1640–1634 1615–1592
19a 1490–1478 1490–1471
19b 1542–1525 1461–1437
hard coke is difficult to burn off and high temperatures of
around 823 K are usually required. However, in order not
to sinter the catalyst in the regeneration process, it was
heated to only 773 K.
We analyzed the surface of the catalyst to clarify the
mechanism of the plastic decomposition reaction.The acidic
character of the TiO2/SiO2 was proved by the pyridine
adsorbed on the catalyst using FT–IR spectroscopy. In
general, pyridine combines with Lewis acid sites to form
coordinated pyridine (PyL), and with Brønsted acid sites
to form pyridinium ion (PyB). The assignment of infrared
absorption bands of adsorbed pyridine in the range
1700–1400 cm-1 is shown in Table 1. Infrared spectra of
TiO2/SiO2 catalyst surfaces before and after adsorption of
pyridine and their differential spectrum are shown in Fig. 8.
The peaks were found to be at 1446, 1490, and 1608 cm-1, as
shown in Fig. 8. They correspond to the peaks of coordi-
nated pyridine shown in Table 1.4 Although the peak at
1490 cm-1 may be considered to be the Brønsted acid site,
we considered it to be the Lewis acid sites because no other
peaks for Brønsted acid sites were found on the TiO2/SiO2
catalyst from these spectra. Consequently, we conclude that
the acid sites on the TiO2/SiO2 catalyst are almost identical
to the Lewis acid sites.
Lewis acid sites are known to abstract hydrides from
adsorbed hydrocarbons to break down long-chain hydro-
carbons via b-scission reaction.5 In a previous paper,1 we
found that hydrogen was formed in the gas phase when
Pt–TiO2/SiO2 catalysts were used. This phenomenon is
92
thought to be due to the surface migration of hydrides to
react with protons on the platinum surface. We therefore
suggest that the production mechanism of oil from mixed
plastics consisting of PP and PET over a TiO2/SiO2 catalyst
is as follows. First, pyrolysates of PP and PET are separately
adsorbed on the catalyst surface. Second, the hydride is
abstracted from the PP pyrolysates on the Lewis acid sites
and moved to the PET pyrolysates.5 Finally, the PET
pyrolysates pick up the hydride and form hydrogen-rich
compounds which break down into lighter hydrocarbons
via b-scission reaction. The rest of the pyrolysates are left
on the catalyst surface as a coke precursor or “adsorbed
substance.”
The action of the Brønsted acid sites, however, is cur-
rently still being investigated using an Al2O3 catalyst. More
research is needed in order to understand the relationship
between the acid sites of the catalyst and the oil production
mechanism.
Conclusion
Mixed plastics consisting of PP and PET were converted
into oils up to PET/(PP + PET) = 0.45, without the forma-
tion of solids, over a TiO2/SiO2 catalyst at 698 K in a nitro-
gen stream. The yield of the oil produced was about 70%,
and this oil contained large amounts of C18+ hydrocarbons.
The yield of oils and their carbon-number fractions changes
with changes in PET/(PP + PET) ratios and catalyst weight.
The TiO2/SiO2 catalyst could be regenerated and used
repeatedly. Oil and gas production is due to the reaction of
hydrides abstracted from PP pyrolysates on the Lewis acid
sites with PET pyrolysates. The oil and gas produced could
be used as fuel after this catalytic transformation.
Acknowledgments We would like to thank the Plastic Waste Manage-
ment Institute for their financial support.
References
1. Obuchi E, Nakano K (1994) Catalytic decomposition of plastic
wastes into fuel oils over titania supported on silica. Proceedings of
the Taipei-Kyushu Joint Symposium on Chemical Engineering and
on Transport Phenomena and Applications, Taipei, 253–257
2. Matsuo K, Nakano K (1988) Performances of platinum metal
catalysts supported on titania-coated silica prepared from metal
organics. Appl Surf Sci 33/34:269–276
3. Obuchi E, Sakamoto T, Nakano K, Shiraishi F (1999) Photocatalytic
decomposition of acetaldehyde over TiO2/SiO2 catalyst. Chem Eng
Sci 54:1525–1530
4. Rajagopal S, Marzari JA, Marinda R (1995) Silica–alumina-
supported Mo oxide catalyst: genesis and demise of Brønsted–Lewis
acidity. J Catal 151:192–203
5. Guerzoni FN, Aboot J (1994) Catalytic cracking of a Gippsland
reduced crude on zeolite catalysts. J Catal 147:393–403