Article

pubs.acs.org/EF

Inuence of Zeolites and Mesoporous Catalysts on Catalytic Pyrolysis

of Brominated AcrylonitrileButadieneStyrene (Br-ABS)
Chuan Ma, Jie Yu,* Ben Wang, Zijian Song, Fei Zhou, Jun Xiang, Song Hu, and Lushi Sun*
State Key Laboratory of Coal Combustion, Huazhong University of Science and Technology, Wuhan, Hubei 430074, Peoples
Republic of China
ABSTRACT: Three zeolite materials (HY, H, and HZSM-5) and two mesoporous solids (all-silica MCM-41 and active Al2O3)
with dierent textural properties were investigated for their catalytic eects on the pyrolysis of brominated acrylonitrile
butadienestyrene (Br-ABS). The results indicated that, in the absence of a catalyst, the maximum liquid yield was obtained from
the pyrolysis of Br-ABS, including oil and wax. The addition of HY and H zeolites signicantly decreased the oil yield from 63.6
to 45 and 44.3 wt %, respectively, with a corresponding increase in the yields of wax and gas. HZSM-5 zeolite slightly changed
the product distribution and increased the gas yield at the expense of wax. Noteworthy, the mesoporous catalyst of all-silica
MCM-41 retained the oil production while signicantly reduced the wax yield to 7.9 wt %. In terms of the composition of the
oils, the catalysts could promote the formation of valuable single-ring aromatics in oils. Moreover, the catalysts exhibited
pronounced debromination eciency, especially the zeolites, which could achieve the removal of bromine in oils by over 50%
compared to thermal pyrolysis. The results indicated that the product distributions of Br-ABS had interrelationship with the
textural properties of catalysts.

1. INTRODUCTION
The electronics manufacturing industry has become an
emerging and fast growing sector in the world, because of the
rapid development of technology innovation and ever-shortening product lifespans. Subsequently, large consumption of
electronic products results in a great number of electronic
wastes, which have been taken into the agenda for waste
management in many countries. It is estimated that the total
quantity of waste electrical and electronic equipment (WEEE)
in 2014 was 41.8 million tons, and it is expected to hit 50
million tons by 2018 at an annual growth rate of approximately
5 wt %.1 China, as one of the largest electronic manufacturing
countries and one of the emerging economies in the world, is
rising up as the second biggest entry of WEEE generation.2 To
solve this great challenge, WEEE has been legislatively required
to be recycled and reused in a proper way in the European
Union (EU) according to the WEEE Directive.3 In general,
approximately 30% of the total WEEE consists of plastics,4 and
thereby, the growing volume of plastics from WEEE has been
taken into an imperative recycling treatment to meet these
targets. In terms of the plastic fraction of WEEE, acrylonitrile
butadienestyrene (ABS) and high-impact polystyrene (HIPS)
plastics make up a signicant proportion of 55% of the plastic
fraction in WEEE,5 which generally include toxic brominated
ame retardants (BFRs) and antimony trioxide (Sb2O3)
synergist for the re safety performance of polymer materials.6
Nevertheless, the presence of BFRs in WEEE plastics has been
the major impediment for recycling treatment because of the
potential health risks and environmental impacts.7 For the sake
of hazardous plastic wastes, advanced handling methods are
essential to eliminating the toxic ame retardant additives
during the recycling process of WEEE plastics.
Feedstock recycling by means of pyrolysis is one of the
promising technologies for WEEE plastics treatment, with the
aim of converting the WEEE plastics into fuels or chemical
2016 American Chemical Society

feedstocks. Considering the high-value chemicals and high

energy density of plastics, investigations on feedstock recycling
of WEEE plastics have been performed to convert the
polymeric materials into valuable chemicals and fuels over
recent decades.811 However, WEEE plastics containing BFRs
are especially prone to produce a great quantity of brominated
compounds in the oil, for example, SbBr3, HBr, and
organobromine compounds during the pyrolysis process
without any additive or catalyst.1214 Thus, researchers have
been attempting to improve the feedstock recycling process and
bring back waste plastics for commercial applications by
generating high-quality bromine-free chemicals and alternative
clean fuels.1517
In the last few decades, extensive studies on catalytic
pyrolysis of plastics were carried out to investigate the
eectiveness of the catalyst and the degradation mechanisms
over various catalytic systems. A wide range of catalytic
materials has been used for plastic degradation: metallic
oxides,1820 zeolites,2124 uid catalytic cracking (FCC)
catalysts,25 mesoporous materials, and silicaalumina.2630
Zeolites are the most used catalysts and exhibited outstanding
cracking performances in polymer degradation, particularly
HZSM-5, as a result of its inherent microporous structure and
acid property.22,23 Mesoporous catalysts, e.g., MCM-41, with
larger pores and surface areas than zeolites were also applied for
polymer degradation, which were benecial to macromolecules
entering the channel of the catalyst and cracking into liquid
fuels.26,27 ZSM-5 and Y-zeolite catalysts have been used for the
catalytic pyrolysis of ame-retarded plastics.21 It was reported
that both zeolite catalysts can achieve a remarkable removal of
Received: February 26, 2016
Revised: May 3, 2016
Published: May 5, 2016
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mm). The catalysts were characterized by dierent techniques and

presented in Table 2. The details of the characterization of the
catalysts have been illustrated previously.10 The physical properties of
the catalysts were characterized by N2 adsorptiondesorption
measurement (ASAP 2010, Micromeritics). The BrunauerEmmettTeller (BET) surface area of the catalysts followed the trend:
all-silica MCM-41 > HY > H > HZSM-5 > Al2O3. The acid
properties of the catalysts were obtained using temperatureprogrammed desorption of NH3 (NH3-TPD) performed on the
ChemiSorb 2720 (Micromeritics). The total acidity of the catalysts
followed the trend: HZSM-5 > HY > H > Al2O3 > all-silica MCM-41.
2.2. Experimental Procedures. The xed-bed reactor composed
of a quartz tube (height, 46 cm; inner diameter, 41 mm) was used in
this work, as shown in Figure 1. Before the catalytic pyrolysis
experiments, the Br-ABS sample and the catalyst were mixed
thoroughly (the catalyst and the Br-ABS sample at a mass ratio of
1:9) and then a quartz crucible (height, 50 mm; inner diameter, 30
mm) containing 10 g samples was placed inside the reactor. For
comparison, the thermal degradation of Br-ABS without a catalyst was
carried out under the same experimental conditions. Prior to the
experiment, high-purity nitrogen (100 mL min1) was continuously
fed into the system for 30 min to form an inert atmosphere.
Experiments were performed from ambient to the target temperature
(410 C) at 10 C min1 with high-purity nitrogen (30 mL min1) as a
carrier gas. For the isothermal stage, the target temperature stayed for
90 min. The parameters used in the paper are optimized operating
conditions and were well-established by the authors centered on this
subject.
The products from the pyrolysis of Br-ABS were classied as oil,
wax, gas, and char residue. The volatile products were rst cooled by
an ice/salt bath condenser. The mass of oil products collected in the
tar trap and the mass of heavy waxy products coated on the walls of
the reactor (namely, wax) were measured separately. A small amount
of trapped product coated on the U-tube was dissolved in chloroform
and ltered to distill at a reduced pressure to separate the oil and wax,
which was weighed accurately.33 A ber lter was used to remove any
pyrolysis oil from the gas stream, and the alkali solution ask was used
to trap HBr or Br2. After each experiment, the solid residue that
remained in the crucible was weighed and dened as char residue. The
yield of char derived from the pyrolysis of raw materials was calculated
as follows:

bromine in the oil, and Y-zeolite exhibited a better

debromination performance than ZSM-5. However, the yield
of oil and the composition of the pyrolysis products was
signicantly inuenced by the catalysts. In fact, the authors also
claimed that the composition of the pyrolysis oil was not greatly
altered and the organobromine compounds were reduced in the
presence of the FCC catalyst.25 Fe-modied zeolite catalysts
were investigated in the catalytic pyrolysis of brominated HIPS,
and it was found that modied zeolite catalysts could enhance
the debromination performance during the pyrolysiscatalysis
process.9 Marcilla et al.30 investigated the particular pyrolysis
performance of HIPS with the Al-MCM-41 catalyst and found
that the catalyst had a signicant inuence on the
decomposition of each polymeric constituent in the HIPS
copolymer, including the polystyrene (PS) and polybutadiene
(PB) phases. However, the ABS copolymer is a composite
material consisting of a styreneacrylonitrile (SAN) continuous phase, partially grafted to a dispersed PB rubber phase,
which usually contains BFRs and Sb2O3 synergist. The catalytic
eects of dierent solid acid catalysts on the pyrolysis of
brominated ABS (Br-ABS) have scarcely been investigated as a
result of its specic thermal degradation characteristics and the
formation of brominated products.21,25,31 However, these solid
acid catalysts with dierent catalytic activities can be closely
associated with their textural properties. Acidity, particularly the
strength and number of active acid sites, is also demonstrated
to play an vital role in the catalytic cracking performance of
polymers.26,32 Understanding the behavior of catalytic pyrolysis
of Br-ABS is crucial to promote the potential commercial
application of catalytic treatment for feedstock recycling of
plastics from WEEE.
In this work, catalytic pyrolysis of Br-ABS over various solid
acid catalysts was conducted in a xed-bed reactor at 410 C.
Three zeolite materials (HY, H, and HZSM-5) and two
mesoporous solids (all-silica MCM-41 and active Al2O3) with
dierent textural and acid properties were applied to investigate
the catalytic eects of solid acid catalysts on the pyrolysis of BrABS. Meanwhile, the migration and transformation behaviors of
bromine during the pyrolysis process of Br-ABS were
demonstrated to enhance the potential benets of feedstock
recycling for high-quality bromine-free fuel oils.

yield of char (wt%) =

2.1. Materials. The Br-ABS plastics (PA-765A) were supplied by

Qimei Co., Ltd., Zhenjiang, China. Br-ABS contained the ame
retardant additive of tetrabromobisphenol A (TBBPA) and synergist
Sb2O3. The particle size of the plastic sample was ground to <0.6 mm
in a pulverizer. The proximate and ultimate analyses of Br-ABS are
presented in Table 1. The all-silica MCM-41 and zeolite catalysts (HY,
H, and HZSM-5) with the particle diameter of <5 m used in this
study were provided by the plant of Nankai University Catalyst Co.,
Ltd., China. Active Al2O3 was obtained from Sigma-Aldrich (<0.15

Table 1. Main Characteristics of the Br-ABS Sample

wt %

ultimate analysisa

wt %

moisture
volatile matter
xed carbon
ash

0.2
98.2
0.3
1.3

C
H
N
Ob
Br
Sb

77.5
7
2.8
1.4
8.6
2.7

(1)

The mass of gaseous products was obtained by dierence.

2.3. Analytical Methods. The ultimate and proximate analyses of
the sample were respectively determined using an elemental analyzer
(Vario Micro cube, Elementar, Inc., Germany) and TGA-2000 (Las
Navas Instruments, Spain). The bromine content in the raw sample
and the pyrolysis products were determined using the United States
Environmental Protection Agency (U.S. EPA) method 5050.8,10 To
analyze the antimony content in the sample, acid digestion followed by
inductive coupled plasma with mass spectrometry was used. An aliquot
of the sample was rst mixed with sulfuric and nitric acids and then
was digested in a microwave digestion system (Milestone ETHOS E).
Pyrolysis oils were dissolved in chloroform (1:10, v/v) and analyzed
by gas chromatography/mass spectrometry (GC/MS, Agilent 7890A/
5975C) to determine the components of oils obtained from the
pyrolysis and catalytic pyrolysis of Br-ABS. The detailed operating
conditions of the instrument have been illustrated elsewhere.10 The
identication of the unknown compounds was carried out by
comparing their MS spectra to those of the standards injected and/
or those in the National Institute of Standards and Technology
(NIST) library. The standards injected were toluene, ethylbenzene,
styrene, cumene, -methylstyrene, 1,3-diphenylpropane, 1,3-diphenylbutane, 1,3-dipheny-1-butene, naphthalene, bibenzyl, 1-phenylnaphthalene, 1,3,5-triphenylbenzene, and brominated compounds, such as
1-(bromoethyl)benzene, 2-/4-bromophenol, 2,4-/2,6-dibromophenol,
and 2,3,5-tribromophenol.

2. EXPERIMENTAL SECTION

proximate analysis

m(residue) m(catalyst)
100%
m(BrABS)

Dry and ash-free basis. bBy dierence.

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Table 2. Properties of the Catalysts

catalyst

HY

HZSM-5

all-silica MCM-41

Al2O3

BET surface area (m2 g1)

micropore area (m2 g1)
external surface area (m2 g1)
micropore volume (cm3 g1)
total pore volume (cm3 g1)
average pore size (nm)
SiO2/Al2O3a (mole ratio)
total acidityb (mmol g1)

670.97
589.93
81.04
0.275
0.377
2.25
5.74
0.517

525.04
392.95
132.09
0.183
0.371
2.83
21.0
0.484

287.27
249.78
37.49
0.116
0.164
2.27
25.8
0.746

1091.98
36.03
1055.96
0.003
0.958
3.51

215.52
227.87
0.434
8.05
0.473

From the XRF measurement. bFrom the NH3-TPD measurement.

Figure 1. Schematic diagram of the experimental setup.

The functional groups of pyrolysis oils were also determined using
VERTEX 70 Fourier transform infrared spectroscopy (FTIR, Bruker,
Germany). A small quantity of oil was coat on a KBr disk and then
analyzed over 4004000 cm1.
Char residues were examined with a powder X-ray diraction
(XRD) XPert PRO diractometer with monochromatic Cu K
radiation (PANalytical B.V., 40 kV and 40 mA) to determine the
crystal structures of the reacted catalysts and the presence of inorganic
crystalline compounds exiting in the char residues. The XRD spectra
were recorded over a range of 2 from 5 to 80 with a scan rate of
12 min1. Scanning electron microscopy (SEM) images of the char
residues were obtained on SIGMA eld-emission scanning electron
microscopy (FE-SEM, Zeiss) to determine the morphologies of the
char residues and the reacted catalysts.

3. RESULTS AND DISCUSSION

3.1. Product Distribution. The product yields from
pyrolysis and catalytic pyrolysis of Br-ABS over dierent
catalysts are present in Figure 2. Without a catalyst, Br-ABS
plastic produced the maximum liquid yield of 77.8 wt %,
including the oil and wax, amounting for the main fraction of
the pyrolysis products. When Br-ABS was pyrolyzed with the
HY and H catalysts, respectively, the oil yield decreased from
63.6 to 45 and 44.3 wt %, respectively, with a corresponding
increase in the wax yield. The formation of yellowish brown
wax indicated that intense secondary cross-linking reactions
occurred in the presence of the acid catalysts.26 The large BET
surface areas of HY and H (670.97 and 525.04 m2 g1,
respectively) ensured more acidic sites to be involved in
secondary cross-linking reactions, and large pore volumes
(0.377 and 0.371 m2 g1, respectively) enhanced bigger
molecules to be accessible to enter the active sites. Noteworthy,
the presence of the HZSM-5 catalyst showed less inuence on

Figure 2. Product distribution from the pyrolysis and catalytic

pyrolysis of Br-ABS.

the overall product distribution compared to the other zeolites,

which slightly decreased the oil yield to 62.9 wt % and
increased the gas yield from 10 to 14 wt %. This behavior could
be well-related to the special pore structure and strong acidity
of HZSM-5 zeolite, the inherent nature of the SiOSi
framework, and the high total acidity of 0.746 mmol g1, which
was in favor of converting heavier pyrolysis products into
lighter pyrolysis products.10,22 The above results showed well
performance of zeolite catalysts in terms of catalytic cracking. In
comparison to the three zeolite catalysts, the product
distribution was in accordance with specic properties of the
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zeolites, such as acidity, BET surface area, and pore volume.
Large BET surface areas and pore volumes of HY and H were
more important to promote high cracking activity compared to
HZSM-5 zeolite, whereas HZSM-5 with a higher acidity
content dominated the catalytic cracking performance, in which
more monomolecular cracking took place to produce lighter
products.
In comparison to the zeolites, the mesoporous catalysts had
less impact on the product distribution. The addition of allsilica MCM-41 catalyst to the catalytic pyrolysis of Br-ABS
retained the oil yield of 63.4 wt % and signicantly reduced the
wax production to 7.9 wt %. Simultaneously, the production of
char and gas increased to some extent compared to the thermal
pyrolysis. Active Al2O3 exhibited negligible inuence on the
product distribution and retained the oil yield to 63.7 wt %. A
higher catalytic activity on the product distribution of Br-ABS
in the presence of all-silica MCM-41 than Al2O3 can be wellcorrelated with the dierence in the nature of their mesoporous
structures. It was clear that all-silica MCM-41 without active
acid sites resulting in higher oil than the zeolite catalysts can be
attributed to its largest BET surface area (1091.98 m2 g1) and
uniform mesoporous structure. Macromolecules can overcome
the steric hindrances to faster access to the catalyst structure
and can be favorable to participate in the interaction with the
bridging oxygen atoms lining the channels via a carbenium ion
mechanism, which is primarily promoted by a solid acid
catalyst.27,29 The results suggested that the mesoporous catalyst
of all-silica MCM-41 with a large BET surface area and pore
size played an key role in transforming the Br-ABS sample into
liquid oil.
It was suggested that thermal decomposition of the polymer
mainly proceeds via free-radical reactions involving chain
scission, propagation, and termination,13 while solid acid
catalysts took place through the carbenium mechanism, scission, and inter-/intramolecular hydrogen transfer, which is
deeply dependent upon their textural and acid properties.26,29
The catalytic pyrolysis of Br-ABS not only proceeded through
the primary carbenium ion chemistry involving dierent
reactions, such as -scission, isomerization, alkylation, cyclization, and aromatization, but also deeply depended upon the
synergistic eect between the polymer and ame retardant
additives. The dierent properties of the zeolites and
mesoporous catalysts, varying by pore structure and acidity,
exhibited signicantly inuence on the product distribution of
Br-ABS pyrolysis.
3.2. Characterization of Pyrolysis Oil. Figure 3 shows the
FTIR spectra of the oils derived from Br-ABS pyrolysis over
4004000 cm1. The results were on the whole similar in the
experiments with or without catalyst. From the FTIR
spectrograms, a typical OH vibration was detected in all
oils at 3522 cm1 related to the formation of phenols, which
was associated with the pyrolysis of TBBPA. Typical CH
stretches in benzene rings were observed at 3026, 3059, and
3083 cm1. The CH stretches assigned to methyl and
methylene groups were detected at 2962 and 2926 cm1,
respectively. The typical four peaks between 1660 and 2000
cm1 were substitution patterns in aromatic rings. The CC
skeleton-bond vibrations of substituted aromatics were present
at 1452 and 1494 cm1. The bands in the interval of 1400
1000 cm1 were assigned to polycondensed substituted
aromatics. The peak at 1376 cm1 may be CCH3 deformation
with a single methyl group attached to a carbon atom. The
strong bands at 754 and 698 cm1 reected the monosub-

Figure 3. FTIR spectra of oil products from the pyrolysis of Br-ABS:

(a) thermal, (b) HY, (c) H, (d) HZSM-5, (e) all-silica MCM-41, and
(f) Al2O3.

stituted benzene rings. The weak bands at 10001075 cm1

might be related to aryl CBr presented in the spectrograms.12
The results suggested that the typical functional groups present
in the oils showed little change with the addition of the
catalysts.
The single- to four-ring aromatic compounds in the oils were
established by the peak area using GC/MS (percent area), as
shown in Figure 4. The oil from Br-ABS plastic pyrolysis
without catalysts contained about 46.5% area of single-ring
aromatic compounds, higher than that from Br-HIPS plastic
pyrolysis under the same conditions, which reached 42% area of
single-ring aromatics in pyrolysis oil.10 Obviously, the presence
of the catalysts changed the distribution of the oils and

Figure 4. Aromatic compound composition of oil products from the

pyrolysis of Br-ABS (single- to four-ring aromatic compounds).
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Table 3. Main Compounds of Br-ABS Degradation over Various Catalysts by GC/MS (wt %)
catalytic degradationa

thermal

compound

toluene
ethylbenzene
p-/m-/o-xylene
styrene
cumene
bromobenzene
-methylstyrene
indane
2-bromophenol
1-(bromoethyl)benzene
naphthalene
4-bromophenol
2-methylnaphthalene
2,4-dibromophenol
2,6-dibromophenol
diphenylmethane
bibenzyl
2,3,5-tribromophenol
1,3-diphenylpropane
1,3-diphenylbutane
1,4-diphenylbutane
1,3-diphenyl-1-butene
1-phenylnaphthalene
1,3-diphenylbenzene
1,2,4-triphenylbenzene
1,3,5-triphenylbenzene

9.13
20.00
c
3.30
10.68
c
c
c
c
1.42
0.20
c
0.09
1.12
0.21
0.17
0.36
0.50
17.07
5.97
1.08
4.94
2.82
0.36
1.39
3.03

HY

HZSM-5

all-silica MCM-41

Al2O3

13.04
24.15
0.12
7.90
8.06
0.03
0.05
0.09
0.90
2.71
0.33
c
0.30
1.07
0.70
0.24
0.32
0.78
10.42
c
0.70
5.61
0.53
0.26
0.29
0.59

11.37
24.25
0.17
1.50
10.13
0.02
0.07
0.38
c
7.02
0.58
0.09
c
1.28
0.45
0.26
0.35
1.17
11.55
c
0.96
4.26
2.17
0.17
0.98
0.61

10.77
21.15
0.17
7.00
6.83
0.08
c
c
0.15
1.23
0.40
c
0.39
0.91
0.19
0.40
0.51
0.60
14.89
5.77
1.22
9.90
1.56
0.31
0.40
0.59

9.72
24.58
0.06
2.44
11.68
0.00
0.08
0.06
3.37
0.76
0.19
c
0.31
1.6
0.69
0.31
0.55
0.11
13.31
1.74
0.86
6.55
2.91
0.12
0.65
1.02

9.76
26.10
c
4.30
9.48
c
c
c
c
1.77
0.10
c
0.10
0.22
0.13
0.13
0.40
0.43
16.50
5.81
0.90
4.92
2.01
0.15
0.55
1.08

Catalytic conditions: m(catalyst)/m(Br-ABS) = 1:9. bM = Br-ABS. cLess than 0.01 wt %.

more single aromatic compounds than HZSM-5. In contrast,

the mesoporous catalysts produced more single-ring aromatics
in the oil from Br-ABS than that from Br-HIPS. This may be
due to the larger pore sizes of all-silica MCM-41 and Al2O3
(3.51 and 8.05 nm, respectively), which were benecial to the
catalytic cracking of macromolecules, thereby preventing the
steric hindrance eect of coke deposition on the catalysts.39 In
comparison to the zeolites, the large BET surface areas and
uniform mesoporous structures of all-silica MCM-41 and Al2O3
played a key role in the production of single aromatic
compounds.
The identied main components in the oils were quantied
in Table 3 (weight percent). The valuable chemical feedstocks
in oil were dominated by toluene, ethylbenzene, styrene, and
cumene, derived from the styrene-based ABS plastics. The
presence of 2-/4-bromophenol, 2,4-/2,6-dibromophenol, and
2,3,5-tribromophenol was attributed to the pyrolysis of TBBPA.
A little amount of hexadecanenitrile instead of the typical N
compound of benzenebutanenitrile was detected, which might
be the consequence of the low proportion of acrylonitrile in the
sample corresponding to a low nitrogen concentration by
elemental analysis. The catalysts exhibited a signicantly
inuence on the yield of the components in the oils, as
shown in Table 3. In comparison to thermal pyrolysis, the
presence of catalysts promoted the formation of toluene and
ethylbenzene. In contrast, the zeolite catalysts also slightly
increased the yield of styrene. It was proposed that the
interaction between the polymer radicals and the BFR and
Sb2O3 additives could inhibit the formation of styrene,13,14
whereas the presence of zeolites would promote the TBBPA
decomposition and weaken the synergistic eect of the

increased the single-ring aromatics up to 50% area, especially

the zeolite catalysts, which exhibited high cracking activities for
the isomerization and aromatization reactions as a result of
their microporous structures and high acidities.22,34 However,
in comparison to the catalytic pyrolysis of Br-HIPS, the zeolite
catalysts exhibited less impact on Br-ABS in terms of the
formation of single-ring aromatics. The reason could be related
to the presence of the BFRs in the plastics, which would also
inuence the components of the pyrolysis oil.35,36 The higher
content of the BFR in Br-ABS (approximately 14.6 wt %
TBBPA) compared to the Br-HIPS sample (9.4 wt %
decaDBE) was more likely to deactivate the catalysts and
inhibit the catalytic cracking performance, resulting in less
production of lighter aromatics derived from Br-ABS pyrolysis.
Muhammad et al.23 indicated that the high conversion of
aromatic products during the catalytic pyrolysis of plastics was
attributed to high acidities of the zeolites, which promoted
more aromatization reactions to occur. Ates et al.37 suggested
that the catalyst properties of the pore structure and Si/Al ratio
dominated the catalytic eciency in the formation of aromatic
hydrocarbons in the pyrolysis oil, indicating that a higher Al
content in the catalyst was in favor of producing higher
aromatic compounds. However, Lee38 studied the eect of
dierent zeolites with various physicochemical properties on
the upgrading of pyrolysis wax oil obtained from municipal
waste plastics and indicated that the composition of the
upgraded products were inuenced by not only the acidities of
the catalysts but also the dierent surface areas and pore
structures. In comparison to the zeolite catalysts, in addition to
the acidities of the zeolite catalysts, the HY and H catalysts
with larger BET surface areas and pore volumes could produce
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additives on the initial thermal cracking of the ABS matrix,
leading to styrene formation.40,41 The presence of mesoporous
catalysts showed dierent impacts on the products in the oil.
All-silica MCM-41 resulted in an increased yield of ethylbenzene and cumene at the expense of styrene. However, active
Al2O3 exhibited little inuence on the products in the oil, which
only slightly increased the single- and two-ring group aromatics.
It was suggested that two competing reactions between crosslinking reactions and intermolecular hydrogen transfer took
place for the polymer cracking. The presence of mesoporous
catalysts could promote the former reactions and inhibit the
latter reaction.26,32
Few studies investigated the reaction pathways of catalytic
pyrolysis of Br-ABS in the presence of zeolites or mesoporous
catalysts.21,23,25 However, it was suggested that the main
polymeric structure found in Br-ABS was based on the PS
structure, which has been well-discussed by several authors.2426 Ojha et al.24 investigated the selectivity of the
products from catalytic fast pyrolysis of PS with dierent
zeolites using a micropyrolyzerGC/MS setup. They indicated
that the shape selectivity of zeolites promoted the high
conversion of value-added products, which can be attributed
to their specic properties, such as acidities and textural
properties. Furthermore, the possible reaction pathways were
proposed, indicating that there were two competing pathways
between cross-linking reactions and intermolecular hydrogen
transfer for the polymer cracking. Serrano et al.26 also proposed
that the catalytic pyrolysis of PS was involved in complex
reactions, including the primary radical mechanism resulting in
carbenium ions and then undergoing -scission and hydrogen
transfer, whereas competitive cross-linking reactions can be
promoted by the acidic catalysts. The two competing pathways
were also dominated by the reaction temperature and catalyst
type.28 Lopez et al.42 indicated that aromatic compounds can
not only be formed by the thermal mechanisms but also be
promoted by further secondary reactions to a greater extent
because of the solid acid catalyst. High catalytic activity of
mesoporous catalysts can be correlated well with their large
BET surface areas and uniform mesoporous structures.28,32
In this work, larger BET surface areas and pore volumes of
HY and H determined more single-ring aromatics produced in
pyrolysis oil than HZSM-5 in addition to the total acidities of
the zeolite catalysts. Moreover, the cross-linking reactions were
promoted by the zeolite catalysts, which resulted in more wax
produced than the mesoporous catalysts. The mesoporous
catalyst of all-silica MCM-41 with high catalytic activity was in
accordance with its largest BET surface area and uniform
mesoporous structure. However, as a result of the synergistic
eect between the polymer and the ame retardant additives, it
is dicult to distinguish the role played by the acidic sites and
the specic textural properties in selectively promoting the
involved reaction pathways for the catalytic pyrolysis of Br-ABS.
The results suggested that the dierent behaviors of the
catalysts on thermal cracking reactions can be explained by
their textural properties and acidity as well as the chemical and
structural nature of the polymers.
However, the total production of each compound in
pyrolysis oils is quite dierent from the content of each
compound in pyrolysis oils. It is suggested that the total
recovery production can be the denite function of the recovery
eciency for the feedstock recycling of plastics.21 The main
production of individual components in the pyrolysis oils is
depicted in Figure 5 and calculated by the following formula:

total production (mg/g plastic)

=

yield (wt%) m(oil)

1000 mg/g
m(plastic)

(2)

Figure 5. Main components of the oils from the pyrolysis of Br-ABS.

In comparison to thermal pyrolysis, the total production of

ethylbenzene and cumene tended to decrease in the presence of
HY and H zeolites, which might be due to the lower yields of
oil in the catalytic pyrolysis experiments. The HZSM-5 catalyst
obtained the highest production of toluene, ethylbenzene,
styrene, 1,3-diphenylpropane, and 1,3-diphenyl-1-butene than
the other two zeolite catalysts. The mesoporous catalysts
showed the highest production of alkyl aromatic compounds,
such as ethylbenzene, cumene, and 1,3-diphenylpropane, than
the zeolite catalysts. The results suggested that the HZSM-5
and all-silica MCM-41 catalysts might make the best recycling
use of Br-ABS plastic for chemical feedstocks.
3.3. Characterization of Char Residues. XRD and SEM
results of the char residues from the pyrolysis and catalytic
pyrolysis of Br-ABS are present in Figures 6 and 7, respectively.
The XRD patterns of the char residue obtained from the
pyrolysis of Br-ABS without catalysts in curve a of Figure 6
showed the presence of Sb and Sb2O3, which was due to the
existence of Sb2O3 additive in the raw material of Br-ABS. The
traces of Sb4O5Br2 were detected in the pyrolysis char, which
may indicate that the bromination reaction happened between
Sb2O3 and HBr released from the decomposition of TBBPA.40
Noteworthy, the presence of NH4Br was identied with small
intensity peaks, conrming the formation of this product
derived from the interaction between acrylonitrile in the ABS
matrix and the BFR additives. Furthermore, as a result of the
impurities of the ABS plastic, some small impurity peaks were
detected, such as the TiO2 additive.11,12,25 In the case of BrABS char residues from the catalytic pyrolysis by zeolite
catalysts in curves bd of Figure 6, the presence of Sb, Sb2O3,
and Sb4O5Br2 can also be detected with much weaker peaks
than that from the thermal pyrolysis. Moreover, the typical
peaks representing the standard phases of zeolites were
weakened or even disappeared in comparison to the fresh
zeolites.10 Considering that the zeolite catalysts are mainly
composed of SiO2 and Al2O3, which would not react with
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antimony tribromide was formed and soluble in the pyrolysis

oils, which was dicult to be detected using GC/MS.12,20,21
Thus, the total content of bromine in the pyrolysis oils should
be further investigated.
The bromine distribution in the pyrolysis products from
pyrolysis and catalytic pyrolysis of Br-ABS is illustrated in
Figure 8. In general, the bulk of bromine was found in the oil
and wax, followed by char and gas with very low
concentrations, as reported previously.10 During the thermal
pyrolysis of Br-ABS, approximately 99% of the bromine atoms
were found in the oil and wax products. The addition of
catalysts resulted in an apparently large decrease of the bromine
content in the oils accompanied by an increase of that in the
wax, especially the zeolite catalysts, which could transfer more
than 57.9% of total bromine into the wax. On the other hand, it
was found that the bromine concentration was slightly
increased in the char residues. It could be suggested that the
addition of catalysts may intensely enhance the secondary
reactions between the BFR additives and the volatile pyrolysis
products, thereby promoting the formation of organobromine
compounds in the wax. The presence of HY, H, and HZSM-5
zeolites signicantly reduced the bromine concentration in the
oil from 11.4 to 5.2, 4.4, and 5.67 wt %, respectively. However,
the presence of all-silica MCM-41 and Al2O3 catalysts reduced
the bromine content to 8.11 and 5.76 wt %, respectively. It was
clear that the H catalyst exhibited the most optimal
debromination performance, which transferred only 22.66%
of bromine in the Br-ABS polymer into the product oil. The
low content of bromine in the product oil was not only related
to the low yield of product oil but may also be attributed to the
secondary cross-linking reactions promoted by the acidic
catalyst, especially when the H zeolite was added, which
transferred much more bromine into wax.
The migration behavior of bromine during the Br-ABS plastic
pyrolysis depends signicantly upon the reaction conditions.21
Figure 8 suggests that a high bromine content in the oil without
catalysts was detected, whereas the catalysts exhibited great
eciency in removing bromine from the oils. The signicant
decrease of the bromine content in the oils with the addition of
zeolite catalysts might be attributed to their high porosities and
acidities, which enhanced the catalytic cracking performance of
brominated organic compounds.10,21 However, the high
bromine concentration in the oils still requires further
upgrading as clean fuels and feedstocks for commercial
applications.

Figure 6. XRD patterns of char residues from the pyrolysis of Br-ABS:

(a) thermal, (b) HY, (c) H, (d) HZSM-5, (e) all-silica MCM-41, and
(f) Al2O3.

evolved HBr and Sb2O3 synergist, the disappeared peaks of the

reacted zeolites could be related to the coke accumulation on
the surface of the catalysts, which may aect the textural
properties of the catalysts. With regard to the char residues in
the presence of mesoporous catalysts, the XRD patterns at 2
values from 5 to 80 were similar to that of the char residue
from the Br-ABS pyrolysis without catalysts.
From the SEM images of the char residues in Figure 7a, it
was clear that the char residue from the thermal pyrolysis of BrABS was aggregated with relatively uniform and compacted
small particles. However, the pyrolysis char exhibited inuence
on the morphologies of the zeolite catalysts, as shown in panels
bd of Figure 7. The reacted zeolites retained their particle
sizes and structures while partially covered with the carbon
residue. The particles of the zeolites were tightly aggregated
with amorphous impurities, which could be the inorganic
particles adhering to the char carbon particles, such as Sb2O3
and Sb4O5Br2. In contrast, the char residues exhibited less
impact on the morphologies of the mesoporous catalysts, as
shown in panels e and f of Figure 7. Most of the char was
accumulated outside of the catalysts; thereby, the morphologies
of the catalysts were similar to the fresh catalysts, as illustrated
in our previous work.10 The results indicated that part of
bromine, released from the pyrolysis of Br-ABS, could react
with Sb2O3 synergist by forming inorganic bromine compounds
left in the char residue. Moreover, the morphologies of the
zeolite catalysts were more easily inuenced by the char residue
than those of the mesoporous catalysts.
3.4. Distribution of the Total Br in the Pyrolysis
Products. In all of the experiments, only a relatively small
quantity of typical brominated compounds, for example,
bromobenzene, 1-(bromoethyl)benzene, 2-/4-bromophenol,
and 2,3,5-tribromophenol, was detected in the oils by GC/
MS with similar indexes of >90%, as shown in Table 3.
However, it is dicult to qualify and quantify all of the
organobromine compounds existing in the oils. It was found
that the yields of identied brominated compounds slightly
increased through the further degradation of TBBPA promoted
by the catalysts, resulting in a larger number of detectable
brominated organic compounds. On the other hand, plenty of

4. CONCLUSION
Three zeolite materials and two mesoporous solids with
dierent textural properties were investigated for their catalytic
eects on the pyrolysis of Br-ABS. The results indicated that
the presence of the zeolite catalysts exhibited greater inuence
on the product distribution of Br-ABS than the mesoporous
catalysts. The addition of HY and H zeolites tended to
decrease the oil yield, accompanied by an increase in the yields
of wax and gas. The HZSM-5 catalyst was favorable to
converting heavier hydrocarbons into lighter products, which
was due to the severity of the shape selectivity of zeolite
catalysts. The mesoporous catalyst of all-silica MCM-41
retained the oil production while signicantly reducing the
wax yield, which may be related to its largest BET surface area
and uniform mesoporous structure, allowing macromolecules
easier access to the catalyst channels for catalytic cracking.
Active Al2O3 exhibited negligible inuence on the product
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Figure 7. SEM images of char residues from the pyrolysis of Br-ABS: (a) thermal, (b) HY, (c) H, (d) HZSM-5, (e) all-silica MCM-41, and (f)
Al2O3.

distribution and preserved the liquid products. In terms of the

composition of the oil, the presence of catalysts promoted the
formation of valuable single-ring aromatics in oils. For the sake
of high-value material recovery, HZSM-5 and all-silica MCM-41
catalysts exhibited optimal performance for feedstock recycling
of Br-ABS plastic. In addition, the catalysts exhibited
pronounced debromination eciency, particularly the zeolite
catalysts, which could reduce bromine in the oil by over 50%
compared to thermal pyrolysis. Furthermore, the XRD and
SEM results indicated that the morphologies of the zeolites
were more easily inuenced by the char residue than those of
the mesoporous catalysts.
However, further investigations are required on the feedstock
recycling of ame-retarded plastics for the sake of resource
utilization and environmental conservation. Meanwhile, the
deactivation and recyclability of the spent catalyst need to be
further investigated as well as the upgrading process of pyrolysis
oils. Thus, this work could provide a framework for further

Figure 8. Distribution of total Br in the pyrolysis products from the

pyrolysis of Br-ABS.
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(19) Brebu, M.; Uddin, M. A.; Muto, A.; Sakata, Y.; Vasile, C. Energy
Fuels 2001, 15 (3), 565570.
(20) Bhaskar, T.; Matsui, T.; Uddin, M. A.; Kaneko, J.; Muto, A.;
Sakata, Y. Appl. Catal., B 2003, 43 (3), 229241.
(21) Hall, W. J.; Williams, P. T. J. Anal. Appl. Pyrolysis 2008, 81 (2),
139147.
(22) Lopez, A.; De Marco, I.; Caballero, B. M.; Laresgoiti, M. F.;
Adrados, A.; Aranzabal, A. Appl. Catal., B 2011, 104 (34), 211219.
(23) Muhammad, C.; Onwudili, J. A.; Williams, P. T. J. Anal. Appl.
Pyrolysis 2015, 113, 332339.
(24) Ojha, D. K.; Vinu, R. J. Anal. Appl. Pyrolysis 2015, 113, 349
359.
(25) Hall, W. J.; Miskolczi, N.; Onwudili, J.; Williams, P. T. Energy
Fuels 2008, 22 (3), 16911697.
(26) Serrano, D. P.; Aguado, J.; Escola, J. M. Appl. Catal., B 2000, 25
(2), 181189.
(27) Seddegi, Z. S.; Budrthumal, U.; Al-Arfaj, A. A.; Al-Amer, A. M.;
Barri, S. A. Appl. Catal., A 2002, 225 (1), 167176.
(28) Imani Moqadam, S.; Mirdrikvand, M.; Roozbehani, B.;
Kharaghani, A.; Shishehsaz, M. Clean Technol. Environ. Policy 2015,
17 (7), 18471860.
(29) Liu, M.; Zhuo, J. K.; Xiong, S. J.; Yao, Q. Energy Fuels 2014, 28
(9), 60386045.
(30) Marcilla, A.; Gomez-Siurana, A.; Quesada, J. C. G.; Berenguer,
D. Polym. Degrad. Stab. 2007, 92 (10), 18671872.
(31) Blazso, M.; Czegeny, Z. J. Chromatogr. A 2006, 1130 (1), 91
96.
(32) Aguado, J.; Serrano, D. P.; Miguel, G. S.; Escola, J. M.;
Rodrguez, J. M. J. Anal. Appl. Pyrolysis 2007, 78 (1), 153161.
(33) Predel, M.; Kaminsky, W. Polym. Degrad. Stab. 2000, 70 (3),
373385.
(34) Murata, K.; Brebu, M.; Sakata, Y. J. Anal. Appl. Pyrolysis 2010, 89
(1), 3038.
(35) Brebu, M.; Bhaskar, T.; Murai, K.; Muto, A.; Sakata, Y.; Uddin,
M. A. Chemosphere 2004, 56 (5), 43340.
(36) Czegeny, Z.; Jakab, E.; Blazso, M.; Bhaskar, T.; Sakata, Y. J. Anal.
Appl. Pyrolysis 2012, 96, 6977.
(37) Ates, F.; Miskolczi, N.; Borsodi, N. Bioresour. Technol. 2013,
133, 44354.
(38) Lee, K. H. J. Anal. Appl. Pyrolysis 2012, 94, 209214.
(39) Castano, P.; Elordi, G.; Olazar, M.; Aguayo, A. T.; Pawelec, B.;
Bilbao, J. Appl. Catal., B 2011, 104 (12), 91100.
(40) Rzyman, M.; Grabda, M.; Oleszek-Kudlak, S.; Shibata, E.;
Nakamura, T. J. Anal. Appl. Pyrolysis 2010, 88 (1), 1421.
(41) Brebu, M.; Bhaskar, T.; Murai, K.; Muto, A.; Sakata, Y.; Uddin,
M. A. Polym. Degrad. Stab. 2004, 84 (3), 459467.
(42) Lopez, A.; De Marco, I.; Caballero, B. M.; Adrados, A.;
Laresgoiti, M. F. Waste Manage. 2011, 31 (8), 18528.

upgrading of pyrolysis oils for obtaining high-quality brominefree fuel oils.

AUTHOR INFORMATION

Corresponding Authors

*Telephone: +86-27-87542417. Fax: +86-27-87545526. E-mail:

yujie@hust.edu.cn.
*Telephone: +86-27-87542417. Fax: +86-27-87545526. E-mail:
sunlushi@hust.edu.cn.
Notes

The authors declare no competing nancial interest.

ACKNOWLEDGMENTS
This research was supported by the National Natural Science
Foundation of China (5156073), the Independent Research
Funds of the State Key Laboratory of Coal Combustion
(SKLCC) (FSKLCCB1503), and the Funds of Graduate
Innovation and Entrepreneurship Program of Huazhong
University of Science and Techno logy (HUST)
(0118650043). The authors acknowledge the extended help
from the Analytical and Testing Center of HUST and also
thank Chong Xiao at the Key Laboratory of Analytical
Chemistry for Biology and Medicine (Ministry of Education),
Wuhan University, for her help with the FE-SEM test.

REFERENCES

(1) Balde, C.; Wang, F.; Kuehr, R.; Huisman, J. The Global E-waste
Monitor2014; United Nations University, IASSCYCLE: Bonn,
Germany, 2015.
(2) McCann, D.; Wittmann, A. Solving the E-Waste Problem (Step)
Green Paper: E-waste Prevention, Take-back System Design and Policy
Approaches; United Nations University/Step Initiative: Bonn,
Germany, 2015.
(3) European Union (EU).. EC Directive 2002/96/EC of the
European Parliament and of the Council on Waste Electrical and
Electronic Equipment. Off. J. Eur. Union, L: Legis. 2003, 46, 2438.
(4) Ongondo, F. O.; Williams, I. D.; Cherrett, T. J. Waste Manage.
2011, 31 (4), 714730.
(5) Freegard, K.; Tan, G.; Morton, R. Develop a Process To Separate
Brominated Flame Retardants from WEEE Polymers; Waste & Resources
Action Programme (WRAP): Banbury, U.K., 2006; Project PLA-037.
(6) Tang, Z.; Huang, Q.; Cheng, J.; Yang, Y.; Yang, J.; Guo, W.; Nie,
Z.; Zeng, N.; Jin, L. Environ. Sci. Technol. 2014, 48 (3), 15081516.
(7) Yang, X.; Sun, L.; Xiang, J.; Hu, S.; Su, S. Waste Manage. 2013, 33
(2), 462473.
(8) Ma, C.; Sun, L.; Jin, L.; Zhou, C.; Xiang, J.; Hu, S.; Su, S. Fuel
Process. Technol. 2015, 135, 150156.
(9) Wu, H.; Shen, Y.; Ma, D.; An, Q.; Harada, N.; Yoshikawa, K.
Open J. Ecol. 2015, 05 (04), 136146.
(10) Ma, C.; Yu, J.; Wang, B.; Song, Z.; Xiang, J.; Hu, S.; Su, S.; Sun,
L. Fuel Process. Technol. 2016, DOI: 10.1016/j.fuproc.2016.01.018.
(11) Wu, H.; Shen, Y.; Harada, N.; An, Q.; Yoshikawa, K. Energy
Environ. Res. 2014, DOI: 10.5539/eer.v4n3p105.
(12) Hall, W. J.; Williams, P. T. Energy Fuels 2006, 20 (4), 1536
1549.
(13) Jakab, E.; Uddin, M. A.; Bhaskar, T.; Sakata, Y. J. Anal. Appl.
Pyrolysis 2003, 6869, 8399.
(14) Hall, W. J.; Bhaskar, T.; Merpati, N. M.; Muto, A.; Sakata, Y.;
Williams, P. T. Environ. Technol. 2007, 28 (9), 10451054.
(15) Wang, R.; Xu, Z. Waste Manage. 2014, 34 (8), 145569.
(16) Lam, S. S.; Liew, R. K.; Jusoh, A.; Chong, C. T.; Ani, F. N.;
Chase, H. A. Renewable Sustainable Energy Rev. 2016, 53, 741753.
(17) Buekens, A.; Yang, J. J. Mater. Cycles Waste Manage. 2014, 16
(3), 415434.
(18) Brebu, M.; Uddin, M. A.; Muto, A.; Sakata, Y.; Vasile, C. Energy
Fuels 2001, 15 (3), 559564.
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