CHARACTERIZATION OF PLASTIC MATERIALS PRESENT IN

MUNICIPAL SOLID WASTE: PRELIMINARY STUDY FOR THEIR

MECHANICAL RECYCLING
Mónica Calero 1, María Ángeles Martín-Lara 1, Verónica Godoy 1,*, Lucía Quesada 1,
David Martínez 2, Francisco Peula 2 and José Manuel Soto 2
1
Department of Chemical Engineering, University of Granada, Avenida Fuentenueva s/n, 18071, Spain
2
INGESIA Ingeniería y Medio Ambiente S.L., C/Parque de las Ciencias, 1, 18014, Granada, Spain

Article Info: ABSTRACT

Received: In the EU, 25.8 million tons of plastic wastes are generated each year and more than
6 June 2018
Revised:
30% end up in landfills. In Spain, this percentage rises up to 50%. Mechanical recy-
31 August 2018 cling is currently one of the best alternatives to reduce problems associated with
Accepted: poor management of plastic waste. In this paper, an analytical laboratory study of
12 November 2018 several samples of municipal plastic waste from Granada (Spain) was presented.
Available online:
The samples were supplied by the Waste Treatment Plant (Ecocentral). The study
21 November 2018
was based on the measurement of the moisture and dirt content of the selected
Keywords: plastic waste. Those parameters were determined by washing and drying the waste
Characterization and analyzing the washing wastewater; in order to determine/justify the need of a
Dirt
Moisture washing step and a post-treatment of the washing water. The results showed that
Plastic waste the differences in moisture and dirt content were significant between the different
Polymer types of polymers, which could influence in the economic profitability of mechan-
Recycling ical recycling. Polystyrene (PS) is the material that loosed the most weight while
polypropylene (PP) loosed least weight. Moreover, the washing wastewater shows
parameters that comply with the discharge regulations of Granada (Spain), except
for the case of polyethylene film, whose wastewater would require pre-treatment pri-
or to discharge. Overall, the results were satisfactory, as they show that most of the
ordinary plastic waste can be recycled without high cost.

1. INTRODUCTION et al., 2016). It is estimated that 80% of the waste present

in seas are plastics which come from land (Rojo-Nieto and
Since the Second World War, plastic has been estab- Montoto, 2017). The problem is that it takes between 100
lished as one of the essential materials in many areas of and 1000 years to degrade plastics, so they suppose a real
everyday life, gaining strength in sectors such as auto- threat for sea flora and fauna.
motive industry, clothing and decoration. From the 1960s In 2015, 322 million tons of plastic were produced
to the present day, the demand for plastic products has worldwide. Europe is the second largest producer behind
grown continously. The annual production of plastic has China. Its production reached 58 million tons that same
increased twenty-fold in the last fifty years. Among the year. Of this amount, 25.8 million tons were introduced
most commonly used polymers today, different typologies annually into the municipal waste stream, which supposed
can be cited (Table 1). a 12.4% of the total municipal solid waste (MSW). A 30.8%
One of the major environmental problems is the large of this plastic waste was deposited in landfills, 39.5% was
amount of plastic waste generated. Both, the production of utilized for energy recovery and 29.5% was recycled (Plas-
this material and the incorrect waste management cause ticsEurope, 2016). In Spain the situation is even worse
several environmental problems. One of those problems than in the EU. In fact, the amount of plastic waste that
is the amount of oil needed to manufacture virgin poly- ends up in landfills is over 50% in Spain (PlasticsEurope,
mers (up to 6% of world oil production). Other problems 2015).
are greenhouse gas emissions during manufacture (more The statistics show that the production of plastics and
than 1% of the world total), low recycling rates of waste the plastic waste recycling do not grow in the same way.
and dumping of this waste at sea (World Economic Forum Increasing the percentages of mechanical recycling would be

* Corresponding author: Detritus / Volume 04 - 2018 / pages 104-112

Verónica Godoy https://doi.org/10.31025/2611-4135/2018.13732
email: [email protected] © 2018 Cisa Publisher. Open access article under CC BY-NC-ND license
TABLE 1: Most commonly used polymers.
Society of the
Plastics Industry Polymer Applications
(SPI) Code

Polyethylene terephtalate Food packaging, carbonated soft drink bottles, water bottles, oil bottles, etc.

High density polyethylene Bags, detergent bottles, dairy bottles, etc.

Polyvinyl chloride Pipes, cards, sanitary fittings, etc.

Low density polyethylene Bags, film, packaging, etc.

Polypropylene Food packaging, lids, reusable cups, etc.

Polystyrene Single-use plates and cutlery, yogurts, butter packaging, etc.

Other plastics Multiple applications

a good alternative for reducing the amount of oil used and selectively. Municipal solid waste in Granada is made up
greenhouse gas emissions, as well as reducing landfill waste. of different fractions (Figure 1), among which the organic
The aim of this study is the characterization of the matter (34.4%) stands out, while plastic represents 12.6%
various plastic materials existing in mixed municipal solid of the total. This information comes from periodical char-
waste and to assess the need of the washing/drying steps acterizations carried out in the plant.
and their potential impact as preliminary preparation steps Figure 2 shows the different fractions of the plastic
on the global recycling process line. waste.Among them, polyethylene film is the most import-
ant, representing approximately 43% of the total. Plastic
2. MATERIALS AND METHODS waste from all fractions except for rigid high-density-poly-
ethylene, HDPE (mainly bottles) and plastics belonging to
2.1 Materials the category “Others” were analysed in the laboratory. The
The raw material used in this study came from the category “Others” includes many multilayer plastics, fibres
municipal solid waste collected and treated at the Waste and other polymers which are not the focus of this study.
Treatment Plant (Ecocentral) in Granada (Spain), and At the Waste Treatment Plant of Granada, plastic waste
corresponded to the fraction that had not been collected is mechanically pre-treated to separate one type from

FIGURE 1: Composition of municipal solid waste in Granada FIGURE 2: Composition of plastic fraction present in municipal
(Spain). solid waste of Granada (Spain).

M. Calero et al. / DETRITUS / Volume 04 - 2018 / pages 104-112 105

another to facilitate the subsequent recycling and baling. order to separate and classify it. Several techniques were
The samples analysed in the laboratory came from the used for this purpose. At the municipal waste treatment
bunker corresponding to each type of plastic separated plant, the plastic waste obtained from the bunkers was
inside the plant (Figure 3). The plastic types analysed are: analyzed directly by Near Infrared Spectroscopy (NIR)
using a portable Panatec Thermo Scientific microPhazir
• Polyethylene (PE) film (mostly bags and packaging AG, with a wavelength range of 1600-2400 nm. The analy-
film); sis was performed on the materials while they were in the
• Polyethylene terephthalate (PET) packaging; waste stream, i.e. dirty and wet. This portable NIR spec-
• Polypropylene (PP) packaging; trometer gives a reference spectrum with a correlation
• Polyestirene (PS) and Expanded Polystyrene (EPS) coefficient that indicates the similarity between the two
packaging. spectra, appart from the measured spectrum.
Only the measurements with coefficients higher than
2.2 Methods
0.90 were considered. This value indicates that the mate-
The first step was the characterization of the plastic rial of the polymer can be considered to be the same as
waste in the Waste Treatment Plant of Granada (Spain). the reference material. However, this equipment does not
The plastic waste was then transferred to the laboratory, provide the numerical values of the absorption peaks. In
where a series of analyses were carried out in the following addition, moisture and dirt present in the material can lead
order (Figure 4): 1) measurement of moisture content, 2) to erroneous absorption peaks, which do not correspond
grinding, 3) washing and 4) measurement of dirt content. to the polymer.
In parallel, the wastewater from the washing of each type Thus, in the laboratory, this technique was complement-
of plastic material was analyzed, measuring the dissolved ed with Fourier Transform Infrared spectroscopy (FTIR),
solids content, the total solids content and the chemical once the materials were washed and dried, to avoid distur-
oxygen demand (COD). bances caused by moisture and dirt. In addition, this equip-
ment provides the values of the main absorption peaks,
2.2.1 Characterization of raw material in the treatment plant which allows comparing them with those in the literature
and in the laboratory (Bozaci et al., 2012; Rodríguez-Bruceta et al., 2014; Smith,
The purpose of this characterization was to determine 1999; Vahur et al., 2016; Zieba-Palus, 2017) and confirming
the type of polymer that make up the waste material in the type of polymer that compose the waste.

FIGURE 3: Scheme of mechanical pre-treatment carried out inside the Waste Treatment Plant of Granada (Spain).

106 M. Calero et al. / DETRITUS / Volume 04 - 2018 / pages 104-112

 FIGURE 4: Experimental sequence of the study.

The analysis was performed with a Perkin-Elmer FT-IR tonne for high-density polyethylene (HDPE), 43 kL/tonne
Spectrometer model Spectrum 65, which has a wavelength for polypropylene (PP), 66 kL/tonne for (PET) and 140 kL/
range of 4000-400 cm-1 and a resolution of 2 cm-1. tonne for polystyrene (PS).
In the laboratory, tests were also carried out using Dif- Washing was carried out using water from the urban
ferential Scanning Calorimetry (DSC) on the samples in network, which has a total dissolved solids (TSD) of 74.4
order to obtain the melting points of the different polymers mg/l.
that compose the plastic waste, a technique that is also With regard to temperature, the plastic was washed at
widely used to complement the previous ones. The analy- room temperature (23-25°C) and using hot water (60°C) fol-
sis was performed on Perkin-Elmer Thermobalance model lowing the recommendations given by other authors in the
STA 6000, in accordance with the standard ISO 11357- literature (Al-Sabagh et al.,, 2016; Awaja and Pavel, 2005;
3:2018. Kratofil et al., 2014; Luijsterburg, 2014; Rodríguez-Bruceta
et al., 2014) (Table 2).
2.2.2 Determination of moisture
2.2.4 Determination of dissolved solids, total solids and
Moisture content was determined according to stan-
COD in wastewater
dard UNE-EN ISO 18134-3:2016 using a drying oven at a
temperature of 105 ± 2 °C during 24 hours. After the washing, the wastewater was analyzed and
the following parameters were measured: dissolved solids,
2.2.3 Washing process total solids and chemical oxygen demand (COD). These
Three samples of each of the plastic materials parameters were measured because they are the ones that
described in section 2.1 were taken and washed. In order determine the quality of the wastewater before it is dis-
to determine the amount of water used in the washing charged into the network. The methodology used to deter-
process, several companies expert in the design of wash- mine each of these parameters is described below:
ing machines for the mechanical recycling of plastic were • Dissolved solids: They were determined gravimetrically
consulted. The minimum quantity acceptable for a correct by vacuum filtration, according to UNE 77031:2015, us-
washing is 1 L per 100 g of plastic. This quantity was com- ing a Filter-Lab 1240 filter, with a pore size of 14-18 µm.
plied for all the polymers except for EPS. A solid:liquid ratio The filtered water was then allowed to dry in a 105°C
of 1:40 was used for this material, because it is very bulky oven and the remaining solid residue was weighed. The
and it has a very low density, so it takes large amounts result is expressed in g/L.
of water to submerge it completely and wash it properly. • Total solids: They were determined by the difference in
The duration of each wash was 30 minutes. Similar to our weight between dirty plastic and clean plastic. The re-
methodology, different water quantities were reported for sult is expressed in g/L.
diverse polymers. For example, after performing a cradle- • COD: This parameter has been determined in accor-
to-gate life-cycle inventory (LCI) (EU data) for polymer recy- dance with ISO 6060:1989, using the dichromate meth-
cling from post-consumer sources, Hopewell et al., (2009) od. The chemical oxidizer was added to the waste-
found that the amount of consumed water was 32 kL/ water and boiled. It remained in this state for a time,
after which it was reduced through a reducing agent.
TABLE 2: Washing conditions. Finally, it was evaluated in order to measure the amount
of chemical oxidant consumed, expressed in mg/L of
Polymer Temperature Ratio (plastic:water)
equivalent oxygen.
PE film Room; 60°C 1:10

PET packaging Room; 60°C 1:10 2.2.5 Determination of dirt loss

PP packaging Room; 60°C 1:10 Dirt loss was determined considering the weight loss
PS packaging Room 1:10
of the plastic after the washing process. This parameter
corresponds to the total solids parameter, as both measure
EPS packaging Room 1:40
the same solid fraction, but expressed in different units.

M. Calero et al. / DETRITUS / Volume 04 - 2018 / pages 104-112 107

This is why the same values are presented in Table 3 for 6. In the case of PS and EPS, the temperature obtained in
dirt loss as in Tables 4 and 5 for total solids. the DSC is the glass transition temperature since they do
The loss of dirt is expressed in percentage. not have melting temperature because they are amorphous
polymers (Oliveira et al., 2013; Parres-García, 2005). This
3. RESULTS AND DISCUSSION value is usually around 100°C, which is in accordance to
the value obtained in the present investigation.
3.1 Identification of polymers existing in raw mate-
It should be noted that, within the PE, the DSC technique
rial
could be used to distinguish between HDPE and LDPE
The infrared spectra obtained by the NIR technique in whose melting temperatures are different. HDPE may have
the plant revealed that the majority of plastic materials melting temperatures between 120-130°C (Chianelli et al.,
analysed were composed of PE, PET, PP, PS, EPS and PA. 2013), but in most cases the values are closer to 130°C
This result coincides with the characterization presented or even higher, such as those obtained by some authors
in Figure 2, so it can be stated that the majority of plastic (Araújo et al., 2008; Shnawa et al., 2015) and in the DSCs
wastes contained in MSW are composed of PE, PET, PP, PS, presented in this article. On the other hand, the melting
EPS and PA (Figure 5). temperature of low-density polyethylene is usually between
However, due to the heterogeneity and characteristics 115-125°C (Batra, 2014), but it can fluctuate slightly above
of the sample in the field analysis with the NIR equipment, or below these values since other authors have obtained
in some cases FTIR technique in the laboratory was per- melting temperatures of 113°C or 127°C (Ashraf, 2014;
formed as well (Figure 6). The spectra obtained were com- Poley et al., 2004). These values are also in accordance
pared with spectra from the literature of pure polymers with those shown in Figure 6 for the LDPE.
(Bozaci et al., 2012; Rodríguez-Bruceta et al., 2014; Smith, All the results obtained by these three techniques
1999; Vahur et al., 2016; Zieba-Palus, 2017). It was found allowed to separate and quantify precisely the composition
that the absorption peaks coincided with those described of the fraction of plastic material contained in the MSW, as
for PE, PET, PP, PS and PA by these authors. In the case of well as to confirm the results of Figure 2.
PE, in the characterization with FTIR, it was possible to dif-
ferentiate between high density polyethylene (HDPE) and 3.2 Moisture and dirt content of plastic materials
low density polyethylene (LDPE), since there is at least one Table 3 shows the data related to moisture and dirt
different absorption peak between both, according to oth- obtained for all types of plastic materials separated from
er authors (Kochetov et al., 2017; Rodríguez-Bruceta et al., mixed municipal solid waste of the province of Granada
2014; Smith, 1999). (Spain). The samples with the highest moisture content
Another method used to verify the type of polymer, were PS, EPS and PE film. Other authors such as Carranza
as described in section 2.2.1, was the DSC. This method et al.,, 2010 obtained moisture values of 10-20% for PE film
is considered as the most decisive in polymer character- waste from greenhouses.
ization, since it provides the melting temperature. All the With regard to the dirt present in plastics, it was found
polymers analyzed gave consistent results except PA. In that most of it was made up of organic matter (soil, plant
the characterization phase, this material was detected only debris, etc.), paint and chemical residues, as well as labels
in multilayer products, containing PET or PE in addition to and glue residues. Organic matter was more abundant in
PA, and the layers could not be separated. This resulted PE waste, paint and chemicals were present in PP waste,
in numerous overlapping and difficulties to identify fusion while labels and glue residues were more abundant in PET,
peaks in the DSC. For that reason, the DSC of these materi- PS and EPS. The labels were removed after the material
als has not been included in the results. had dried, as they were easily detached. After removal they
Figure 6 shows the results obtained in the laboratory. were weighed. They represent between 10-14% of the plas-
In the case of PET, the melting temperatures reported by tic material and they are therefore an important parameter
other authors (Awaja and Pavel, 2005; EAG Laboratories, to take into account for mechanical recycling. Organic mat-
2018) were between 250-265°C, although slightly lower ter and paint residues were removed during washing.
temperatures can be obtained,which is consistent with the The waste that contains the most dirt is PE film, fol-
results presented in this paper. For PP, the melting tem- lowed by PS. PP had very low dirt loss values. This causes
perature is usually higher than 160°C (Hindle, 2018; Mofo- the viability of mechanical recycling and the quality of the
keng et al., 2011), coinciding with the DSC shown in Figure final product can vary from one material to another. The

TABLE 3: Moisture and dirt content at different temperatures for TABLE 4: Characteristics of washing water at room tempera-
each polymer. ture.
PE PET PP PS EPS PE PET PP PS EPS
Moisture Total dissolved
11.78 8.90 1.58 20.98 16.10 5.64 3.52 0.59 5.71 1.00
(%) solids (g/l)
Dirt (%) at room Total solids
13.79 8.50 2.65 10.20 7.91 13.79 8.50 2.65 10.20 7.91
temperature (g/l)
Dirt (%) in hot
13.17 6.45 1.53 -- -- COD (mgO2/l) 1920 851.57 208.67 526 340.25
water

108 M. Calero et al. / DETRITUS / Volume 04 - 2018 / pages 104-112

TABLE 5: Characteristics of hot washing water.
PE PET PP PS EPS
Total dissolved
5.68 2.04 0.40 - -
solids (g/l)
Total solids
13.17 6.45 1.53 - -
(g/l)

COD (mgO2/l) 1733 510.29 210 - -

loss in weight of dirt is not necessarily determined by the

temperature of the washing.
Washing with hot water did not imply a greater loss
of dirt in terms of weight. In fact, the opposite effect was
observed (Table 3). It was found no significant difference
in the loss of dirt from the material when washing PE, PET
and PP at room temperature or in hot water. Therefore, PS
and EPS were washed only at room temperature, in order
to save water and electricity. However, the use of hot water
made it possible to better remove paint and glue residues
and improved the loss of fat, giving the washed material a
brighter appearance.
Differences in overall weight loss were significant
between different types of waste: While PP had an overall
weight loss of approximately 4%, the weight loss measured
for PS was 30% of its weight after drying and cleaning by
water. These results are of special interest from the point
of view of the recycling process of these materials.

3.3 Determination of dissolved solids, total solids

and COD on washing water
Tables 4 and 5 show the characteristics of the wash-
ing waters at room temperature and hot temperature. Dis-
solved solids, total solids and COD were determined for the
different kinds of water. Washing in hot water did not imply
a greater presence of dissolved solids in the water.
The wastewater will need to be pre-treated depending
on the legislation concerning discharge to the sewerage
networks of each city or country.
In the case of Granada, the Spanish province where this
study was carried out, both the values of dissolved and
total solids and the COD value comply with the limits estab-
lished by the Municipal Ordinance regulating discharges to
the sewage network of the Granada City Council, except in
the case of polyethylene film. The COD values obtained for
this material exceed the limits (1400 mgO2/L), so its waste-
water will need to be pre-treated prior to discharge. This
pre-treatment would include several steps of decantation
and aerobic degradation designed in order to achieve the
discharging limits. The need of these steps will increase
the initial cost of the recycling plant. In those cases, where
a separate discharging network for industrial waste stream
exists, purifying equipment will not be necessary.

4. CONCLUSIONS
The study carried out in this work is the first part of
an investigation for the mechanical recycling of different FIGURE 5: NIR spectra of the different plastic waste identified in
types of plastic materials in order to promote this type of MSW of Granada (Spain).

M. Calero et al. / DETRITUS / Volume 04 - 2018 / pages 104-112 109

 A) FTIR HDPE B) FTIR LDPE

C) FTIR PET D) FTIR PP

E) FTIR PS/EPS F) FTIR PA

G) DSC HDPE H) DSC LDPE

110 M. Calero et al. / DETRITUS / Volume 04 - 2018 / pages 104-112

 I) DSC PET J) DSC PP

K) DCS PS/EPS

FIGURE 6: A-E) FTIR spectra obtained in laboratory of plastic waste present in MSW of Granada (Spain); F-I) DSC obtained in laboratory of
plastic waste present in MSW of Granada (Spain).

recycling among plastic waste from mixed municipal sol- be washed at room temperature to reduce energy costs,
id waste. Mechanical recycling is a good alternative today since their main source of dirt is organic matter (plant
to reduce the amount of waste that ends up in landfills in debris and soil). Finally, it should be noted that, in most
order to reduce the amount of oil needed to make virgin cases, the waste water from the plastic washing process
polymers and to contribute to reducing greenhouse gas would not require further treatment for discharge in Granada
emissions. (Spain). However, it would be necessary in the case of the PE.
The characterization of the raw material carried out
with various Infrared Spectroscopy and DSC techniques ACKNOWLEDGEMENTS
showed that the plastic fraction of the MSW from Granada The authors are grateful to the companies Ingesia S.L.
(Spain) was composed mainly of PE, PET, PP, PS and PA. and STUC S.L. for their contribution to this research.
With regard to the data found during the washing pro-
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