ASB Pyrolisis

R&D NOTES
Fuel Oil from AcrylonitrileButadieneStyrene

Copolymers Using a Tandem PEG-Enhanced
DenitrogenationPyrolysis Method
Q. Zhou, J. W. Yang, A. K. Du, and Y. Z. Wang
State Key Laboratory of Polymer Materials Engineering, Center for Degradable and Flame-Retardant Polymeric
Materials (ERCEPM-MoE), College of Chemistry, Sichuan University, Chengdu 610064, China
J. M. N. Van Kasteren
TU/e Innovationlab, Eindhoven University of Technology, 5600 MB Eindhoven, The Netherlands
DOI 10.1002/aic.11947
Published online August 11, 2009 in Wiley InterScience (www.interscience.wiley.com).
Keywords: degradation, catalysis, pyrolysis, recycling, denitrogenation, hydrolysis,

poly(ethylene glycol)
Introduction
Recycling of waste electric and electronic equipments
(WEEE) polymers has drawn much attention recently.
Various recycling methods have been adopted, and among
them, thermal degradation of WEEE polymers into fuel has
been regarded as one of the most promising methods.1 However, in the process of recycling of acrylonitrilebutadiene
styrene (ABS) copolymers, which is a widely used polymer
in electric and electronic industry, thermal degradation will
produce HCN, NOX, as well as complicated nitrogen-containing organic compounds that will not only cause environmental pollution but also cause the produced liquid to fail as
fuel.2 Therefore, the denitrogenation of WEEE plastics is a
must for this process. Catalysts such as a-FeOOH, Fe-C,
Ca-C, CaCO3, and Y zeolite were used during pyrolysis, but
the denitrogenation effects are limited.3,4 Moreover, the catalysts may encounter the problems, such as poisoning, short
catalyst life, and poor regeneration ability, which increases
the difculties of this process. On the other hand, hydrothermal methods were adopted for denitrogenation both before
and after pyrolysis,57 but the denitrogenation effects are still
unsatisfying. Moreover, relative high temperatures and
pressures are needed, which requires the use of expensive
facilities. Therefore, the development of highly efcient
Correspondence concerning this article should be addressed to Q. Zhou at
qzhou@scu.edu.cn.
C 2009 American Institute of Chemical Engineers
V
3294
denitrogenation of ABS under mild conditions is an area of

considerable importance.
By analysis of the molecule structure of ABS, it can be
seen that the complicated nitrogen-containing compounds
during pyrolysis just come from the nitrile group of ABS.
Therefore, it is reasonable to assume that to replace the
nitrile group with other groups without nitrogen element
before pyrolysis can effectively reduce the nitrogen
content in oil. In this article, ABS is treated using a tandem poly(ethylene glycol) (PEG)-enhanced alkaline denitrogenationpyrolysis method according to the structure
and thermal degradation properties of ABS, that is, rst
ABS is denitrogenated using PEG as a phase-transfer catalyst to enhance the denitrogenation efciency, then the
denitrogenated ABS (DABS) is pyrolyzed to get clean
fuels (Scheme 1). This method has the advantage of high
denitrogenation efciency under mild reaction conditions
and of decreasing the probability of forming complicated
nitrogen-containing compounds during pyrolysis, which
are difcult to eliminate. In addition, it is benecial to
obtain clean fuel without using expensive denitrogenation
catalysts during pyrolysis.
Experimental
Materials
Acrylonitrilebutadienestyrene (ABS) 0215A, Sinopec
Group, China, N%:7.4 wt % was used. All other chemicals
were of analytical grade.
December 2009 Vol. 55, No. 12
AIChE Journal
Scheme 1. A two-step process for thermochemical recycling of ABS.
PEG-enhanced alkaline denitrogenation

Alkaline denitrogenation of ABS was carried out at 160 C

for 2 h in a 60-mL stainless reactor equipped with a thermometer. In a typical experiment, 1 g NaOH was dissolved
in 5 mL PEG600, and then added to the ABS solution of
dioxane (ABS/DOA 1 g/5 mL). After reaction, the product
was precipitated in acetic acid solution and separated, then
washed with distilled water until pH 7, then dried under
vacuum at 60 C for 24 h before characterization.
The thermogravimetric analysis (TGA) experiments were

performed with a TA SDTQ600 thermogravimetric analyzer
(TA, USA). For each run, about 10 mg of samples was
heated from 30 to 600 C at a heating rate of 10 C min1
under nitrogen with a owing rate of 30 mL min1. The
thermogravimetric weight loss curve (TG, %) and the derivative curve of the weight loss (DTG, %/ C) were recorded as
a function of time and temperature.
Thermal degradation procedures
Results and Discussion
The thermal degradation reaction was carried out in a

glass reactor by batch operation as reported earlier.8 In a
typical experiment, about 10 g of materials was added to the
reactor. The air of the reactor was purged out with a nitrogen ow of 30 mL min1. The reactor was heated from
room temperature to 120 C during 20 min and the temperature was held for 30 min. Then, the temperature was
increased from 120 to 500 C at a heating rate of 10 C
min1 and held until no liquid was produced. The products
of degradation were classied into three groups: liquid products, which are condensable at 0 C, gaseous products, and
residue.
Before pyrolysis, alkaline denitrogenation of ABS was

conducted. The enhancing effects of PEG on denitrogenation
of ABS are clearly shown in Figure 1. For ABS/DOA/NaOH
system, the infrared spectrum of the product is similar to
that of ABS, suggesting that the conversion of nitrile group
is very low with only NaOH at mild conditions. However,
with the addition of PEG600, the strength of the ACN
stretching band (2245 cm1) obviously decreases, at the
same time new peaks assigned to ACOANH2 (1670 cm1 )
and ACOOH (1705 cm1) appear, indicating a readily transformation of nitrile groups. Accordingly, element analysis
proves that the nitrogen content is decreased from 7.4 wt %
for ABS to 3.5 wt % for DABS using PEG, resulting a
52.7% denitrogenation efciency. The weight increase of
Product characterization
The Fourier transform infrared spectra of ABS and DABS
were measured with a NICOLET6700 apparatus (Thermo
Electron Corporation, USA). Elemental analysis (C, H, and
N) of the ABS, DABS, and pyrolysis oils was determined
with an elemental analyzer (Thermo electron Flash EA1112,
USA).
The pyrolysis oils were analyzed using an Agilent HP
6890N gas chromatography equipped with a 30 m 0.25
mm 0.25 lm DB-5 capillary column. Helium was the carrier gas at a ow rate of 0.8 mL min1. The column temperature was programmed from 35 (kept for 5 min) to 210 C at
5 C min1 and then to 290 C at 10 C min1. The nal temperature was held at 290 C for 20 min. Based on the GC
analysis, the carbon number distribution of the liquids was
determined using NP-gram method.9
AIChE Journal
Figure 1. Infrared spectra of ABS and its alkaline denitrogenation products.
Published on behalf of the AIChE
DOI 10.1002/aic
3295
Figure 2. The TGA and DTG curves of ABS and DABS.
ABS after hydrolysis (6.9 wt %) is lower than the theoretical

value (9.6 wt %) because of use of small amounts of samples and the losses during sample handling. It is reported
that for cyano-containing polymers in which the nitrile
groups are mostly isolated, alkaline hydrolysis is analogous
to the hydrolysis of low-molecular-weight mononitriles.
The nitrile groups are rst transformed to amide groups,
then to carboxylate groups.10 Akimoto et al.7 obtained
40.1% denitrogenation efciency through hydrothermal
treatment with alkaline aqueous solution at the temperature
as high as 300 C. In our process, PEG probably forms
chelates like 18-crown-6-like structure occurring at the
terminus of the polymer chain,11 therefore resulting in the
more effective solvation of the sodium cation that
increases the reactivity of the base for nitrile group hydrolysis in dioxane, thus enhance the denitrogenation
efciency of ABS. Consequently, highly efcient denitrogenation can be realized at low temperatures when compared with normal denitrogenation processes, which
reduces the energy consumption of the process and due to
the mild conditions the corrosion effects, thus lowering the
overall process costs signicantly.
The DABS is used for pyrolysis experiment, and the
results are compared with those of pyrolysis of ABS. Interestingly, as high as 94.1% decrease of nitrogen content in oil
was obtained (from 1.7 wt % for ABS to 0.1 wt % for
DABS). Thermal degradation of polyacrylamide and its
copolymers produce a multitude of compounds including
NH3, H2O, glutarimides, and CO2.12 Therefore, for DABS, a
copolymer of polyacrylamide, most part of nitrogen originally in DABS is transferred to the gas phase as ammonia,
which was proved by the smell of ammonia released during
experiment. Ammonia can be easily absorbed in water and
used for industrial applications or environmentally sound disposal. It was reported that even though the iron-based and
calcium-based catalysts possess good dechlorination abilities,
they only exhibited 1030 wt % of denitrogenation ability
for pyrolysis oil.4 Our results conrm that effective denitrogenation of ABS before pyrolysis is benecial to produce
clean oil even without using denitrogenation catalysts during
pyrolysis.
Moreover, the DABS shows different thermal degradation
behaviors compared with ABS. From TGA tests (Figure 2),
it can be seen that the initial degradation temperature of
ABS (Ti: 5% weight loss) is shifted from 370.2 to 302.7 C,
and the peak temperature (Tmax) from 416.8 to 400.9 C.
These results strongly prove an easier degradation of DABS
compared with that of ABS.
In addition, the product yield is obviously changed (Table
1), that is, the liquid yield is decreased from 84.9 to 64.3 wt
%, whereas the gas yield is sharply increased from 7.9 to
21.7 wt %. For the liquid product distribution (Figure 3), it
can be seen that the heavy components obviously decrease,
particularly the [C25 components are prominently decreased
from 24.6 wt % (ABS) to 2.9% (DABS), and the light
components increase, suggesting a more effective pyrolysis
process and better oil quality for DABS. More research is
underway conrming these facts.
Conclusions
In conclusion, the tandem PEG-enhanced alkaline denitrogenationpyrolysis method possesses high denitrogenation
efciency under mild reaction conditions, which is benecial
to produce clean oil via pyrolysis. Moreover, the DABS
shows different thermal degradation behavior compared with
ABS, that is, thermal degradation at lower temperatures
and better oil quality with almost 10 times lower quantities
of heavy components. Optimization of the hydrolysis
conditions will decrease the nitrogen content in DABS,
stressing more the potential of this method for denitrogenation
of N-containing polymers.
Table 1. Product Yields from Thermal Degradation of ABS

and DABS
Product Yield (wt %)
Samples
ABS
DABS
3296
Liquid
(L)
Residue
(R)
Gas
(G)
Nitrogen Content
in Liquid (wt %)
84.9
64.3
7.2
14.0
7.9
21.7
1.7
0.1
DOI 10.1002/aic
Figure 3. Carbon number distribution of thermal degradation of ABS and DABS.
AIChE Journal
Acknowledgments
The authors thank the nancial support of the 863 program (Contract
No: 2007AA06Z325) and the National Science Fund for Distinguished
Young Scholars (50525309).
Literature Cited
1. Kaminsky W, Hartmann F. New pathways in plastics recycling.
Angew Chem Int Ed. 2000;39:331332.
2. Brebu M, Uddin MA, Muto A, Sakata Y, Vasile C. Composition of
nitrogen-containing compounds in oil obtained from acrylonitrile-butadiene-styrene thermal degradation. Energy Fuels. 2000;14:920928.
3. Bozi J, Czegeny Z, Blazso M. Conversion of the volatile thermal
decomposition products of polyamide-6,6 and ABS over Y zeolites.
Thermochim Acta. 2008;472:8494.
4. Brebu M, Bhaskar T, Murai K, Muto A, Sakata Y, Uddin MA. Removal of nitrogen, bromine, and chlorine from PP/PE/PS/PVC/ABSBr pyrolysis liquid products using Fe- and Ca-based catalysts. Polym
Degrad Stab. 2005;87:225230.
5. Akimoto M, Sato T, Nagasawa T. Hydrothermal denitrogenation of
fuel oil derived from municipal waste plastics in a continuous
packed-bed reactor. Ind Eng Chem Res. 2003;42:20742080.
AIChE Journal
6. Akimoto M, Murayama Y, Ochiai Y, Inomata S, Sakai T, Sangu T,

Yanagi K. Fuel oil production from municipal waste plastics pretreated with aqueous alkaline solutions. J Chem Eng Jpn. 2004;37:
14781487.
7. Akimoto M, Yanagi K, Sangu T. Behavior of the nitrogen atoms in
nylon, polyurethane and ABS during fuel oil production from
municipal waste plastics. J Chem Eng Jpn. 2005;38:947951.
8. Zhou Q, Lan WW, Du AK, Wang YZ, Yang JW, Wu YH, Yang KK,
Wang XL. Lanthania promoted MgO: simultaneous highly efcient
catalytic degradation and dehydrochlorination of polypropylene/polyvinyl chloride. Appl Catal B Environ. 2008;80:141146.
9. Murata K, Makino M. Nippon Kagaku Kaishi. 1975;1:192200.
10. Zilberman EN. The reaction of nitrile-containing polymers. Russ
Chem Rev. 1986;55:3948.
11. Kimura Y, Regen SL. Poly(ethy1ene glycols) are extraordinary catalysts in liquid-liquid two-phase dehydrohalogenation. J Org Chem.
1982;47:24932494.
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Manuscript received Dec. 2, 2008, and revision received Apr. 19, 2009.
DOI 10.1002/aic
3297

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R&D NOTES

Fuel Oil from AcrylonitrileButadieneStyrene

Keywords: degradation, catalysis, pyrolysis, recycling, denitrogenation, hydrolysis,

denitrogenation of ABS under mild conditions is an area of

December 2009 Vol. 55, No. 12

Scheme 1. A two-step process for thermochemical recycling of ABS.

PEG-enhanced alkaline denitrogenation

Alkaline denitrogenation of ABS was carried out at 160 C

The thermogravimetric analysis (TGA) experiments were

Thermal degradation procedures

Results and Discussion

The thermal degradation reaction was carried out in a

Before pyrolysis, alkaline denitrogenation of ABS was

December 2009 Vol. 55, No. 12

Figure 1. Infrared spectra of ABS and its alkaline denitrogenation products.

Published on behalf of the AIChE

Figure 2. The TGA and DTG curves of ABS and DABS.

ABS after hydrolysis (6.9 wt %) is lower than the theoretical

Table 1. Product Yields from Thermal Degradation of ABS

Figure 3. Carbon number distribution of thermal degradation of ABS and DABS.

Published on behalf of the AIChE

December 2009 Vol. 55, No. 12

December 2009 Vol. 55, No. 12

6. Akimoto M, Murayama Y, Ochiai Y, Inomata S, Sakai T, Sangu T,

Published on behalf of the AIChE

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