BROMINATED FLAME RETARDANTS (BFRS)

REDUCTION IN PLASTICS FROM

ELECTRONIC AND ELECTRIC EQUIPMENT
WASTE (WEEE) FRACTION AS A
TREATMENT METHOD PRIOR TO
PYROLYSIS

P. EVANGELOPOULOS*a, S. ARATO**, H. PERSSON*, E. KANTARELIS° AND

W. YANG*

* Royal Institute of Technology (KTH), Department of Material Science and Engineering,

Brinellvägen 23, 100 44 Stockholm, Sweden
** The City College of New York, Department of Mechanical Engineering, Steinman Hall
Room 249 160 Convent Avenue,New York, NY 10031
° Royal Institute of Technology (KTH), Department of Chemical Engineering,
Teknikringen 42, 100 44 Stockholm, Sweden
a
Corresponding author: email: pev@kth.se

SUMMARY: Recycling of waste electrical and electronic equipment (WEEE) has been a global
concern during the last decades, not only because of their increasing production but also
because of the toxic compounds that usually are being produced during their handling. Different
recycling techniques have been adapted on commercial scale in order to be able to overcome
this issue, but the recycling of WEEE still lacks of technologies that can treat different kind of
feedstocks in order to maximise the recycling rates. Pyrolysis is an alternative that has not yet
been commercialised for recycling applications eventhough it seems promising for several
factors. By implementing pyrolysis would for example enhance the feedstock recycling in terms
of chemicals that can be produced, it can reduce the production of dioxins and lowering the
energy required for their thermal treatment compared with other alternatives. One of the
drawbacks with this process for this application is the brominated pyrolysis products, which
derives from brominated flame retardants and thereby limits the downstream feedstock
recycling and thereby the utilization of the process products. This study focuses on the
reduction of brominated compounds in the pyrolysis oil through pretreatment of WEEE by
solvent extraction method. Two solvents have been experimentally investigated: isopropanol for
its chemical properties and toluene for its abundance in the pyrolysis oil. The results indicate
that tetrabromobisphenol A (TBBPA), which is one of the main flame retardants used for WEEE,
is extracted during pretreatment and thereby reducing the bromine content in pyrolysis products.

1. INTRODUCTION

Waste electrical and electronic equipment (WEEE), or e-waste, has become a global concern

Proceedings Sardinia 2017 / Sixteenth International Waste Management and Landfill Symposium/ 2 - 6 October 2017
S. Margherita di Pula, Cagliari, Italy / © 2017 by CISA Publisher, Italy
Sardinia 2017 / Sixteenth International Waste Management and Landfill Symposium / 2 - 6 October 2017

the last years. Their increasing amounts in combination the last years together with their high
concentration of toxic substances in this waste stream has made them a high priority risk for
environment and human health (Perkins et al., 2014). Policymakers globally are struggling to
find new strategies for minimizing their production, while on the same time scientists and
engineers are focusing on improving the waste treatment techniques for minimizing their
environmental impact (Bhutta et al., 2011).
One of the main concerns when it comes to recycling of WEEE, a topic that has been
intensively investigated is the high concentration of brominated flame retardants (BFRs) in this
waste fraction, which limits the recycling from the existing technologies (Birnbaum and Staskal,
2004). Such compounds have proven to be very persistent leading to long-term compounds
traces found both in water and soil nearby to waste treatment facilities(Segev et al., 2009).
Moverer, there are numerous studies relating human exposure to those compounds might be
related to endocrine-, reproductive- and behavioral effects (Lyche et al., 2015).
The use of flame retardants in electric and electronic applications is in general vital due to
safety reasons. The devices are usually subject to thermal stress and thereby flammability.
Reducing the amount of flame retardants in the manufacturing process can therefore not be
considered as an option since it will limit their activity. Therefore, end-of-life solutions should be
applied in order to reduce their environmental impact.
Various recycling technologies are applied on WEEE recycling, mostly focusing on
mechanical separating the different components. After several steps of sorting, size reduction
and mechanical recycling, an inhomogeneous mixture of flame retarded plastics, metals and
ceramic materials constitute the most challenging fraction of the WEEE. For this mixture,
several recycling techniques have been proposed such as (1) landfilled, which is considered to
be the worse choice of recycling because of the toxic compounds that might escape in the
aquifier (Osako et al., 2004), (2) incineration, which only targets the energy recovery and
produces dioxins due to the high temperature and the oxidative atmosphere (Birnbaum and
Staskal, 2004), and (3) chemical recycling (E.Kantarelis, 2015). Chemical recycling such as
pyrolysis is among the previously mentioned alternatives the most environmentally friendly
technology, yet not fully studied (Ma et al., 2016).
Pyrolysis has been referred in previous studies as a valuable alternative for recycling of the
organic content for mixture of waste that cannot further be separated in other means. One of the
main benefits of pyrolysis is that valuable condensable liquid fractions are being produced
derived from the initial composition of the pyrolysed material, which can be used either for
feedstock recycling or for liquid fuel production (Chen et al., 2014; Williams, 2013). On the other
hand, waste fractions that include BFRs produce pyrolysis oils mixed with brominated
compounds and this limits their direct recovery.
Various ways of removal these brominated compounds from the pyrolysis oil mixture has
been studied the previous years. Several studies has been focucing on one pot solutions by
adjusting several conditions of pyrolysis process, they have manage to minimise their transfer to
the liquid fraction(Evangelopoulos et al., 2015). Other studies has been focusing on end of pipe
solution by checking various catalysts both for capturing brominated species and for oil
upgade(Yecheskel et al., 2013). Moreover, pre treatment of flame retardants from polymeric
matrixes has been also investigated previously. Zhang et al. have investigated the removal of
BFRs in plastics through solvothermal technique and has concluded that alcohols can efficiently
remove the tetrabromobisphenol A, which is one of the main flame retardants used in the
manufacturing process of electrical and electronic plastic components (Zhang and Zhang,
2012). Vilaplana et al have been thouroughly investigated the solvent extraction of specific
additives such as the TBBPA and Decabromodiphenyl ether from polymers, subject to
microwave extraction at different temperatures and time. This work has concluded that the most
important factors that influence the extraction was the time and the temperature of the process
Sardinia 2017 / Sixteenth International Waste Management and Landfill Symposium / 2 - 6 October 2017

(Vilaplana et al., 2009).

This study investigates the removal of TBBPA from real WEEE fractions through soxhlet
solvent extraction method as treatment prior to pyrolysis. The degree of removal is evaluated
both by the liquid effluent analysis and by analyse the bromine content of the treated and
untreated material. Furthermore, this work aims to correlate the products of pyrolysis with the
removal of TBBPA, which has not been investigated in previous studies.

2. MATERIALS AND METHODS

2.1 Material composition

Three different fractions of brominated WEEE have been collected from a recycling site at
different separation stages. All of them contain relatively high percentage of bromine which
derives from the high concetration of brominated flame retardant on their plastics. On the
recycling site, after the first sorting and detoxification, the WEEE is shredded and the plastics
are being separated acoording to their physical properties. The first fraction of WEEE are
brominated plastics which has been separated from recyclable plastics with density separation
methods. The second fraction of WEEE which has been investigated is Modem Wifi plastics,
derived from the recycling process of those devices. The last examined fraction is printed circuit
boards (PCBs), which is considered to be one of the most challenging fraction in recycling of
WEEE and has been previously investigated in previous studies by the authors
(Evangelopoulos et al., 2015). All the different examined fractions have been homogenized
through intensive mixing and their particle size was reduced to particle size of >0,09mm in order
to be used both for the extraction and for the pyrolysis experimnets.

2.2 Methods

Two solvents were chosen for the liquid extraction based on their chemical properties.
Isopropanol was selected because of its polarity and its low toxicity. Toluene was chosen
because it is one of the condensable products that derived from pyrolysis of the three examined
WEEE fractions. In terms of liquid extraction being an industrial application for WEEE treatment,
this solvent can be separated from the pyrolysis products and be recirculated to the initial
material for the solvent extraction. Both of the solvents were of 99.9% HPLC purity grade
purchased by VWR and the thimbles used for the soxhlet apparatus were high purity glass
microfiber thimbles (300mm x 100mm) in order to be totally inert from the process.
Liquid extraction from the three investigated fractions was performed on Soxhlet extractor. 1g
of the WEEE sample was placed in the thimble and in the Soxhlet apparatus, while a spherical
flask was filled with 100ml of solvent according to the examined case. The flask was then
submerged to a heated oil bath. The temperature of the extraction was 132°C for the
isopropanol extraction while for the toluene extraction, the temperature inside the flask was
153°C for all the investigated fractions. The total time of the extraction was 6 hours.

2.2.1 Liquid analysis of the effluent by GC/MS analysis

The liquid obtained by the extraction was filltered and analysed using an Agilent 7890A gas
chromatographer with an Agilent 5975C MSD mass spectrometer (GCMS). The column used for
the chromatographic separation was an HP5ms fused with phenyl methyl silox (30m, 250 μm
film thickness, x 0.25mm inner diameter), while the temperature profile used had as starting
temperature of 125 °C, holding up for 1 min and then with 10 °C/min heating rate to the final
temperature of 325 °C for 5 min. SIM analysis was performed targeting on the specific ions (63,
Sardinia 2017 / Sixteenth International Waste Management and Landfill Symposium / 2 - 6 October 2017

76, 89, 151, 152, 181, 196, 212, 277, 291, 293, 295, 525, 527, 529, 530, 531, 533, 542, 544,
546) which according to NIST11 library indicates its presence.

2.2.2 Pyrolysis experiments

The initial sample and the samples treated with the soxhlet extraction were pyrolysed using a
Pyrola® 2000 pyrolyzer coupled to the GC/MS. The pyrolyzer consists of a Pt filament, which
makes it possible to adjust the temperature of pyrolysis with a heating rate similar to flash
pyrolysis. The chromatograms obtained from the pyroysis experiments were analysed in order
to evalute the degree of the extraction of brominated flame retardants and the influence of
solvent extraction in the composition of derived pyrolytic vapors. The temperature of pyrolysis
was set to be 700°C.

2.2.3 Bromine content analysis of the WEEE fractions through SEM-EDS

The samples were further investigated by a scanning electron microscope (SEM) coupled
with an Energy-dispersive X-ray spectroscopy (EDS) detector for both observing the difference
on the surface of the original plastic sample in comparison with the treated samples, and for
identifying differences in the elemental composition to evaluate the degree of bromine removal.
The equipment used was a Hitachi Analytical TableTop Microscope / Benchtop SEM TM3030.

3. Results and discussion

3.1 Material characterisation

The elemental composition of the three examined fractions are presented inTable 1.The
chosen WEEE fractions are representative since they have been collected by the real recycling
plant. The fraction of brominated plastics have passed through a certain separation steps and
they mainly contain plastic material, which is visible on their high volatile content. Moreover, the
high quantity of oxygen indicates that the plastics in this fraction are mainly oxygen-containing
polymers or plastics that contain oxides as additives. Similarly, the examined fraction Modem
Wifi plastics has also high volatile matter but a relatively low oxygen content, which indicates
that the major part of the plastics might have more hydrocarbon segments than the Brominated
plastics fraction. The PCBs fraction contains high quantity of metal and ceramic materials,
which can be observed from the high ash content. All of the examined fraction contains
relatively high amount of bromine, which derives from the flame retardant that has been used
during their manufacturing process.

Table 1 Proximate and Ultimate analysis of the tested fractions

Proximate analysis (wt%)

Printed
Brominated Modem Wifi
Circuit
Plastics Plastics
Boards

Ash 550°C 9,70% 21,00% 79,70%

Volatile 86,50% 74,50% 17,00%
Fixed Carbon 3,80% 4,50% 3,30%
Ulimate analysis (wt%)
Printed
Brominated Modem Wifi
Circuit
Plastics Plastics
Boards
Sardinia 2017 / Sixteenth International Waste Management and Landfill Symposium / 2 - 6 October 2017

Carbon (C) 67,40% 66,00% 12,90%

Hydrogen (H) 6,50% 6,10% 1,30%
Nitrogen (N) 2,05% 3,67% 0,47%
Chlorine (Cl) 0,96% 0,31% 0,04%
Sulphur (S) 0,06% 0,05% 0,16%
Bromine (Br) 0,78% 1,75% 1,63%
Oxygen (O) 12,55% 1,12% 3,81%

3.2 Liquid analysis on the effluent solvent

The liquid analysis of the effluent solvents after the extraction is summarised in Figure 1.
Since the method of analysis was focusing on only one compound (TBBPA), only the results for
this specific compound are presented and compared for the different cases. The results are
illustrated on logarithmic scale in order to make the comparison more visible on the graph.
Moreover, the results are also normalized according to the volatile fraction of each WEEE
sample since TBBPA exists in the organic part.
The results indicate that the TBBPA compound has been succesfully extracted from all the
examined WEEE samples and for both solvents used. For all examined WEEE fractions it is a
clear trend of toluene being a more efficient solvent for extracting TBBPA compared to
isopropanol. This indicates that eventhough, the polarity of the solvent place a significant role on
the extraction (Vilaplana et al., 2009), the extraction temperature might have enhanced more
the extraction of TBBPA from these WEEE waste fractions.

100000000

10000000
Absolute area detected

1000000

100000

10000

1000

100

10

1
Brominated Plastics Modem Wifi plastics Printed circuit boards

Isopropanol Toluene

Figure 1 Liquid analysis of the solvents after the extraction

3.3 Pyrolysis experiments

Numerous organic compounds have been identified from the pyrolysis of WEEE fractions.
The pyrolysis of plastic materials can produce compound fragments from the initial polymeric
chain. Hydrocarbons and aldehydes are usually expected to be found. In terms of waste
management, all these compounds can be easily utilised for production of other chemicals and
polymeric materials after a proper separation technology is applied. On the other hand, another
Sardinia 2017 / Sixteenth International Waste Management and Landfill Symposium / 2 - 6 October 2017

alternative might be the production of liquid fuels. For this specific study, the brominated
compounds that are being produced during the pyroslysis of WEEE materials are the main
focus. Therefore, a comparison of the brominated compounds is to be followed. A typical
pyrogram from these tests is presented on the Figure 2.

BROMINATED PLASTICS RAW 700

12000000

10000000

8000000

6000000

4000000

2000000

0
0 10 20 30 40 50 60 70 80 90 100

Figure 2 Typical pyrogram obtained by Py-GC/MS for the WEEE fraction of the raw Brominated
plastics

The lightest compound that is usually produced during the decomposition of brominated
plastics is hydrogen bromine (HBr), which is one of the main products based on similar studies
(Wu, 2014). Unfortunatelly, the parameters and the set up of the GC/MS does not allowed us to
detect this compound. The first peak that is seen in the pyrogram is bromomethane (CH3Br),
which is one of the lightest detectable organic compound that is being produced due to the
thermal decomposition pathway of the brominated flame retardants. More specifically it has
been detected on the 4,79 minutes according to the method used for the analysis.
Several brominated species that are originated from the TBBPA has been detected. In all the
investigated cases, the trend was clear that less brominated compounds are being produced
from the pre-treated samples in comparison with the raw materials. Table 2 illustrates the
brominated compounds that have been found in the pyrolysis products from GC/MS analysis as
well as their degree of reduction compared to raw materials. In specific cases, the brominated
compounds have not been detected (refered as BDL), which shows that the removal of TBBPA
have influence the initial material’s decomposition. This is also observed on the decomposition
of Modem & Wifi fraction, which in the case of toluene, eventhough all the brominated species
has been reduced, the bromomethane has been increased. This indicates that the
decomposition mechanism has changed. This result is based on the detected total peak area
and it has been normalised based on the mass used for each test.
Sardinia 2017 / Sixteenth International Waste Management and Landfill Symposium / 2 - 6 October 2017

Table 2 Detected compounds on the Pyrograms and their deduction based on their area
detected

Isopropanol
Compounds Toluene treated
treated
Brominated Plastics
Bromomethane 55,57% 64,94%
TBBPA 24,06% 88,86%
2,4,6 tribromophenol 89,58% BDL*
2,5-Dibromobenzo(b)thiophene BDL* BDL*
Modem & WiFi Plastics
Bromomethane 49,09% -15,76%
TBBPA 77,05% 67,60%
2,4,6 tribromophenol 90,44% 61,76%
Phenol 2,4-dibromo- 95,30% 90,46%
3,5-Dibromobenzo(b)thiophene 83,65% 71,64%
Printed Circuit Boards
Bromomethane 54,95% 46,69%
TBBPA 63,17% 30,20%
Phenol 2,4-dibromo- 55,81% 32,75%

Bicyclo[4.2.0]octa-1,3,5-triene, 7,8-
44,98% 65,38%
dibromo-

*below detection limit

The total removal of TBBPA was achieved based on the detected pyrolysis products. On the
other hand, both solvents have been proven to efficiently reduce the concentration of this
compound on the pyrolysis products. Moreover, some of the brominated compounds that have
been produced during the decomposition of the raw materials were not found on the pyrolysis
products of the treated samples

3.4 SEM EDS analysis

The examined waste fractions have also been analysed through SEM EDS for elemental
composition analysis. The results indicates that the bromine content has been reduced in the
treated samples. This trend is clear eventhough the standard deviation is rather high and not so
reliable conclusions can be made. Both of the solvents, at least for the tested conditions have
not succed to effectively reduce the bromine content of the plastic materials.
Sardinia 2017 / Sixteenth International Waste Management and Landfill Symposium / 2 - 6 October 2017

10
9
8

Bromine (wt.%)
7
6
5
4
3
2
1
0
Brominated Plastics Modem Wifi plastics Printed circuit boards

raw isopropanol toluene

Figure 3 SEM EDS analysis of the raw samples and treated with isopropanol and toluene

4. CONCLUSIONS

The removal of the bromine from three different fractions of WEEE has been succeded
throught soxhlet extraction. The results have been been verified from the liquid effluent solvent
analysis, the pyrolysis products and the SEM-EDS analysis. Although the degree of removal is
relatively low, the trend clearly shows that by adjusting other operation parameters, such as the
time or the temperature, the extraction can be improved for the extraction of TBBPA. Moreover,
this treatment might have influenced the decomposition of those materials, since some
compounds have not been produced in the pyrolysis of treated samples, something that needs
to be further investigated.

AKNOWLEDGEMENTS

The authors would like to aknowledge the Swedish Energy Agency (Energimyndigheten) for the
financial support (project number 36880 -2) and Stena Recycling AB for providing the WEEE
material for the experimental investigation

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