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Waste Management 32 (2012) 826832

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

Pyrolysis of plastic packaging waste: A comparison of plastic residuals


from material recovery facilities with simulated plastic waste
A. Adrados , I. de Marco, B.M. Caballero, A. Lpez, M.F. Laresgoiti, A. Torres
Chemical and Environmental Engineering Department, School of Engineering of Bilbao, Alameda Urquijo s/n, 48013 Bilbao, Spain

a r t i c l e

i n f o

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

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A. Adrados et al. / Waste Management 32 (2012) 826832

of them have been conducted using individual plastics or plastic


mixtures, which likely respond differently than real waste plastics
to pyrolysis. In this paper, a sample of real waste plastics is studied
and its pyrolysis behavior is compared with that of a plastic
mixture.

Table 1
Composition of the real sample (wt%) coming from a material recovery facility.

2. Experimental research and design


2.1. Origin and characteristics of samples
The real sample used for the experiments was provided by BZB, a
material recovery facility located in Bizkaia (Spain). This plant
performs all separation and classication of packing and packaging
waste from Bizkaia. The waste is separated into groups based on
material type (e.g., steel cans, tetra-brik, aluminum cans, and different plastics). Autosorters, optical readers that identify materials as
they pass on conveyor belts and separate them using air currents,
are particularly important in this process. These machines, along
with other ballistic and magnetic separators, can make the process
of separation and classication very efcient; however, it is not
possible to accurately separate 100% of the material in the waste
stream. There always remains a rejected portion, which amounts
to 2030% and is composed of several different materials (e.g., PE,
PP, PS, PVC, PET, ABS, tetra-brik, aluminum, and lm). As noted
earlier, this portion is typically composed of several materials,
tightly intermingled, so its separation is not technically or economically feasible. Typically, this rejected material ends up being
incinerated or put in a landll.
A 25 kg sample was taken from the material recovery facility.
Then, representative samples of 6 kg were selected from it, dividing
the sample into four parts, and the composition of a representative
6 kg sample was analyzed. Manual separation of components was
completed using visual identication, infrared spectroscopy and
simple identication tests, such as fume characteristics and the
observation of ame color.
A quantitative analysis of the composition of the real sample is
presented in Table 1. The components of this sample have been
classied into three groups. The group called packaging plastics,
the largest group (60 wt%), is mainly composed of PE and PP, together with PS, PET and PVC. Other packaging materials are nonplastic materials that are also used in the packaging industry; this
group includes metals (e.g., iron and aluminum) and complex
packaging materials, consisting of more than one material. The
third group, called inappropriate materials includes those materials that should not have been placed in the municipal container
where plastic and metallic packing and packaging materials were
collected. Inappropriate materials primarily consist of paper, glass,
clothing waste, wood waste and other types of plastic waste.
To better understand the thermochemical phenomena that take
place during the pyrolysis of plastic waste, a simulated homogeneous, invariable and predened sample with a known composition was also tested. This sample was created with a mixture of
the plastics that are usually present in municipal wastes. Various
actual plastic waste samples were taken into account for establishing the composition of the simulated sample (De Marco et al.,
2009; Lpez et al., 2010; Miskolczi et al., 2004; Kaminsky and
Nuez, 2007; Carvalho et al., 2009).
The composition of the simulated sample is presented in Table 2
together with the composition of the sample from the actual waste
stream, taking into account only the ve most important plastics of
those included in the plastic packaging waste portion. As shown in
Table 2, the proportion of plastics found in the simulated sample is
quite similar to those of the real waste sample used in this study.
All the plastics contained in the simulated sample had a particle
size of 23 mm. Once the components of the real waste sample

Material

Real sample

Plastic packaging waste


Polyethylene (PE)
Polypropylene (PP)
Polystyrene (PS)
Expanded PS
Polyethylene terephthalate (PET)
Polyvinyl chloride (PVC)
PE lm
PP lm
Subtotal

18.77
21.94
8.36
3.02
3.23
0.79
2.14
1.73
59.98

Other packaging waste materials


Complex materials
Aluminum lm
Non-ferrous metal (Al)
Ferrous metal (Fe)
Subtotal

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

wt% with respect to just packaging plastics.

were identied and quantied, the entire 25 kg sample was ground


in a mill suitable for cutting plastic with a grid size of 8 mm, which
generates a particle size small enough (68 mm) to extract homogeneous samples for the pyrolysis experiments. Representative 100 g
samples were extracted for the experiment by dividing subsamples
into quarters.
Table 3
Moisture, ash, elemental composition (wt%) and HHV (MJ kg

) 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.

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A. Adrados et al. / Waste Management 32 (2012) 826832

Finely cryogenically ground samples (<1 mm) from simulated


and real samples were then characterized. These results are presented in Table 3. Both samples have relatively low moisture contents. The most signicant difference between the two samples is
the ash content, which is much higher in the real sample due to
the presence of more inorganic components, including metals
and inappropriate materials. Accordingly, the quantities of carbon
and hydrogen are proportionally much higher in the simulated
sample. The high heating value (HHV) is much lower in the real
sample due to the fact that it contains a higher proportion of inert
material than the simulated sample.
2.2. Catalyst

2.4. Analytical techniques

Catalytic cracking of plastic waste has been studied in recent


years in an attempt to encourage thermal cracking (Aguado et al.,
2006). The mechanism by which the plastic is decomposed in the
presence of catalysts depends on the type of catalyst used. Until
now, the more well-studied catalysts have been solid acids (especially zeolites) because their acidity favors cracking reactions
(White, 2006). However, zeolites are expensive and can inuence
the economic viability of the process. Thus, it is of interest to study
alternative catalysts such as byproducts of industrial processes like
Red Mud. This byproduct has been used as hydrogenating catalyst
for the liquefaction of various materials (e.g., biomass, coal, and
anthracene) (De Marco et al., 2009; Legarreta et al., 1994, 1997;
Eamsiri et al., 1992; Klopties et al., 1990; Llano et al., 1994), and
also tested as a catalyst for PVC pyrolysis (Yanik et al., 2001, 2006).
Red mud, which is a byproduct of the Bayer process for alumina
production from bauxite, has been evaluated as a pyrolysis catalyst
with the simulated sample in this paper. This catalyst was used in
liquid phase, contact mixed with the plastic waste in a proportion
of 10 wt%. The composition of the red mud used in the experiment
is presented in Table 4. The catalyst particle size was 5100 lm,
and its BET surface area was 27.49 m2 g 1. Shusil and Batra
(2008) have reported that the specic BET surface area of red
mud is generally in the range of 2030 m2 g 1, which is in agreement with the results obtained in this study.
2.3. Pyrolysis experiments
In a typical experimental run, a 100 g sample, particulated to a
size of 68 mm, was placed into a stainless steel unstirred 3.5 dm3
reactor. The pyrolysis experiments were carried out in a N2 atmosphere that was created by passing N2 gas through the reactor area
at a rate of 1 dm3 min 1. The system was heated at a rate of
20 C min 1 to 500 C, and then this temperature was maintained
for 30 min. Previous studies (De Marco et al., 2007, 2008, 2009;
Laresgoiti et al., 2004) of other polymer wastes (e.g., SMC of polyester and berglass, used tires, and shredded residue from cars)
have indicated that 500 C is the optimum temperature for the
treatment of polymeric waste by pyrolysis because at lower temperatures, complete decomposition of organic matter is not
achieved, and at higher temperatures, there is an increase in the
gas yield at the expense of the liquid yield. These studies also
showed that no more pyrolysis products evolve from the autoclave
after 30 min (De Marco et al., 1995; Legarreta et al., 1995).
The vapors generated during the experiment were swept out of
the reactor by the nitrogen to a series of gasliquid separators,
Table 4
Composition of red mud used in experiments (wt%) (dried basis).

where they were condensed at room temperature and collected


as liquid. The non-condensed gases passed through an activated
carbon column and were collected in Tedlar plastic bags to be
tested by gas chromatography with FID and TCD detectors.
The solids (products remaining in the reactor) and liquids obtained were weighed. The yields were calculated as a weight percentage with respect to the raw material pyrolyzed. The gas
yields were calculated by difference. Each result presented in this
paper is the mean value of the data obtained in at least two equivalent experiments, which did not vary by more than three percentage points for any of the measured values.

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.

3. Results and discussion


3.1. Pyrolysis yields
The mean values of liquid, gas and solid yields obtained in the
experimental runs utilized in each sample (and which did not vary
more than three percentage points) are presented in Table 5. The
liquid and gas yields are higher in the simulated sample, while
the solid yield is higher in the real sample due to its high content
of inorganic components.
In the case of the simulated sample with red mud, the liquid
yield decreased and the gas yield increased relative to the non-catalytic run. This result is likely due to a cracking effect caused by the
red mud, which has also been observed by authors of similar studies (Yanik et al., 2001; De Marco et al., 2009).
There was some char formation, both in the simulated sample
(0.60.8 wt%) experiment and in the real sample (5.3 wt%) experiment. Other authors (De Marco et al., 1995; Legarreta et al., 1995)
and research groups (Williams and Williams, 1997; Sakata et al.,
2004) have also observed char formation as a result of pyrolyzing
polymeric materials. In one study (Van Krevelen and Te Nijenhuis,
2009) analyzing the thermal decomposition of polymers, it was concluded that char is formed in the decomposition of certain polymers,
and the tendency to form char depends on the chemical structure of
the polymer. That tendency increases when the polymer contains
groups capable of reacting with hydrogen atoms of the polymeric
structure, such as OH and @O. These types of functional groups
are typical in paper, wood and gardening, ABS and PC. All these
materials sum to 11.29 wt% in the real sample, which explains its
high char formation relative to the simulated sample. The tendency
of cellulosic materials (e.g., paper and wood) to form char has been
conrmed by another experiment in which another real waste sample, mainly composed of cellulosic materials (85.93 wt% of
paper + wood + gardening waste), was pyrolyzed and yielded
23.1 wt% char. Similarly, in a previously published paper (Lpez

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A. Adrados et al. / Waste Management 32 (2012) 826832


Table 5
Pyrolysis yields (wt%).
Fraction

Real sample

Simulated sample

Simulated sample + red mud

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

>70% polyolens. This circumstance is due to the dehydrogenation


that occurs as a result of pyrolysis and cyclization reactions. The
formation of aromatics from the pyrolysis of plastic has been reported by many other authors (Buekens and Huang, 1998; Kaminsky and Kim, 1999; Kaminsky and Nuez, 2007; Lee, 2006; Angyal
et al., 2007; Williams and Williams, 1997; Pinto et al., 1999).
The relative amounts of aromatics found in the real sample and
in the simulated sample with red mud were signicantly higher
than that of the simulated sample alone. Red mud seems to have
a catalytic effect that promotes aromatization reactions and, in
the case of the real waste sample, the high level of aromatization
may be attributed to a catalytic effect from the metals and glasses
contained in it. As previously mentioned, red mud and inorganic
materials in the real waste sample promote cracking and cause free
radicals to be produced more rapidly. These free radicals can either
cycle or capture H+ from other molecules to stabilize themselves,
and both cyclization and dehydrogenation reactions lead to the
formation of aromatics. In a previous test carried out by the
authors with a real waste sample that did not contain glass or metal (Lpez et al., 2010), the content of aromatics (74.9 wt%) was
much lower than that of other real samples that did contain aromatics (9396 wt%). This corroborates the idea that metals and/
or glasses in real samples exert some type of catalytic effect.
The main components of the liquids obtained by pyrolysis,
identied by GCMS, are presented in Table 7. Only those compounds with a percentage-quantied area greater than 3% have
been included in the table. The names of the compounds correspond to the tentative assignments provided by the MS search engine and have been compared with bibliographic data and
chemical analytical standards.
Table 7 shows that in every case, styrene is the most abundant
component. The next most common components found are toluene
and ethyl-benzene. These results were also observed from four
other real waste samples tested by other authors (Lpez et al.,
2010): styrene was the most abundant component obtained in
the liquid products followed by toluene and ethyl-benzene. The
possibility of obtaining valuable aromatic hydrocarbons, such as
the three mentioned above, from plastic waste, makes pyrolysis
more attractive, even though it is known that the achievement of
an efcient extraction of such chemicals is not easy.
The liquids from the real waste sample and the simulated sample with red mud have a lower quantity of 2,4-dimethyl-1-heptene
than those from the non-catalytic (simulated) sample. This is an
expected result because this is an aliphatic compound and the real
waste samples yield highly aromatic (8993 wt%) liquids. On the
other hand, the real waste samples also contain more ethyl benzene and less styrene than the simulated sample without a catalyst. It seems that the hydrogenation reaction presented in Fig. 1
is favored in the case of the real sample and the simulated sample
with red mud. The content in toluene is also higher because this
compound has a lower carbon number than the others. This indicates once again that greater amounts of cracking occur in the simulated sample with red mud than in the one without a catalyst.
The liquids from the real waste sample have more naphthalene
and methyl naphthalene in them than those of the non-catalytic
(simulated) sample, which is in accordance with their more aromatic nature because both compounds are condensed aromatics.

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A. Adrados et al. / Waste Management 32 (2012) 826832

Table 7
GCMS analysis of pyrolysis liquids (compounds with more than 3% area).
Major compounds

Molecular formula

Real sample

Simulated sample

Simulated sample + red mud

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.

The effect of red mud on the waste material can be summarized


as follows: it produces less >C13, more C5C9 and more aromatics
than waste materials without a catalyst. Also, more toluene, ethyl
benzene and naphthalene, and less dimethyl heptane and styrene
than without catalyst, is obtained. Therefore, the following effects
of red mud on pyrolyzed waste streams can be noted:
 Greater cracking: This is attributable to the alumina (Al2O3),
which is known to have cracking effect.
 Greater aromatization.
 Modication of equilibrium constants for hydrogenation, such
as styrene to ethyl benzene. This might have been expected
because red mud has been traditionally used as a catalyst in
coal and biomass hydrogenation processes (Legarreta et al.,
1994, 1997; Eamsiri et al., 1992; Klopties et al., 1990).
As has been discussed throughout this section, the liquids obtained from the simulated sample with red mud are paradoxically
very similar to those obtained from the real waste sample. The conclusion drawn from this observation is that inorganic ingredients
(e.g., metals, glasses) in a real waste sample can have a catalytic effect analogous to that of red mud.
Table 8 shows the elemental composition of the pyrolysis liquids.
It can be observed that there are important differences between the
results obtained with the real waste sample and the simulated one,
either with or without red mud. The liquids obtained from the real
waste sample have a relatively low carbon content and a high percentage of others. The others portion likely consists primarily
of oxygen from oxygenated organic compounds that were identied
by GCMS analysis but have not been included in Table 7 because
they were less than 3% of the sample or were from an aqueous phase,
which was derived from the cellulosic materials of the real waste
sample and mixed with the organic phase. The oxygenated organic
compounds are likely derived from the cellulosic materials contained in the real waste sample (e.g., paper, wood waste and gardening waste) and from oxygenated polymers, such as PMMA, PUR, PA
and PC. The authors have tested other real waste samples with high
paper, wood waste and gardening waste content and have also obtained both oxygenated organic liquids and aqueous liquid phase.
When the sample with 85.93 wt% of cellulosic materials was pyrolyzed, an aqueous phase level of 30.1 wt% was obtained, and when
a sample with 33.77 wt% cellulosic materials was tested (Lpez
et al., 2010), an aqueous phase level of 12.4 wt% was obtained. Several other authors (Demirbas, 2007; Luik et al., 2007; Xi-Feng et al.,
2009) have also reported that water is formed to a signicant extent
in the pyrolysis of cellulose-rich samples.
Notably, the three liquids obtained from pyrolysis have a considerably high HHV, which indicates great value as alternative fuels to

) of pyrolysis liquids.

Parameter

Real sample

Simulated sample

Simulated sample + red mud

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

n.d. = not detected.


a
Determined by difference.

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

A. Adrados et al. / Waste Management 32 (2012) 826832


Table 9
GC-TCD/FID analysis (%v/v) and HHV (MJ kg

) 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 the composition of pyrolysis solids. In the case of the simulated


sample with red mud, the pyrolysis solids could be used again as
a catalyst in the pyrolysis process. In the case of the real waste sample, metals could be recovered for recycling, and char could be used
for the applications previously mentioned (e.g., solid fuel and pigments); the remaining materials, mainly ceramics and glass, would
be an inert waste that most likely would be placed in a landll.
4. Conclusions

) 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

n.d. = not detected.


a
Determined by difference.

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

Pyrolysis is an attractive option for recycling the residue from


the separation and classication of packaging waste at material
recovery facilities. These non-recyclable residues yield high conversions to liquids and gases in the pyrolysis process. The pyrolysis
liquids have high HHV levels so that they can be used as an alternative to fossil fuels. They contain signicant amounts of styrene,
toluene and ethyl-benzene; therefore, they are also of great interest as a source of chemicals. The pyrolysis gases also have high
HHV levels, so they can supply the energetic demand of the processing and the surplus may be used for additional power generation. The solid product of pyrolysis is composed of inorganics (e.g.,
metals and glasses) that are contained in the raw material and of
char formed during the process. Metals can be recovered for recycling processes, and char may nd applications such as solid fuels,
pigments, activated carbon and low-quality carbon black.
Red mud, which is an industrial byproduct, performs a catalytic
function in the pyrolysis of plastic waste. It promotes cracking and
aromatization reactions yielding more gases and lighter, more aromatic and more uid (not waxy) liquids. It also modies the composition of the liquids, favoring the formation of toluene and ethylbenzene at the expense of styrene.
Real plastic waste from the residue of a material recovery facility responds differently to pyrolysis than simulated samples, composed of just a few pure plastics. Real industrial waste gives rise to
higher solid yields as a result of pyrolysis due to the greater
amounts of inorganics that, in such samples, cannot be converted
to gases or liquids. The real plastic waste yields a higher gas/liquid
ratio and lighter, more aromatic and less viscous liquids that may
be attributed to some type of catalytic effect of the metals and
glass from the real sample. Real plastic waste yields liquids that
have a higher content of oxygenated organic compounds and that
contain an aqueous phase. These qualities are both due to the presence of cellulosic materials and oxygenated polymers in the real
waste sample. The gases generated from the pyrolysis of the real
waste sample have lower HHV levels due to their higher CO2 content, which stems from the cellulosic materials of the real sample.
Acknowledgments
The authors thank the Spanish Ministry of Education and Science (MEC) (CTQ 2007-67070/PPQ) as well as the Basque Country
Government (ETORTEK 2007 IE07-207, GIC 07-09-IT-354-07 and
the Researchers formation program 2008, 2009, 2010) for nancial assistance for this work.
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