Waste Management 31 (2011) 1848–1851

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Waste Management
journal homepage: www.elsevier.com/locate/wasman

Recovery of polypropylene and polyethylene from packaging plastic wastes

without contamination of chlorinated plastic films by the combination process
of wet gravity separation and ozonation
Mallampati Srinivasa Reddy a,⇑, Tetsuji Okuda a, Satoshi Nakai b, Wataru Nishijima a, Mitsumasa Okada b
a
Environmental Research and Management Center, Hiroshima University, 1-5-3 Kagamiyama, Higashi-Hiroshima, Hiroshima 739-8513, Japan
b
Department of Chemical Engineering, Graduate School of Engineering, Hiroshima University, 1-4-1 Kagamiyama, Higashi-Hiroshima, Hiroshima 739-8527, Japan

a r t i c l e i n f o a b s t r a c t

Article history: Wet gravity separation technique has been regularly practiced to separate the polypropylene (PP) and
Received 22 September 2010 polyethylene (PE) (light plastic films) from chlorinated plastic films (CP films) (heavy plastic films).
Accepted 28 March 2011 The CP films including poly vinyl chloride (PVC) and poly vinylidene chloride (PVDC) would float in water
Available online 6 May 2011
even though its density is more than 1.0 g/cm3. This is because films are twisted in which air is some-
times entrapped inside the twisted CP films in real existing recycling plant. The present research
improves the current process in separating the PP and PE from plastic packaging waste (PPW), by reduc-
ing entrapped air and by increasing the hydrophilicity of the CP films surface with ozonation. The present
research also measures the hydrophilicity of the CP films.
In ozonation process mixing of artificial films up to 10 min reduces the contact angle from 78° to 62°,
and also increases the hydrophilicity of CP films. The previous studies also performed show that the arti-
ficial PVDC films easily settle down by the same. The effect of ozonation after the wet gravity separation
on light PPW films obtained from an actual PPW recycling plant was also evaluated. Although actual light
PPW films contained 1.3% of CP films however in present case all the CP films were removed from the
PPW films as a settled fraction in the combination process of ozonation and wet gravity separation.
The combination process of ozonation and wet gravity separation is the more beneficial process in recov-
ering of high purity PP and PE films from the PPW films.
Ó 2011 Elsevier Ltd. All rights reserved.

1. Introduction
In household waste, container and packaging plastic waste is a
big social obligation because of the large volume percentage. The
volume of container and packaging waste is about 60% from total
household waste and 68% of plastic films generating in Japan
(PWMI, 2005, 2007; JPIF, 2003). Nearly about 100 million tons of
plastic waste has been discarded in Japan, in which nearly 51 mil-
lion tons of plastic waste generating from households (PWMI,
2007; JPIF, 2003). Hence a stringent Containers and Packaging
Recycling Law was enforced in Japan, which came into effect in
the year 2000 to recycle all container and packaging waste. A sep-
arate collection of packaging waste began in 1997. Polyethylene
(PE) and polypropylene (PP) represent the largest volumes of
commodity plastics film, followed by polyvinyl chloride (PVC),
polyvinylidene chloride (PVDC), polyethylene terephthalate
(PET), polystyrene (PS), and polyacetylene (PA) in products
⇑ Corresponding author. Fax: +81 82 424 6195.
E-mail addresses: srireddys@hiroshima-u.ac.jp, srireddys@hotmail.com (M.S.
Reddy).
amount. Chlorinated plastics films (CP film) i.e., PVC and PVDC
films contain 8–10% by weight in plastic packaging waste (PPW).
CP films widely used in packaging include disposable bottles (for
oil, mineral water, vinegar, etc.), wrapping film, trays and boxes,
bottles and jars, blister packaging, crown cork, transportation
packaging, etc., (APC, 1996; Ogaki, 2002). These CP films lead to
generation of environmentally hazardous compounds such as
hydrogen chloride and dioxins during the thermal energy recovery
and melting process for material and chemical recycling (Andricic
and Kovacoc, 1999; Anthony et al., 2001). Therefore, these CP films
must be isolated from PPW films. Japan Containers and Packaging
Recycling Association has required PPW for its material recycling,
contains less than 0.3% of total chlorine content (JCPRA, 2007). In
addition, dye, paper and lime industries are using Refuse Paper
and Plastic Fuel (RPF) as alternative fuel instead of coal and coke;
however these industries require RPF with less than 0.2% chlorine
content (PWMI, 2005). Hence it is necessary to bring down the
chlorine content for recycling of PPW. Therefore, CP films need
to be isolated from PPW.
The typical specific gravities are approximately 0.92, 0.94, 1.42,
1.71, 1.03, 1.22 and 1.41 g/cm3 for PE, PP, PVC, PVDC, PS, PA and

0956-053X/$ - see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.wasman.2011.03.018
 M.S. Reddy et al. / Waste Management 31 (2011) 1848–1851
PET, respectively (Shen et al., 2001). Therefore, the CP films are gen-
erally separated from light plastic film like PP and PE by a wet gravity
separation process. However, in wet gravity separation plant,
usually in the process light films are contaminated with CP films
even though the gravity of the CP films is more than 1.0 g/cm3,
because the air is sometimes entrapped inside the twisted CP films
(Srinivasa Reddy et al., 2010).
It is well known that the CP films twist by self-aggregation
because of the electrostatic properties resulting from the presence
of chlorine group in their structure (APC, 1996). Our recent study
revealed that the ozonation could selectively increase the
hydrophilicity of the PVC surface among pellet polymer mixture
including PET, PC (polycarbonate) and PMMA (poly (methyl meth-
acrylate) (Okuda et al., 2007). Hence, the objective of this research
is to recover PP and PE films from the PPW without the CP films
contamination by the combination process of the wet gravity sep-
aration and ozonation. The effects of ozonation time, twisted area,
and mixing speed on the separation efficiency of the CP films from
the PP and PE films were studied.
2. Materials and methods
2.1. PPW films
The actual light weight PPW films about 1 kg have been
collected in household plastic waste recycling plant in Japan and
analyzed. Samples were shredded before wet gravity separation,
the size distribution of shredded sample was about 3–50 mm,
but most of the sample was about 1 cm  1 cm size. These light
plastic films originated from the container and packaging, and
mainly consist of PE and PP films, however some other films (like
PVC, PVDC, PET, PS, etc.) contamination also occur.
In this method of float sink separation the PPW films having
lower density (<1.0 g/cm3) compared to other CP films (>1.0 g/
cm3) were separated by retaining the composite waste in wet
gravity separation for low retention hours, respectively, during
lab scale experimentation. In fact some of CP films even though
its gravity is more than >1.0 g/cm3 were not able to sink in water,
because there is an entrapment of air in twisted CP films (Srinivasa
Reddy et al., 2010). Therefore the actual light PPW films also con-
tained 1.3% of the CP films (PVC and PVDC) as shown in Fig. 1.
For these studies a homogenized sample of PPW at about 10 g
was taken to identify the composition of plastics, a 1:1 ratio of
mixture of PVC and PVDC among PP, PE and CP films was
considered for experimentation. The individual plastics composi-
tion piece by piece analysis was also done by using ATR-FTIR
(Attenuated Total Reflectance-Fourier Transform Infrared Spec-
Other 2.5%
CP films
1.3%
PP
36.3%
High density
PE 38.9%
PE 21.0%
Fig. 1. The composition of actual light PPW films (wt.%).
1849
trometer), Spectrum One, Perkin Elmer. On the basis of the compo-
sition of PP, PE and CP films in actual light PPW films, PP, PE and CP
films (1:1 mixture of PVC and PVDC) were obtained from commer-
cial wrap, food and beverage covers and considered as artificial
PPW films. These artificial films were cut to 1–5 cm size and used
for further experiments.
2.2. Twisted films
An artificially twisted PPW film was prepared by using a kitchen
mixer at a revolving speed of 15,000–18,000 rpm under dry condi-
tion (Hamilton Beach, HBB908). During the period of study, twists
were apparently formed only in CP films rather than PP and PE
films. The visuals of twisted and non-twisted PVDC films were pre-
sented in Fig. 2. Elasticity is generally expressed as the ability of
the material to return to its original shape. Plasticized PVC and
PVDC with chlorine group in their structure are known to have
low elasticity and high tensile strength, while the elasticity of
other plastic films is high but tensile strengths is very low (APC,
1996). The difference of elasticity and tensile strength between
chlorinated plastics and other plastics will cause selective twist
formation for CP films (APC, 1996). The experiments were carried
out at different strengths and at different revolving speeds to
determine the effect of twisted area on floatation. The twisted area
was classified by visual observation.
2.3. Density analysis
The apparent density of films was defined as the density of the
film with air on the surface and/or inside twists. This was mea-
sured immediately after adding the films in water without any
mixing. The true density of films was also determined after re-
moval of the entrapped air from the films in water by mixing at
300 rpm under vacuum condition. The density of films was mea-
sured used by specific gravity bottle method (ISO, 2004), using
IWAKI, 420 specific gravity bottle for samples of 0.1–0.5 g of film.
2.4. Ozonation for increasing surface hydrophilicity
Surface hydrophilization of PPW films by ozonation was con-
ducted in a volumetric glass reactor with a capacity of 3.0 dm3
by providing 30 cm height and 15 cm diameter (Okuda et al.,
2007). The reactor with ceramic bubble diffuser plate has pore
diameter of 10–16 lm, was arranged at the bottom of a reactor.
An average flow rate of 50 ml/min ozone gas was feed in a reactor
through diffuser produced by an ozone generator (POX-10,
Fuji-electric). Ozonation was applied to the films for 30 min
retention period. The effectiveness of ozonation in terms of
hydrophilicity, contact angle of film surface was measured before
and after ozonation. The contact angle was measured by using Con-
tact angle meter (CA-XP, Kyowa Interface Science), FAMAS (Face
Measurement & Analysis System).
2.5. Wet gravity separation
Settling and floating behavior of each artificial and actual PPW
films were studied by the wet gravity separation method. Wet
gravity separation was conducted in a reactor used for ozonation.
In this method, a sample of 10 g of both artificial and actual PPW
was introduced individually in a reactor filled with Demineralised
Water and evaluated. During the period of study, the reactor was
agitated by a 3 pin sphere shaped paddle for 2 min with a revolving
speed of 300 rpm. The arrangement of agitation mechanism was
kept 1–5 cm below the water surface in a reactor.
After completion of experiment the floated and settled films
were segregated. The films were identified with ATR-FTIR and
1850 M.S. Reddy et al. / Waste Management 31 (2011) 1848–1851

Fig. 2. Twisted and non-twisted PVDC films.

weighed for their composition. For the actual floatable films, sepa-
rate experiments were conducted sequentially with and without
ozonation.
3. Results and discussion
3.1. Apparent density
The apparent and true densities were determined for artificially
blend CP films in a ratio of 1:1 PVC:PVDC which was collected in
commercial wrap, after preliminary screening as treatment to
reproduce the twist shape similar to the actual PPW film treating
at a large scale recycling plant. During the period of study it was
found, that the true density of CP blended films was about
1.61 g/cm3 and apparent density was about a 0.77 g/cm3 as shown
and flexible PVC pellets after 120 min of ozonation with sufficient
mixing was also studied and shown in Fig. 4. It was observed while
passing the ozone gas up to 10 min the contact angles of flexible
and rigid PVC pellets was decreased to 5° from 25° to 20°, respec-
tively. During the period of study the surface hydrophilicity was in-
creased on both the pellets and the films. The difference in
hydrophilicity of pellets and films is due to the addition of caused
plasticizer. The increase in surface hydrophilicity is due to the
change of chloride groups on the surfaces of PVC and PVDC into
100
90
PVC pellets (rigid)
Contact angle (degrees)

in Fig. 2. The large quantity of air was entrapped inside the twists PVC pellets (flexible)
and also on the surface of the films was observed and measured for PVDC films
apparent density. The variation of the apparent density was also 80
studied for twisted CP blend films for a mixing time up to 10 min
as shown in Fig. 3. The apparent densities of the CP films were ob- 70
served (<1.0 g/cm3) even after mixing up to 10 min (Srinivasa Red-
dy et al., 2010).
60
3.2. Surface hydrophilization with ozonation and separation of PVDC
films 50
0 20 40 60 80 100 120 140
The contact angle of the artificial PVDC film was measured and Ozonation time (min)
shown in Fig. 3. After passing of ozone gas up to 10 min sufficient
Fig. 4. Contact angles of PVDC films and virgin PVC pellets before and after
mixing time the contact angle of PVDC film was decreased to 16°
ozonation.
from 78° to 62°, respectively. The contact angles of virgin rigid

2.0
percentage of floated fraction of PVDC (%)

100
1.6
Density (g/cm3)

80
1.2
60

0.8
40 With-out ozonation
Apparent density
Ozonation
0.4 True density
20

0.0 0
0 2 4 6 8 10 12 100% 75% 50% 25% 0%
Mixing time (min) Twist area

Fig. 3. True and apparent densities of the twisted blend CP films with twist at Fig. 5. Floatation behavior of PVDC films without and with 10 min ozonation at
different mixing time. different twisted area (average values in three times analysis).
 M.S. Reddy et al. / Waste Management 31 (2011) 1848–1851 1851

Table 1 of ozonation and wet gravity separation process can be useful for
The polymer composition in initial, after mixing and ozonation (actual light PPW the recovery of PP and PE films with high purity from CP films.
films).

Material Initial After mixing After ozonation and mixing

(wt.%) (wt.%) 4. Conclusions
Floated Floated Settled Floated Settled
At present, an attempt was made to separate the CP films
PE 21.0 21.0 0.0 21.0 0.0
among PP and PE films by ozonation and wet gravity separation
PE high density 38.9 33.9 5.1 32.1 6.9
PP 36.3 36.3 0.0 36.3 0.0
method. During the period of study, it was found that there was
PVC/PVDC 1.3 1.3 0.0 0.0 1.3 an increase in hydrophilicity and decrease in contact angle 16°
Other 2.5 1.3 1.2 0.5 2.0 from 78° to 62° of CP films. Ozonation method was also applied
for separation of twisted films and found that it was easily settled
down after 2 min mixing time. The sequential application of ozon-
hydrophilic functional groups like carbonyl groups (Kurose et al., ation after wet gravity separation of light PPW films sourced from
2008). large scale recycling plant was evaluated. Even though, in large
Fig. 5 describes the effect of twisted area on floating behavior of scale recycling plant the fraction of PPW films contain 1.3% of CP
an artificial PVDC film with and without ozonation process. The films. This occurred when a combination of ozonation and wet
twisted area was estimated visually during the period of study. gravity separation with 2 min-mixing was performed. The combi-
The ozonation was conducted for 10 min and observed that, the nation of ozonation and wet gravity separation methods would
large part of PVDC films were floating on the surface even though be useful to recover the PP and PE films with high purity from
the PVDC films have been twisted from 0% to 25% area. The reason PPW films.
behind this is that there was an entrapment of air on the surface of
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