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a r t i c l e
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Article history:
Received 20 December 2010
Accepted 29 June 2011
Available online 26 July 2011
Keywords:
Pyrolysis
Feedstock recycling
Catalytic decomposition
Plastic waste
Red mud
a b s t r a c t
Pyrolysis may be an alternative for the reclamation of rejected streams of waste from sorting plants
where packing and packaging plastic waste is separated and classied. These rejected streams consist
of many different materials (e.g., polyethylene (PE), polypropylene (PP), polystyrene (PS), polyvinyl chloride (PVC), polyethylene terephthalate (PET), acrylonitrile butadiene styrene (ABS), aluminum, tetra-brik,
and lm) for which an attempt at complete separation is not technically possible or economically viable,
and they are typically sent to landlls or incinerators. For this study, a simulated plastic mixture and a
real waste sample from a sorting plant were pyrolyzed using a non-stirred semi-batch reactor. Red
mud, a byproduct of the aluminum industry, was used as a catalyst. Despite the fact that the samples
had a similar volume of material, there were noteworthy differences in the pyrolysis yields. The real
waste sample resulted, after pyrolysis, in higher gas and solid yields and consequently produced less
liquid. There were also signicant differences noted in the compositions of the compared pyrolysis
products.
2011 Elsevier Ltd. All rights reserved.
1. Introduction
In the last few decades, plastic consumption has increased.
Annual consumption of plastics in Occidental Europe is about 60
million tons, which results in about 23 million tons of plastics
waste. Approximately 63 wt% of this waste comes from packing
and packaging (Cimadevila, 2008). The EU Packing and Packaging
Waste Directive (2004/12/CE) had the objective to reclaim or incinerate (using energy recovery) at least 60 wt% of packaging waste
and to recycle between 55 wt% and 85 wt% of it.
In some European countries these objectives have been achieved.
Plastics are used for packing and packaging, but they are recycled at
one of the lowest rates for recycled materials (just 29% in Spain), and
it is getting more and more difcult to increase this rate because
remaining waste streams are increasingly complex and quite difcult to separate. One of these streams is the residue from material
recovery facilities, where the municipal packing and packaging plastic waste are separated to be individually recycled.
Material recovery facilities separate and classify packaging waste
from recycling bins and the various materials (e.g., steel cans, tetrabrick, aluminum cans, and plastics) are then sent to recycling companies. The portion that is rejected material varies depending on
the efciency of the separation plant, but in any case this portion
is composed of many different materials (e.g., polyethylene (PE),
Corresponding author. Tel.: +34 946017297; fax: +34 946014179.
E-mail address: aitziber_adrados@ehu.es (A. Adrados).
0956-053X/$ - see front matter 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.wasman.2011.06.016
polypropylene (PP), polystyrene (PS), polyvinyl chloride (PVC), polyethylene terephthalate (PET), acrylonitrile butadiene styrene (ABS),
aluminum, and lm) that are intermingled. It is not technically or
economically advantageous to fully separate this waste; therefore,
it is incinerated or placed in a landll.
The general objective of this paper is to study the suitability of
the pyrolysis process for the thermal treatment of plastic residue
from a material recovery facility located in Spain. The plastic residue from the material recovery facility is 2030 wt% of the entire
waste stream.
Pyrolysis processing involves heating the material to moderate
temperatures (400700 C) in the absence of oxygen. The organic
components of the material are then decomposed, generating
liquid (oil) and gaseous products, which can be useful as fuels and/
or sources of chemicals. The inorganic ingredients (e.g., glass and
metals) remain practically unaltered and free of binding organic
matter and therefore can be reused for certain applications (additive
or llers for other plastics) or, as a last resort, it would result in a
much lower volume of waste to be placed in a landll. Pyrolysis is
especially appropriate for products or waste streams that contain
waste plastics, organic waste and inorganic solid waste materials,
as exemplied by the waste stream analyzed in this study.
Several studies have reported on the suitability of pyrolysis as a
thermochemical recycling technique for plastics (Faravelli et al.,
2001; Williams and Williams, 1999; Kaminsky et al., 1997, 2004;
Kaminsky and Kim, 1999; Angyal et al., 2007; Demirbas, 2004;
Kiran et al., 2000; Sakata et al., 2003; Lee, 2007); however, most
827
Table 1
Composition of the real sample (wt%) coming from a material recovery facility.
Material
Real sample
18.77
21.94
8.36
3.02
3.23
0.79
2.14
1.73
59.98
0.22
2.50
1.35
1.27
5.34
Inappropriate materials
Acrylonitrile butadiene styrene (ABS)
Polymethyl methacrylate (PMMA)
Polyurethane (PUR)
Polyamide (PA)
Polycarbonate (PC) (compact disk)
Elastomer
Latex
Medical waste
Paper
Clothing waste
Gardening waste
Wood waste
Glass
Inert
Subtotal
2.39
0.55
0.18
0.25
0.83
2.42
0.97
0.98
4.19
0.08
0.56
3.32
16.18
1.78
34.68
Total
100
Table 2
Composition of plastics according to real and simulated
samples (wt%).
Material
Real samplea
Simulated sample
PE
PP
PS
PET
PVC
35
40
19
5
1
40
35
18
4
3
) of pyrolyzed samples.
Sample
Real sample
Simulated sample
Moisture
Ash
C
H
N
S
Cl
Othersa
H/C rate
HHV
1.0
28.2
58.7
8.7
0.5
<0.1
1.0
1.8
1.8
30.6
0.1
0.0
84.7
12.5
<0.1
0.0
1.1
1.5
1.8
43.9
Determined by difference.
828
Al2O3
TiO2
SiO2
CaO
Fe2O3
Na2O
Othersa
23.8
13.5
8.5
5.3
36.5
1.8
10.6
Determined by difference.
Both the raw materials and the liquid and solid products of
pyrolysis were thoroughly characterized using the following analytical techniques. The moisture and ash contents were determined
by thermogravimetric analysis according to D3173-85 and D317482 ASTM standards, respectively, and the elemental composition
was measured by automatic CHN and S analyzers. The Environmental Protection Agencys (EPA) Method 5050 was used to determine Cl. The HHV was determined using an automatic calorimetric
bomb. Pyrolysis liquids were also analyzed by gas chromatography
coupled with a mass spectrometry detector (GCMS).
The pyrolysis gases were analyzed by a gas chromatograph coupled with thermal conductivity and ame ionization detectors (GC
TCD, FID). The HHV of gases was theoretically calculated according
to their composition.
829
Real sample
Simulated sample
Liquids
Gases
Solids (inorganic + char)
Ratio liquid/gas
40.9
25.6
28.2 + 5.3
1.6
65.2
34.0
0 + 0.8
1.9
57.0
42.4
0 + 0.6
1.3
et al., 2010), it was noted that a real waste sample with 33.77 wt% of
cellulosic materials yielded 11.7 wt% of char.
If solid yields are not considered, the liquid/gas ratio is lower in
the real waste sample and in the simulated sample with red mud
than in the simulated sample alone. This may be attributed to
the catalytic effect of red mud in the case of the simulated sample
and to the presence of glass and metals in the real waste sample,
which probably play a catalytic role in the pyrolysis process.
3.2. Pyrolysis liquids
A summary of results obtained in the GCMS characterization of
liquids is presented in Table 6. All the compounds identied by
GCMS, including those with % area <1%, have been grouped in
three categories according to their number of carbons: C5C9,
C10C13 and >C13; total aromatics have also been quantied. Table 6 shows that the content of heavy compounds (>C13) was higher in the simulated sample than in the real one, while the content
of the lightest compounds C5C9 was lower in the simulated sample than in the real one. The simulated sample liquids were highly
viscous (semi-solid at room temperature) while the real sample
liquids were much less viscous due to their lower molecular
weight. This may be attributed to the cracking caused by inorganics in the real waste sample. This idea is corroborated by the results
found in another study (Lpez et al., 2010), which was performed
with a real waste sample that did not contain inorganic materials.
This study yielded a higher quantity of >C13 and a lower quantity
of C5C9 than other real waste samples that did contain inorganic
materials. This observation indicates that, from the real waste sample, there was more cracking observed for the pyrolyzed products
than for those from the simulated sample. This result was in agreement with the results of this study, as observed by examining the
texture of the liquids after pyrolysis (semi-solid from the simulated sample and a uid liquid from the real waste sample).
The aromatic content was surprisingly high in all cases (>70%)
in spite of the fact that the starting material was composed of
Table 6
Fractions of interest in pyrolysis liquids (% area determined by GCMS).
Fractions
Real
sample
Simulated
sample
Simulated
sample + red mud
C5C9
Aromatics
No aromatics
Total
80.7
1.2
81.9
69.2
10.4
79.6
80.3
3.6
83.9
C10C13
Aromatics
No aromatics
Total
10.6
3.3
13.9
3.1
6.3
9.4
8.0
4.3
12.3
>C13
Aromatics
No aromatics
Total
2.0
2.1
4.1
1.7
5.6
7.3
1.3
1.6
2.9
93.4
6.6
0.0
73.9
22.4
3.7
89.6
9.6
0.9
Total aromatics
Total no aromatics
Non-identied
830
Table 7
GCMS analysis of pyrolysis liquids (compounds with more than 3% area).
Major compounds
Molecular formula
Real sample
Simulated sample
Toluene
2,4-Dimethyl-1-heptene
Ethyl benzene
Xylene
Styrene
a-Methyl styrene
Naphthalene
Methyl naphthalene
C7H8
C9H18
C8H10
C8H10
C8H8
C9H10
C10H8
C11H10
14.9
1.2
16.4
4.1
33.5
7.0
3.1
1.2
8.1
5.9
5.0
1.5
48.4
4.2
0.8
14.2
2.1
9.0
4.2
42.3
4.9
2.9
1.4
81.4
73.9
81.0
Total
Table 8
Elemental composition (wt%) and HHV (MJ kg
Fig. 1. Hydrogenation reaction of styrene.
) of pyrolysis liquids.
Parameter
Real sample
Simulated sample
C
H
N
Cl
Othersa
H/C ratio
HHV
77.3
9.5
0.3
0.2
12.7
1.5
36.6
88.7
9.2
n.d.
0.5
1.5
1.2
43.3
87.5
10.5
n.d.
1.1
0.9
1.4
40.9
the increasingly scarce fossil fuels, with the advantage that because
they come from packaging waste they would not only be a renewable fuel source, but would also solve an environmental problem.
However, it must be mentioned that these liquids unfortunately
contain a certain amount of chlorine derived from the PVC of the
original samples. The higher the PVC content in the original sample
is, the greater the content of chlorine in pyrolysis liquids is. The presence of chlorine in these liquids is a serious problem both for their
immediate application as a fuel and for their admission in reneries
for processing. The problem of chlorine may be reduced by stepwise
pyrolysis, as has been demonstrated by the authors in a previous
paper (Lpez et al., 2011), which showed that the chlorine content
of these pyrolysis-generated liquids can be reduced more than
50 wt% by performing a low-temperature (300 C) dehydrochlorination step before pyrolysis.
3.3. Pyrolysis gases
The composition of the pyrolysis gases is presented in Table 9. It
can be seen that in all cases they are composed of hydrocarbons
(C1C6) together with small quantities of CO, CO2 and H2. Due to
the difculty of discriminating among isomers from C3 to C6, such
discrimination has not been made. The HHV is very high, similar to
that of natural gas (44 MJ kg 1). This gas could potentially provide
for the energy requirements of the processing plant with a surplus
that could be protable.
The real waste sample generated greater quantities of CO and
CO2 than the simulated sample, which is probably due to its
remarkably high content of oxygen-containing materials such as
paper, wood, PA, PC, PUR and PMMA. The formation of CO2 from
pyrolysis of cellulose-based materials has also been reported by
other authors (Fontana et al., 2000; Ahmed and Gupta, 2009; Couhert et al., 2009). Li et al. (2001) and Banyasz et al. (2001) investigated gas evolution and the mechanism of cellulose pyrolysis in a
two heating zone pyrolysis system. The two heating zone experiments indicated that a large proportion of CO was formed from
the decomposition of primary volatile products (aldehydes) during
secondary reactions, while CO2 was formed at the early stages of
cellulose pyrolysis during the primary reactions. Due to the high
content of CO2, the gas produced from the real waste sample had
) of pyrolysis gases.
Compound
Real
sample
Simulated
sample
Simulated sample +
red mud
H2
CO
CO2
Methane
Ethane
Ethene
C3
C4
C5
C6
HHV
8.2
8.3
15.0
13.2
8.5
18.8
17.3
10.3
0.4
0.0
37.2
6.9
0.9
2.2
17.4
11.1
14.6
23.0
12.2
5.4
6.3
48.6
10.8
1.2
4.8
24.9
11.7
17.5
18.0
8.4
2.2
0.3
47.1
Table 10
Moisture, elemental composition in wet basis (wt%) and HHV (MJ kg
solids.
831
) of pyrolysis
Parameter
Real
sample
Simulated
sample
Simulated sample +
red mud
Moisture
C
H
N
Cl
Ash + othersa
H/C ratio
HHV
2.3
29.3
1.2
1.1
4.7
61.4
0.5
11.5
0.2
93.7
3.5
n.d.
0.3
2.3
0.4
38.2
0.9
13.9
0.7
n.d.
3.7
80.8
0.6
6.7
a lower HHV than did the gases from the simulated samples. Other
cellulose-rich samples that were pyrolyzed by the authors also
yielded high levels of CO and CO2: 72.0 wt% (CO + CO2) in the gases
from the sample that contained 88.93 wt% of cellulosic materials
and 44.7 wt% in the gases from the sample that contained
33.77 wt% of cellulosic materials (Lpez et al., 2010).
Both the real waste sample and the simulated sample with red
mud yielded gases with a lower proportion of heavy hydrocarbons
(C4C6) and a higher proportion of light hydrocarbons (C1, C2)
than the simulated sample without a catalyst. This is attributable,
as previously mentioned, to the stronger cracking effect caused by
the red mud in one case and to the catalytic effect of the inorganic
materials in the other case.
The proportions of hydrogen were also somewhat higher from
the real waste sample and the simulated sample with red mud
than they were with the simulated sample without a catalyst. This
may be a result of the aromatization reactions, which are often
accompanied by an increase in the generation of hydrogen.
3.4. Pyrolysis solids
The characteristics of the solids produced from pyrolysis are presented in Table 10. In the case of the simulated sample, which did not
contain inorganic materials, the solid had a very high carbon content
(>90%), which indicates that it is char or a carbonized product
formed during the pyrolysis process. Its HHV is very high so it may
have potential application opportunities as a solid fuel. For example,
other possible applications are pigments, asphalt components, and
activated carbons.
Regarding the solid resulting from the real waste sample and the
simulated sample with red mud, the ash content was very high in
both cases (61.4% and 80.8%, respectively) due to the fact that the
inorganic ingredients (metals and ceramics in the real waste sample, and red mud itself) in the experiment with the catalyst are part
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