Pyrolysis of Polypropylene/Polyethylene/Polystyrene and Polyvinylchloride Mixed Plastics using CaCO3

Pyrolysis of Polypropylene/Polyethylene/Polystyrene
and Polyvinylchloride Mixed Plastics using CaCO3
Thallada Bhaskar, Md. Azhar Uddina, Jun Kaneko, Toshiki Matsuib,
Akinori Muto and Yusaku Sakata*

Department of Applied Chemistry, Faculty of Engineering, Okayama University, 700-8530

Okayama, Japan
aToda Kogyo Co., Ltd., Hiroshima 739-0652, Japan
†Process Safety and Environment Protection Group, School of Engineering, The University

of Newcastle, Callaghan, NSW 2308, Australia

Received: 7 March 2003 Accepted: 3 June 2003

ABSTRACT
The recycling of halogenated waste plastics poses serious problems. The
pyrolysis of PP/PE/PS/PVC was performed by using CaCO3 sorbent to remove
the chlorine content during the process. The presence of water (10 wt%) in the
plastic mixture did not effect the characteristics of liquid products or the
dechlorination efficiency of CaCO3 sorbent. The halogen free liquid products
can be used as a feedstock in refinery or fuel oil.

1. INTRODUCTION
The disposal of waste plastics is a serious environmental problem. The
municipal waste plastic (MWP) contains halogenated (PVC and PVDC) and
non-halogenated plastics (PP, PE and PS etc.). Among the various methods for
the treatment of MWP, feedstock recycling was found to be suitable option for
preserving valuable petroleum resources in addition to protecting the
environment by limiting the volume of non-degradable plastic waste(1). The
degradation of mixed plastics containing PVC produces hydrochloric acid,
which may lead to the formation of halogenated hydrocarbons in liquid
products, which are then unsuitable to use as fuel oil or feedstock in a
refinery(1). The degradation of MWP produces a small amount of water, which
is from the moisture content and will effect the dechlorination catalyst or
sorbent in degradation process. There is a need to develop the dechlorination

*Corresponding author
Tel: +81 86 251 8081; Fax: +81 86 251 8082. email: [email protected]

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 Thallada Bhaskar, Md. Azhar Uddin, Jun Kaneko, Toshiki Matsui, Akinori Muto and Yusaku Sakata

sorbent, which can work in the presence of moisture. Here we report the
pyrolysis of PP/PE/PS mixed with PVC plastics in thermal degradation and
using CaCO3 sorbent. We intentionally added about 10 wt% of water to the
plastic mixture, to see the effect of dechlorination, and any alteration in the
properties of the liquid products.

2. EXPERIMENTAL
Materials: The high density polyethylene (PE) was obtained from Mitsui
Chemical Co. Ltd., Japan; polypropylene (PP) from Ube Chemical Industries
Co. Ltd., Japan; polystyrene (PS) from Asahi Kasei Industries Co., Ltd., Japan;
and Polyvinyl chloride (PVC) from Geon Chemical Co. Ltd. Japan. The grain
sizes of PP, PE, PS and PVC were about 3 mm X 2 mm. The reagent grade
CaCO3 was obtained from Toda Kogyo Co. Ltd., Hiroshima, Japan.

Degradation procedure: The degradation of PP/PE/PS mixed with PVC was

carried out in a glass reactor (length: 350 mm; id 30 mm) under atmospheric
pressure by semi-batch operation. 10 g of mixed plastics (weight ratio: (PP/PE/
PS/PVC=3/3/3/1)) was loaded into the reactor for pyrolysis in vapor phase
contact with CaCO3. The CaCO3 (1 mm av. dia.) was loaded into another
reactor (dechlorination reactor) (Figure 1) and the sorbent bed temperature
was kept at 350°C. The reactor temperature was increased to the degradation
temperature (430°C) at a heating rate of 3°C/min and the dechlorination
reactor temperature (350°C) at a heating rate of 5°C/min. In a similar way, the
thermal degradation of plastics was carried out in the absence of sorbent. A
schematic diagram of the experimental setup is shown in Figure 1. The gaseous
products were condensed (using cold water condenser; Figure 1) into liquid
products and trapped in a measuring jar.

Analysis procedure: The quantitative analysis of the liquid products (collected

once at the end of experiment) was performed using a gas chromatograph
equipped with a Flame Ionization Detector (FID; YANACO G6800; column,
100% methyl silicone) to obtain the quantity of hydrocarbons and carbon
number distribution of the liquid products. The distribution of chlorine
compounds and the quantity of halogen content (organic) in liquid products
were analyzed by a gas chromatograph equipped with atomic emission
detector (AED; HP G2350A; column, HP-1; cross-linked methyl siloxane).
1,2,4-Trichlorobenzene was used as the internal standard for the quantitative
determination of chlorine content using the GC-AED analysis. The amount of
Cl content in NaOH trap (Figure 1) was analyzed using an ion chromatograph
(DIONEX, DX-120 Ion Chromatograph). The weight of a reactor including

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 Pyrolysis of Polypropylene/Polyethylene/Polystyrene and Polyvinylchloride Mixed Plastics using CaCO3

N2 Gas (10 ml/min)

Glass Dechlorination
reactor Reactor
i.d.: 30 mm
i.d.: 30 mm
L: 350 mm
L: 480 mm
Condenser
Cold water
Furnace
Furnace (350°C)
(430°C)

Cold
water
PP/PE/PS/PVC
Sorbent
catalyst
Thermocouple
Thermocouple

Teflon Bag

Graduated NaOH trap

cylinder for liquid
products

Figure 1 Schematic experimental setup for pyrolysis of PP/PE/PS mixed with

PVC by thermal and in the presence of CaCO3

the mixed plastics was measured before and after the degradation process. The
weight difference between before and after the degradation was used for the
calculation of residue. The main liquid products were analyzed by a gas
chromatograph with a mass selective detector (GC-MSD; HP 5973; column,
HP-1; cross-linked methyl siloxane) for the identification of various chlorinated
hydrocarbons in liquid products. The composition of the liquid products was
characterized using C-NP grams (C stands for carbon and NP for normal
paraffin) and Cl-NP gram (Cl stands for chlorine).

3. RESULTS AND DISCUSSION

The pyrolysis of PVC mixed with PP/PE/PS plastics in a weight ratio of
(1:3:3:3) was carried out under atmospheric pressure in a batch process using
CaCO3 sorbent and also thermal degradation (no sorbent) at 430°C. In a
similar way, 10wt% water was added to the above mixed plastics and carried
out the degradation at 430°C. The products of the mixed plastic degradation

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were classified into three groups: gas, liquid, and degradation residue. The
cumulative volume of the liquid products obtained during the above study is
presented in Figure 2. It is clear from the Figure 2 that the addition of water to
the plastic samples yielded more liquid products than in the absence of water.
The thermal degradation gave the less oil yields compared to the above two
experiments. However, the organic content is the same in all the three
experiments (Table 1 and Figure 2), the additional liquid products are only an
aqueous portion, which is due to the presence of water. Table 1 shows the yield
of products (gas, liquid, and residues) and average carbon number (Cnp),
density of liquid products obtained during thermal degradation along with the
total chlorine content in liquid products. The thermal degradation (PVC/PP/
PE/PS at 430°C) produced liquid products (63 wt%), with the average carbon
number of 10.4 and density 0.8 g/cc. The liquid product obtained during the
degradation with CaCO3 sorbent was about 65, with the average carbon
number of 10.6 and density 0.8 g/cc. There is no appreciable change in the
average carbon number (Cnp), and density of liquid products obtained during
both in thermal degradation and degradation using CaCO3 sorbent (Table 1).
The gaseous products obtained during the thermal degradation were
approximately same with the degradation using sorbent (Table 1). There is no
appreciable change in amount of residue for the thermal degradation (13 wt%)

Figure 2 Cumulative volume of liquid products during PP/PE/PS mixed with

PVC pyrolysis at 4300C

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Table 1 Products yield and properties of liquid product from PP/PE/PS mixed
with PVC degradation at 4300C using Ca-C sorbent and thermal degradation

Weight ratio: PP:PE:PS:PVC = Sorbent: CaCO3

3:3:3:1 Dechlorination Temp: 350°C
Degradation Temp: 430°C
Degradation Yield of degradation Liquid Total
Method products [wt%] products chlorine in
liquid
Liquid Gas Residue Cnpb Density
products
[L] [G]a [R] (g/cc)
Thermal 63 24 13 10.4 0.80 360
CaCO3 65 25 10 10.6 0.80 n.d
CaCO3 and water 72 17 11 10.7 0.81 n.d.
in plastic (10 wt%)
a
G = 100 – (L+R)
b
Cnp = Average carbon number of liquid products based on C-NP gram
n.d. not detected

and also degradation using sorbent (10 wt%). The Cnp and density of products
doesn’t change with the addition of water. However, the yield of liquid
products was found to be high (7 wt%), when the water was added with CaCO3.
It is due to the presence of water mixed with the liquid products. Roy et al(2)
reported on the vacuum pyrolysis of commingled plastics (HDPE/LDPE/PP/
PS) containing PVC at a final temperature of 500°C and under a total pressure
of 2 kPa. During their vacuum pyrolysis studies, the pyrolysis oil contained
12 ppm Cl on a pyrolysis oil basis.

The total chlorine content in liquid products obtained during thermal degradation
was about 360 ppm is due to the presence of various halogenated hydrocarbons
in the liquid products. The use of CaCO3 sorbent completely removed the
chlorine content and produced the halogen free liquid products. The liquid
products can be used as a fuel oil or feedstock in refinery. To use the CaCO3
sorbent for the municipal waste plastic pyrolysis, the sorbent should be strong
enough to withstand for the moisture content present in MWP. The intentionally
added water did not change the global characteristics of liquid products and
also the dechlorination ability of CaCO3 sorbent. The analysis of degradation
residue showed the presence of about 1.5 wt% of chlorine in thermal degradation

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and also with CaCO3. Meszaros(3) reported the pyrolysis of municipal plastic
waste (MPW) containing 3% of PVC in an auger kiln reactor (Conrad
recycling process). Lime was used in order to trap the HCl evolved, which
resulted in liquid products with 25 ppm of chlorine. Williams and Williams(4)
studied the pyrolysis of municipal plastic waste (MPW) in a fluidized bed
reactor at atmospheric pressure. A dreschel bottle of de-ionized water was
used in order to trap the evolved HCl, but only 27.5% of the HCl trapped.
Bockhorn et al(5) studied the pyrolysis of a PVC/PS/PE (1:6:3 by wt.) mixture
in three circulated-sphere reactors arranged in a cascade and they detected
44 ppm of chlorine in oil from the third reactor, which mainly contained
aliphatic compounds. However, the chlorine content in the oil from the second
reactor was still high at 210 ppm (by wt.).

The liquid products were characterized by a Normal Paraffin gram (NP-gram)

proposed by Murata et al(6). Figure 3 illustrates the C-NP gram of the liquid
products obtained by analyzing their gas chromatogram. The carbon numbers
in the abscissa of the NP-gram are equivalent to retention values of the
corresponding normal paraffin and the ordinate shows the weight percent of
the corresponding hydrocarbons (g(Cn)X100/g(oil), wt.%). The hydrocarbons
(C6-C11) during the thermal degradation and degradation using CaCO3 sorbent

Figure 3 C-NP gram from the liquid products obtained during PP/PE/PS mixed
with PVC pyrolysis at 4300C

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was 47 wt% (Figure 3) in both cases. As with the C-NP gram, the carbon
number distribution of chlorinated hydrocarbons in the liquid product was
prepared from the gas chromatogram obtained using a gas chromatograph with
an atomic emission detector (Figure 3). The hydrocarbons containing the
chlorine were distributed in the range of C6-C11. The liquid products were
analyzed by GC-MS to identify the compounds. The presence of chlorinated
compounds during the thermal degradation was observed as 2-chloro-2-
phenyl propane, 2-chloro-2-methyl propane, 2-chloro-2-methyl pentane. The
formation of chlorinated hydrocarbons might be due to the reaction between
hydrogen chloride originating from PVC and the hydrocarbons obtained from
the degradation of PE, PP and PS(7). We have earlier reported on the degradation
of various halogenated and non-halogenated plastics and also dechlorination
by various iron oxide catalysts/sorbents(8-11). The X-ray diffraction patterns
(Figure 4) of the CaCO3 before and after degradation shows the formation
CaCl2.nH2O (where n = 2, 4) from CaCO3 by the reaction of chlorine.

Figure 4 X-ray diffraction pattern of CaCl2. nH2O

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4. CONCLUSIONS
The pyrolysis of PP/PE/PS/PVC and PP/PE/PS/PVC with 10% H2O was
performed using CaCO3 sorbent and completely removed the chlorine content
from the liquid products. The presence of water in the municipal waste plastic
mixture did not effect the characteristics of liquid products or the dechlorination
efficiency of CaCO3 sorbent. The applicability of calcium based sorbent for
our municipal waste plastic pyrolysis plant at Mizushima, Japan is under
progress.

ACKNOWLEDGEMENTS
The authors thank New Energy Development Organization (NEDO), Japan
for financial support to carryout this research work under the Chugoku
regional consortium project (2000-2003).

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