Journal of Cleaner Production 271 (2020) 122186

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Journal of Cleaner Production

journal homepage: www.elsevier.com/locate/jclepro

Pyrolysis-gasification of wastes plastics for syngas production using

metal modified zeolite catalysts under different ratio of nitrogen/
oxygen
M. Al-asadi , N. Miskolczi *, Z. Eller
University of Pannonia, Faculty of Engineering, Institute of Chemical Engineering and Process Engineering, MOL Department of Hydrocarbon & Coal
Processing, H-8200, Veszpr
em, Egyetem u. 10, Hungary

a r t i c l e i n f o a b s t r a c t

Article history: The aim of this study was the syngas production by the gasification of plastic waste (polyethylene,
Received 8 January 2020 polypropylene and terephthalate polyethylene). Ca, Ce, La, Mg and Mn were used to promote the Ni/ZSM-
Received in revised form 5 catalyst in order to enhance the production of higher syngas yield. The modified catalysts can enhanced
1 May 2020
the reaction rate of the pyrolysis process and resulting in high syngas in the product yields. Especially
Accepted 10 May 2020
Available online 17 June 2020
cerium, lanthanum promoted catalysts can enhance the yield of syngas. The effect of the reaction
temperature and nitrogen/oxygen ratio of the carrier gas was also investigated. The maximum syngas
Handling editor: Prof. Jiri Jaromir Klemes production was obtained with lanthanum catalyst (112.2 mmol/g (95%N2 and 5%O2), and 130.7 mmol/g
(90%N2 and 10%O2) at 850
C. Less carbon depositions was found at 850
C or even by the using of
Keywords: catalyst and more oxygen in the carrier gas. The oxygen content of the pyrolysis-gasification atmosphere
Syngas had a key role to the syngas yield and affects significantly the carbon-monoxide/carbon-dioxide ratio.
Waste plastic Catalysts can also accelerate the methanization reactions and isomerize the main carbon frame.
Transition metal Increasing in both temperature and oxygen in the atmosphere led to higher n-paraffin/n-olefin ratio and
Pyrolysis-gasification
more multi-ring aromatic hydrocarbons in pyrolysis oils. The concentration of hydrocarbons containing
Nitrogen/oxygen ratio
oxygen and branched compounds was also significantly affected by catalysts.
© 2020 The Author(s). Published by Elsevier Ltd. This is an open access article under the CC BY license
(http://creativecommons.org/licenses/by/4.0/).

1. Introduction minimizing of the pollutants and fossil fuels consumption.

In spite of climate change and the several environmental
problems, fossil fuels are still the main source of energy. For
example in European countries and regardless of the new energy
policies, fossil fuels are still the main source for the energy con-
sumption (Martins et al., 2018). The limitation of fossil fuel re-
sources and the large amount of toxic gases that released to the
atmosphere due to its combustion are the main reasons for the
replacement of the conventional fuel with clean resources. More-
over, serious energetic, economic or social problems can be avoided
by lowering the dependence on the fossil fuel as a source of energy
and mitigate its impact. Thus, many researches are focusing to find
alternative ways to produce energy that can contributes in
* Corresponding author. University of Pannonia, Chemical Engineering and Pro-
cess Engineering Institute, MOL Department of Hydrocarbon and Coal Processing,
Egyetem u. 10, Veszpre
m, H-8200, Hungary.
E-mail address: mnorbert@almos.uni-pannon.hu (N. Miskolczi).
Nowadays, plastic materials are used widely in different appli-
cation including; packaging, bottles, construction, automotive in-
dustry and so on (Anuar Sharuddin et al., 2016). The economic
expansion, fast growing, development and the improvement of
living conditions contributed to significant increasing of global
plastic consumption in dramatically. According to recent statistics,
the worldwide plastic production almost reached the 360 million
tons in 2018 and Europe ranks the second in global plastic pro-
duction with 62 million tons (Plastic Europe, 2019). Large amount
of plastic items are converted into plastic waste annually due to the
consequence of the high production and consumption (Verma
et al., 2016). In spite of the increasing of recycling processes, 25%
of waste plastics are still sending to landfill (Plastic Europe, 2019).
Therefore, huge quantity of plastic wastes are accumulated in the
landfill sites as these wastes are known as non-biodegradable
which have negative effects on the climate and living organisms
€
(Ozsin and Pütün, 2018). Plastics are materials with hydrocarbons
base by petroleum products (Sogancioglu et al., 2017). Polystyrene
(PS), polyethylene terephthalate (PET), polypropylene (PP), high

https://doi.org/10.1016/j.jclepro.2020.122186
0959-6526/© 2020 The Author(s). Published by Elsevier Ltd. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
2 M. Al-asadi et al. / Journal of Cleaner Production 271 (2020) 122186
density polyethylene (HDPE) and low density polyethylene (LDPE)
are classified as the most common used plastics (Hartulistiyoso
et al., 2015).
To utilize plastic wastes and obtain beneficial products, waste to
energy technology is considered as an attractive and feasible way to
produce renewable energy from the unwanted or even contami-
nated waste (Bulgariu et al., 2018). In addition, the recycling of
plastic waste can decreasing the disposal of these wastes and save
the environment from their impacts (Lopez et al., 2018). Energy
recovery via pyrolysis and gasification of waste plastic are known as
the most efficient and sustainable technique among the other
existing and management methods (Yao et al., 2017). In pyrolysis
process, plastics wastes are decomposed at high temperature with
the presence of catalyst to obtain syngas and other valuable prod-
ucts. Plastic wastes should be decomposed in their individual form
or mixed with other wastes or lower value materials (Ng et al.,
2018). On the other hand, high temperature partial oxidation of
coal, hydrocarbons or polymers is also widely used method for
syngas production. The products obtained from pyrolysis process
have lower impact on the environment and can be used as fuel or
feedstock for other petrochemical processes e.g. in the refinery or
other chemical related industry (e.g. ammonia, urea, methanol or
ethanol production). Recently Wang et al. investigated the direct
conversion of syngas to alcohol (Wang et al., 2020). They reported,
that zeolite catalysts containing RhMn nanoparticle showed ad-
vantageous role in the production of oxygenates from syngas. The
properties and yields of pyrolysis products are influenced by many
factors such as type of raw materials, reaction temperature, carrier
gas, reactor and catalyst type. However, syngas production via
partial oxidation of waste plastics can be also promoted by the
addition of the catalysts, especially by transition metal loaded
zeolites.
Different catalysts were used in catalytic pyrolysis and gasifi-
cation of waste plastic in order to improve the product selectivity.
The selection of appropriate catalyst for the decomposition reaction
of plastic waste can improve the conversion rate and promoting the
high gas products and syngas yields. Based on recent literatures,
nickel and metal promoters were proposed as the appropriate
option due to their high stability and activity (Saad and Williams,
2016). Others examined the performance of catalysts after the
addition of various promoters such as Mg, Co, and Cu. Mg promoted
Ni catalyst showed promising results in case of tri-reforming of coal
bed methane to syngas (Sun et al., 2012). While the Pt addition to Ni
catalyst did not result significant change in the dry reforming ac-
tivity of methane, adding Pt to CeZrO2 catalyst showed high sta-
bility due to oxygen spill over (Mahoney et al., 2014). The NiCo/
Al2O3ZrO2 catalyst has higher activity and selectivity compared to
Ni/Al2O3ZrO2 in case of dry reforming (Sharifi et al., 2014). The
hierarchical nanocomposite structure of CuNi/SiO2 presented very
good catalytic activity and thermal stability during dry reforming
reactions above 700
C (Wu et al., 2015). They reported that these
promoters can hinder the formation of carbon on the catalyst sur-
face which enhancing the catalyst activity towards syngas pro-
duction. Also, zeolite catalysts proved their efficiency as catalyst
supporters towards the improvement of pyrolysis products
(Sriningsih et al., 2014). High acidity, high surface area and
advanced pore structure are the main advantages of using synthetic
zeolite catalysts. However, not only synthetic catalysts, but also
natural zeolite and other lower value products, e.g. ash should be
efficiently used for catalyst synthesis to enhanced thy syngas pro-
duction (Loy et al., 2018). The kinetic barrier of CeC cracking re-
action can be decreased by using of zeolite catalysts (Wang et al.,
2020). Yao et al. (2018) performed the pyrolysis of HDPE for syn-
gas production over various zeolite supported Ni catalysts. Among
the different catalysts, ZSM-5 showed high efficiency in terms of
syngas production, thermal stability and coke resistance (Yao et al.,
2018). In addition, Wu and Williams (2009), performed the
pyrolysis-gasification of polypropylene using Ni/ZSM-5 and Ni/
CeO2/ZSM catalyst. They found that the presence of theses catalysts
enhanced the hydrogen production (Wu and Williams, 2009). On
the other hand, the carrier gas or atmosphere is considered as one
of the main process parameters that affected the pyrolysis and
gasification performance. In spite of that pyrolysis process is carried
out in the absence of oxygen but a controlled range of O2 concen-
tration could improve the yields of desired products (Xue et al.,
2017). According to the results of previous studies, the addition of
oxygen carrier would greatly enhance the gasification efficiency
and reduce the tar concentration as well (Rapagna  et al., 2000).
Zhifeng Hu et al., previously studied the effect of oxygen content in
carrier on syngas production through gasification of microalgae
(Hu et al., 2019). They reported that yields of hydrogen and carbon
monoxide were increased with the addition of oxygen carrier.
Regarding the catalyst disadvantages, the deactivation as function
of reaction time, the mixing with the raw material, the cost ne-
cessity and further handling of the used catalysts are the most
important challenges.
There is lack of information about the effect of second metal
promoters on the catalyst performance for waste plastic partial
oxidation-reforming. The aim of the current study is to investigate
the effect of the modified catalysts towards the pyrolysis-
gasification of waste plastic mixture. Ni/ZSM-5 based catalysts
were synthetized and modified by different bimetallic promoters;
calcium (Ca), cerium (Ce), lanthanum (La), magnesium (Mg) and
manganese (Mn). The influence of process parameters; reaction
temperature and carrier gas on the product yield, syngas produc-
tion, gas and pyrolysis oil composition were also discussed.
2. Experimental
2.1. Raw materials
Mixtures of HDPE (14%), LDPE (17%), PP (19%), PET (45%) and
others (5%) were used as raw material obtained from waste bin.
Raw materials were shredded and crashed into particle size up to
3 mm. The results of the proximate and ultimate analyses show that
the raw materials contain carbon of 72%, hydrogen of 11%, oxygen of
16% and nitrogen of 1%. The moisture and ash content was 1.1% and
2.4%, respectively.
To increase the yields of volatiles and syngas (both hydrogen
and CO) or affect the liquid product structure, different
Me(Me ¼ Ca, Ce, La, Mg and Mn)/Ni-ZSM-5 were used. The zeolite
catalyst supporter was loaded with nickel by wet impregnation (1M
Ni(NO3)2∙6H2O), then the obtained Ni/ZSM-5 catalyst was treated
at 650
C for 5 h in air. The Me/Ni/ZSM-5 catalysts were prepared by
dissolution of CaCl2, CeSO4∙4H2O, LaCl3∙7H2O, Mg(NO3)2 and
MnCl2∙4H2O, using the previously synthesized Ni/ZSM-5 catalyst.
The Ni/ZSM-5 catalyst was stirred in the solutions till 4h at 80
C.
Then the Me/Ni/ZSM-5 catalysts were dried for 10 h at 110
C and
then treated at 600
C for 5 h in air. The main properties of the
catalysts are summarized in Table 1. The catalyst morphology was
analysed by N2 adsorption/desorption isotherms (Micromeritics
ASAP 2000-type instrument (ASAP 2000 operational program
V1.03)). The catalyst surface area was measured by Brunauer-
Emmett-Teller method (BET) with nitrogen, while Barrett-Joyner-
Halenda model (BJH) was used to determine the SBJH. A Fritsch
Analysette 22 instrument based on the Fraunhofer theory was used
to calculate the catalyst average grain diameter. The average grain
size of the catalysts was between 1.97 and 2.11 mm. The nickel
content of the catalysts was between 3.73 and 4.82%, while the
metal content was between 1.92 and 2.03%. The incorporation of
 M. Al-asadi et al. / Journal of Cleaner Production 271 (2020) 122186 3

Table 1
The main properties of the catalysts.

SBJH, m2/g Smicro, m2/g BET, m2/g Grain size, mm Si/Al Ni, % Me, %

Ni/ZSM-5 98.1 352 489 0.75 35.02 4.82 e

Ca/Ni/ZSM-5 93.8 210 419 0.73 30.15 3.73 1.92
Ce/Ni/ZSM-5 92.7 311 445 0.83 30.94 4.02 2.03
La/Ni/ZSM-5 90.9 305 408 0.63 31.82 3.76 1.93
Mg/Ni/ZSM-5 89.5 288 404 0.57 30.78 3.84 1.92
Mn/Ni/ZSM-5 92.4 281 395 0.87 30.24 3.79 1.99

second metals on the ZSM-5 structure can modify the catalyst
morphology, because the surface areas can be decreased in the
presence of second metals (Al-asadi and Miskolczi, 2020).
2.2. Pyrolysis process
A horizontal tubular furnace was used for pyrolysis. 550
C and
850
C temperatures were tested with the mass ratio of 5 g (raw
materials) and 2.5 g (catalyst) (Fig. 1). In our current work neither
steam nor CO2 was used, because the syngas production was
enhanced by partial oxidation (95/5 and 90/10 nitrogen/oxygen
ratio as carrier gas) and catalysts. 550 and 850
C were selected for
the pyrolysis, because the results would to be compared with
observation of earlier experiments using CO2 (Al-asadi et al., 2019).
Furthermore the gas and liquid fractions at 550
C and gases at
850
C has to be focussed. The pyrolysis-gasification in the presence
of steam or CO2 (dry reforming) are well investigated in the liter-
ature, but the partial oxidation process for syngas production in the
presence of catalysts is less studied. Therefore the effect of a
significantly lower oxygen ratio needed for the total combustion
with the 95/5 nitrogen/oxygen carrier gas ratio and the reaction
parameter leading to a higher oxidation rate with the 90/10 ni-
trogen/oxygen ratio was investigated. Pyrolysis-partial oxidation
reactions were kept till 20 min after the reactor reached the set
temperature. Gases had been driven through water cooled heat
exchanger (set temperature of 10
C), then the volume measured by
a gas flow meter and then collected in a Tedlar bag for GC-FID and
GC-TCD analyses. After the pyrolysis the products were weighted
and their yields were calculated based on the weight balance.
2.3. Analysis
The hydrocarbon composition of gases were analysed by GC-FID
instrument (DANI GC) using isotherm conditions (T ¼ 30
C). Two
columns were used for the analysis, Rtx PONA (100 m  0.25 mm,
surface thickness of 0.5 mm) and Rtx-5 PONA (100 m  0.25 mm,
surface thickness of 1 mm) columns.
For H2, CO and CO2 analysis a GC-TCD was used (Shimadzu GC-
2010 gas-chromatograph) equipped Carboxen™ 1006 PLOT column
(30 m  0.53 mm). During the analysis, the temperature was
elevated from 35
C (hold time 2 min) to 250
C at 40
C/min
heating rate, with the final temperature maintained for 5 min.
A DANI GC-FID was applied for pyrolysis oil analysis. The in-
strument was fitted with Rtx 1 dimetil-polysiloxan capillary col-
umn (30 m  0.53 mm, thickens of 0.25 mm). Sample was dissolved
in CS2, and then injected to the instrument. The initial temperature
was 40
C for 5 min, then the temperature was elevated by 8
C/min
till 340
C and it was kept at 340
C till 20 min. Both the injector and
detector temperature were 340
C.
3. Results and discussion
3.1. Product yields
The product yields are summarized in Fig. 2. Results well
demonstrate that catalysts have a great influence on the products,
especially the gas yield. The highest gas yield was obtained with the
Ni/ZSM-5 catalyst at 850
C independently from the pyrolysis-
gasification atmosphere, while the La and Mg promoted Ni/ZSM-5
catalyst resulted the highest gas yield at 550
C, in case of both
N2/O2 ratios. The addition of second metal on the Ni/ZSM-5 based
catalyst retained their effect on reducing the cracking reactions at
both temperatures. Therefore, a bit reduction in the amount of
gases was found by the loading of catalyst with the second metal. It
is accordance with results, that metal loading on the synthetic
zeolite supporters led to decreasing in surface area (Iliopoulou
et al., 2012). In general, the lower the catalyst surface area, the
less the cracking activity. Regarding to the effect of temperature, it
is clear, that the increasing in the temperature from 550 to 850
C
and the increasing in oxygen concentration in the carrier gas can
caused a significant change in the product yields.
The yield of gases was 22.4e35.8% at 550
C, while it was in the

Fig. 1. Pyrolysis process layout.

4 M. Al-asadi et al. / Journal of Cleaner Production 271 (2020) 122186
Fig. 2. Yield of products ((a) Gases; (b) Pyrolysis oil; (c) Char; (d) Carbon deposition).
range of 71.8e79.6% at 850
C using 95%/5% N2/O2 ratio or
25.8e37.1% (at 550
C) and 73.1e80.5% (at 850
C) using 90%/10%
N2/O2 ratio. The yields of gases could be significantly increased by
the increasing temperature and a bit by the increasing of the oxy-
gen content of the carrier gas. Regarding the temperature, espe-
cially the lower thermal stability of the CeC bonds at higher
temperature is blamed for more gases.
However, the result showed a visible effect in the amount of
liquid product by introducing the catalyst to the process. In one
hand, the highest liquid product yield (63.1%) was obtained by the
pyrolysis without catalyst at 550
C using 95%/5% N2/O2 ratio. On
the other hand, the liquid product yield could be significantly
decreased in presence of catalyst, while the forming of gas products
was higher due to the high cracking activity of the catalysts. The
cracking activity was caused by the significant acidity of the ZSM-5
catalyst supporter, which favoured to the formation of primary ions
to catalyse the further ionic initiated decomposition of hydrocar-
bons, especially by b-scission. However, the cracking reactions led
to carbon deposition on the surface of the catalyst, especially at
550
C. More char and carbon deposition on the catalyst surface
were found at 550
C. Comparing the two N2/O2 ratios it is
important to note, that significant reduction on the coke formation
was demonstrated by the using of 90%/10% N2/O2 ratio. For less
coke the partial CO2 excess is the reason. Due to the excess of CO2,
there is more possibility for the Boudouard reaction shifted towards
the formation of CO. In case of more oxygen, more CO2 can be ob-
tained (CþO2/CO2). Table 2 well demonstrates the excess of CO2
using 90%/10% N2/O2 ratio. The second metal on the Ni/ZSM-5
catalyst holds back the CeC cracking reactions and less gases and
carbon depositions were measured at both temperatures. There
was a significant char yield (14.5% and 12.9% at 550
C or 11.5% and
10.4% at 850
C) in case of catalyst free pyrolysis.
Compared to the amount of carbon deposits and char yields
obtained at different temperatures, less carbonaceous materials
was found at 850
C or even by the using of catalyst. This phe-
nomenon could be explained by the reverse Boudouard reaction at
high temperature (CO2þC4CO). This reaction reduces the carbon
on the catalyst surface. It is well known, that over 650e700
C the
reaction is shifted toward the production of CO. Regarding the
different metals added to the Ni/ZSM-5 catalyst, it was found, that
the pyrolysis oil yield was the highest at 550
C using Mn/Ni/ZSM-5
catalyst (51.6%, 90%/10% N2/H2 ratio), while the using of Ce/Ni/ZSM-
5 catalyst resulted the highest oil yield at 850
C (9.7%, 90%/10% N2/
H2 ratio). The order of the efficiency of different metals was
different at the two tested temperatures from the aspect of product
yields. It is interesting result that same order in the second metals
was found by the using of both N2/O2 ratios. The yield of liquid
product decreased in the order of Mn>Ce>Ca>Mg>La at 550
C,
while the order was Ce>La>Ca>Mn>Mg at 850
C.
3.2. Gases
In case of the gasification, gases are the main products. The
compositions of gas products were followed by GC-TCD and GC-FID.
Results are summarized in Table 2. It was concluded, that the gas
products contained hydrogen, CO, CO2, methane and C2eC5 hy-
drocarbons. Significant increase in hydrogen concentration was the
main effect of the increased oxygen content in the carrier gas (90%/
10% N2/H2 ratio) in case of Ce/Ni-ZSM-5 and La/Ni-ZSM-5 catalysts.
Regarding the CO2, the higher oxygen content in the carrier gas can
increase the CO2 concentration at lower temperature and
decreased it at higher temperature. For increasing in CO2 concen-
tration the oxidation reaction could be blamed (Eq. (1))
CnHmþ nþm/2 O2 4 n CO2 þ m/2 H2O (1)
It is also well shown, that the syngas and CO2 quantity of the
obtained gases were significantly affected by the bimetallic cata-
lysts at both temperatures. In general, the concentration of CO2 was
lower at higher temperature in each case. Regarding both thermal
and thermo-catalytic pyrolysis, the concentration of methane was
significant at higher temperature. Without catalyst, the methane
concentration was higher at 850
C compared to that of at 550
C.
The increase in the methane concentration was the consequence of
the reverse reforming reaction (Eqs. (1) and (2)).
 M. Al-asadi et al. / Journal of Cleaner Production 271 (2020) 122186 5

Table 2
The composition of gases.

No-catalyst Ni/ZSM-5 Ca/Ni/ZSM-5 Ce/Ni/ZSM-5 La/Ni/ZSM-5 Mg/Ni/ZSM-5 Mn/Ni/ZSM-5

95% N2 e5% O2 T ¼ 550
C H2 7.3 9.9 10.4 15.2 11.5 9.8 10.7
CO 19.4 21.3 20.7 20.2 21.7 20.9 18.8
CO2 24.1 22.9 22.2 23.8 26.4 24.1 25.9
CH4 8.4 6.1 7.5 6.6 8.1 6.3 5.2
C2eC6 40.8 39.8 39.2 34.2 32.3 38.9 39.4
T ¼ 850
C H2 30.5 34.8 33.1 35.2 52.5 34.8 39.8
CO 12.4 22.9 21.1 23.9 25.8 20.6 23.7
CO2 12.1 12.8 14.0 18.9 11.7 12.6 14.2
CH4 8.4 10.2 11.4 9.6 5.5 11.9 12.6
C2eC6 36.6 19.3 20.4 12.4 4.5 20.1 9.7
95% N2 e10% O2 T ¼ 550
C H2 5.1 10.5 8.3 21.6 16.2 9.1 10.5
CO 17.6 18.7 18.2 21.8 24.5 18.6 15.2
CO2 38.6 29.4 30.6 33.8 32.6 31.7 31.6
CH4 6.8 7.3 8.9 5.9 8.4 7.2 6.1
C2eC6 31.9 34.1 34.0 16.9 18.3 33.4 36.6
T ¼ 850
C H2 27.2 38.4 32.2 44.6 55.2 35.1 38.8
CO 15.3 24.7 21.7 25.3 28.5 24.1 25.2
CO2 18.4 10.2 9.8 8.2 5.1 6.8 8.4
CH4 11.8 15.9 14.6 18.3 7.9 19.3 17.2
C2eC6 27.3 10.8 21.7 3.6 3.3 14.7 10.4

CO þ 3H2 4 CH4 þ H2O
CO2 þ 4H2 4 CH4 þ 2H2O
Both reactions are exothermic, the first reaction needs 206 kJ/
mol, while the second 164 kJ/mol energy. It is also clear, that not
only the used catalysts and the reactor temperature, but also the
nitrogen/oxygen ratio has also an important role to the reactions.
The C2eC5 hydrocarbons had the highest concentration at lower
temperature, which was followed by CO2, CO, hydrogen and
methane using 95%/5% N2/O2 ratio at 550
C.
Without catalyst, the temperature increasing from 550
C to
850
C can increase the methane content by 48.0% (using 95%/5%
N2/O2 ratio) and 63.2% (using 90%/10% N2/O2 ratio), which was
98.0% (using 95%/5% N2/O2 ratio) and 117.8% (using 90%/10% N2/O2
ratio) in the presence of Ni/ZSM-5 catalyst. Catalysts can accelerate
the methanization reactions. It is well known, that nickel can in-
crease the reaction rate of methanization, especially at lower
temperature. However the accelerating role is affected by many
factors, e.g. incorporation of other elements. Incorporation of Ce,
Mg and Mn into the Ni/ZSM-5 catalyst showed advanced properties
for methanization reactions, because significantly higher concen-
tration of methane was found by their application (108.7, 124.5 and
173.8% (using 95%/5% N2/O2 ratio) and 210.2, 168.1 and 182.0%
(using 90%/10% N2/O2 ratio), respectively). It is important to remark,
that the effect of calcium was less than that of the nickel-modified
ZSM-5 catalyst, while the presence of lanthanum resulted in a
significant reduction in methane producing. The methane con-
centration in gases obtained at 850
C can increase only by 34.1%
(using 95%/5% N2/O2 ratio) and 15.5% (using 90%/10% N2/O2 ratio) in
case of La/Ni/ZSM-5 catalyst. The more significant methanization
reactions in the presence of higher oxygen contents were primarily
due to the higher partial carbon dioxide content in the reactor.
Based on the before mentioned result, it can be clearly seen that by
the using of higher oxygen content, significantly higher carbon-
dioxide contents in the gas product could be measured without
catalyst. Due to the higher CO2 content, more methane can pro-
duced in the presence of catalysts at higher temperatures by
reverse reforming reaction. Based on the energy conditions of the
methanisation reactions, the CO2 based reactions were more likely
to occur than CO based, since the former requires 164 kJ/mol and
the latter 206 kJ/mol. The amount of CO and CO2 is also largely
determined by the Boudouard reactions (Eq. (4)), which is favoured
(2) by increasing temperature, e.g. shifting the equilibrium towards CO
at higher temperatures.
(3)
C þ CO2 4 2 CO (4)
It is interesting observation, that the incorporation of promoters
into the Ni/ZSM-5 catalyst structure, apart from La/Ni/ZSM-5, lower
CO/CO2 ratio was found at 550
C. However, at 850
C, only the Ca/
Ni/ZSM-5 catalyst had higher CO/CO2 ratios than that of Ni/ZSM-5
catalyst. The highest CO/CO2 ratio was found also in the case of La/
Ni/ZSM-5 (Fig. 3). Glancing data, it is also clear that the CO content
increased and the CO2 concentration decreased at higher temper-
atures, which could be further increased by the presence of cata-
lysts and increasing the oxygen content in the atmosphere. The
higher possibility of the Boudouard reaction was also supported by
the yields, because less carbon deposition both on the catalyst
surface and char was found at higher temperature. The C2eC5 linear
compounds had the highest quantity within the hydrocarbons,
which was the consequence of the high LDPE and HDPE content of
the raw materials (Fig. 4). The summarized concentration of poly-
ethylene was 31% in the raw material. It is well known, that the
linear structured polyethylene chains broken to linear hydrocar-
bons with high proportion, especially without catalysts.
Because of the raw material contain polypropylene, products
have branched hydrocarbon content (e.g. 2,2-dimethyl propane,
2,2-dimethyl butane, 2,3-dimethyl butane or 2-methly pentane).
The most significant effect of the catalysts is the isomerization of
main carbon frame, because the summarized concentration of
linear hydrocarbons significantly decreased, while that of branched
hydrocarbon increased in the presence of catalysts, especially using
550
C pyrolysis temperature (Eq. (5)).
(5)
Regarding the isomerization, the ratio of non-branched and
branched hydrocarbons was lower at higher temperature, which
6 M. Al-asadi et al. / Journal of Cleaner Production 271 (2020) 122186

Fig. 3. The ratio of H2/CO and CO/CO2. ((a) using 95% N2 and 5% O2; (b) using 90% N2 and 10% O2).

Fig. 4. The hydrocarbon composition of gases measured by GC-FID. ((a) Methane; (b) C2eC5 linear; (c) Cyclic; (d) C2eC5 branched).

corresponds to the isomerization of main carbon frame at higher
temperature independently from the oxygen content in the gasi-
fication atmosphere. It is important observation, that the incorpo-
ration of the second metal to the Ni loaded ZSM-5 catalyst had
significant effect to the isomerization reaction at 550
C, while only
slight effect was found at 850
C. The ratio of linear/branched hy-
drocarbons was 3.2 (at 550
C) and 2.0 (at 850
C) using 95%/5% N2/
H2 ratio and 3.9 (at 550
C) and 3.6 (at 850
C) using 90%/10% N2/H2
ratio without catalysts, respectively. However, it can be reduced to
1.5e3.1 and 1.6e3.5 at 550
C and 850
C with catalysts depending
on the atmosphere, respectively. During the isomerization of the
linear C2eC5 hydrocarbons, the intermediates cracked into
methane, hydrogen and carbon deposit. It is also clear, that less
both non-branched and branched hydrocarbons was found using
90%/10% N2/O2 ratio at both temperatures. However to calculate the
ratio of non-branched/branched hydrocarbons it is well shown,
that 95%/5% N2/O2 ratio favoured to the isomerization reactions at
both temperatures. The Ni/ZSM-5 catalyst (at both temperatures)
has the lowest ratio of non-branched/branched hydrocarbons using
95%/5% N2/O2 ratio, while the incorporation of La can supported the
branching reactions in 90% N2/10% O2 atmosphere at both 550
C
and 850
C.
Cyclopropane and cyclopentane was also detected in the
gaseous fraction. Their summarized concentration was less than
3.5%. The oxygen content in the gasification atmosphere did not
affected the concentration of the cyclic compounds at 550
C,
however more cyclopropane and cyclopentane were detected at
higher temperature in the presence of catalysts, while less in
catalyst free gasification.
Fig. 5 summarizes the calculated syngas yield related to raw
material. The yield of syngas (both H2 and CO) is significantly
increased as function of temperature and presence of catalysts.
Furthermore, the incorporation of selected second metals to the Ni/
ZSM-5 catalyst had an advanced effect for hydrogen and CO syn-
thesis. It is also clear, that the yield of syngas without catalyst was
also higher at 850
C, compared to each of the obtained syngas at
 M. Al-asadi et al. / Journal of Cleaner Production 271 (2020) 122186
Fig. 5. The hydrogen and carbon-monoxide yield in gases ((a) H2; (b) CO).
550
C (both without and with catalysts). This phenomenon can be
attributed to the increasing reaction rate in partial oxidation and
further reaction led to hydrogen and CO production. The possible
reaction scheme is summarized in Eqs. (6)e(8).
CnHm þ n/2 O2 4 n CO þ m/2 H2
CnHm þ n/2 H2O 4 n CO þ (mþn)/2 H2
CnHm þ n CO2 4 n CO þ m/2 H2
The catalysts can improve the syngas yield at both tempera-
tures. This observation can be explained by the cracking activity of
ZSM-5 supporter and the presence of transition metals. It is also
well known, that Ni can support the hydrogenation-
dehydrogenation reactions, while Rh has high activity in syngas
production by partial oxidation of hydrocarbons. Based on our
result, it is well shown, that nickel loaded catalysts or the second
metal on the catalyst surface (Al-asadi et al., 2019) can improve the
syngas yield due to the marked increased in the H2 and CO product
compared to non-catalytic process. Presumably, the second metals
on the Ni/ZSM-5 can act as promoter and significantly increase the
rate of the reactions led to elevated hydrogen production.
Comparing the 2 atm, more CO was found using 10% oxygen. This
was the consequence of the higher CO2 partial concentration. The
oxidation reactions were more likely to occur at higher oxygen
contents (90% N2/10% H2 atmosphere), leading to higher amounts
of CO2 in gases. Based on the Le Chatalier’s principle, the Bou-
douard reaction was shifted toward the formation of CO in case of
higher CO2 content of the reaction mixture, resulting in more CO.
The concentration of CO was significantly less than hydrogen at
both 550 and 850
C in all cases. The yield of CO can be increased by
only the incorporation of Ce and La compared that of Ni/ZSM-5 at
both temperatures and gasification atmosphere. However, Mn/Ni/
ZSM-5 catalyst can also increase a bit the CO concentration at
850
C. The relative increasing in the CO concentration was in the
range of 28.6% (decreasing, Mn/Ni/ZSM-5, at 550
C, 90%N2 and
10%O2) and 38.1% (La/Ni/ZSM-5, at 550
C, 90%N2 and 10%O2). The
hydrogen content can be significantly increased by Ce and La on the
Ni/ZSM-5 catalyst. Higher increasing rate (47.2%, (95%N2 and 5%O2)
and 91.1% (95%N2 and 10%O2)) was found in case of Ce at 550
C,
while the La/Ni/ZSM-5 catalyst can also significantly increases the
hydrogen concentration at 850
C in both atmospheres (30.2%, (95%
N2 and 5%O2) and 38.9% (95%N2 and 10%O2)). It is important result,
because hydrogen is valuable syngas component, especially for
energy uses. The highest yield of syngas was resulted by the La/Ni/
ZSM-5 catalyst at both temperatures; it was 23.8 mmol/g (95%N2
and 5%O2), and 28.4 mmol/g (90%N2 and 10%O2) at 550
C or
112.2 mmol/g (95%N2 and 5%O2), and 130.7 mmol/g (90%N2 and 10%
7
O2) at 850
C. This is in agreement with the results obtained by Saad
and Williams, (2017), who performed the pyrolysis of waste (LDPE,
HDPE, PS, PET and PP) at high temperature. They reported that
rising temperature with the presence of NieCoeAl2O3 catalyst
resulted more syngas at 800
C.
(6)
3.3. Pyrolysis oil
(7)
The pyrolysis oil compositions; n-paraffin, n-olefins, aromatics,
(8) oxygenated and branched compounds for the different tempera-
tures and ratio of N2/H2 and each catalyst type are shown in Table 3.
The summarized concentrations of the different type of compounds
are shown in Fig. 6.
It is well shown that high concentration of n-paraffin and n-
olefin can be found in pyrolysis oil, which was the consequence of
the high waste polyethylene content in the raw material. Either the
catalyst type and reaction conditions have a significant effect on the
concentration of n-paraffin and n-olefin. However, in general
higher n-paraffin/n-olefin ratio was occurred by the using of more
oxygen in the pyrolysis-gasification atmosphere. Only in case of La
and Ce containing catalysts was opposite tendency. It is also
important observation, that less n-paraffin and more n-olefin was
obtained in the presence of catalyst using 95%N2 and 5%O2 than
that of without catalysts at 850
C, however opposite tendency can
be concluded under 90%N2 and 10%O2 atmosphere. Regarding the
effect of carrier gas composition on the pyrolysis oil structure, the
ratio of n-paraffin and n-olefin increased as function of O2 content
in case of catalyst free pyrolysis (Fig. 6(a)). This was the same in case
of Ni/ZSM-5 catalyst too. The application of promoters on the Ni/
ZSM-5 showed similar results at 850
C, because the value of the
n-paraffin/n-olefin was significantly higher in case of 10% O2. The
concentration of n-olefins was higher than that of without catalyst
using 10% O2 feed on 550
C at each Me/Ni/ZSM-5 catalysts. The
pyrolysis oil contained more olefinic compounds at 550
C (ratio
was lower than 1.0) than at 850
C. This was occurred by the higher
degree of partial oxidation of hydrocarbons to phenolic compounds
and single-ring aromatics. Increasing of both the temperature and
O2 concentration was favourable for the formation of n-paraffin.
The highest n-paraffin/n-olefin ratio (1.5) was obtained with the
application of Mg/Ni/ZSM-5 catalyst on 850
C using 10% O2. In
general, decreasing in the concentration of n-paraffin and n-olefin
was found with increasing the temperature to 850
C; however the
catalysts have not as significant effect to the concentration of n-
paraffin and n-olefin at lower temperature as it was demonstrated
at 850
C.
The aromatic compounds in the pyrolysis oil were mainly rep-
resented in the form of single and multi-ring aromatics. Results
showed that the highest yield of single ring aromatic (17.8%) was
found over Ca/Ni/ZSM-5 catalyst at 550
C; in contrast the highest
8 M. Al-asadi et al. / Journal of Cleaner Production 271 (2020) 122186

Table 3
The composition of pyrolysis oil.

No-catalyst Ni/ZSM-5 Ca/Ni/ZSM-5 Ce/Ni/ZSM-5 La/Ni/ZSM-5 Mg/Ni/ZSM-5 Mn/Ni/ZSM-5

95% N2 and 5% O2, T ¼ 550
C n-paraffin 15.8 12.7 11.8 15.0 15.1 13.9 13.7
n-olefin 19.5 20.9 17.8 13.7 14.8 18.6 15.9
single ring aromatic 5.1 13.1 17.8 10.5 14.8 11.2 12.5
multiring aromatic 2.4 3.2 4.2 3.0 3.8 4.2 4.9
Biphenil 1.4 1.1 1.5 1.5 1.8 1.5 1.5
Ketone 1.7 1.2 1.4 2.0 2.5 2.1 2.7
Aldehyde 2.4 3.5 3.6 3.6 1.8 1.8 2.1
Phenol 2.7 4.9 3.7 6.0 5.2 4.0 3.7
methyl terephthalate 0.6 0.8 0.4 1.0 0.8 0.7 0.9
Benzoic acid 15.0 9.9 13.3 12.0 12.6 11.2 12.4
Terephtalic acid 10.9 6.9 5.4 7.0 7.2 6.2 7.2
di-n-oktil-phthalate 2.7 2.2 1.6 1.7 1.7 0.9 1.1
Other 20.0 19.6 17.5 23.1 17.8 23.7 21.4
95% N2 and 5% O2, T ¼ 850
C n-paraffin 12.0 10.7 12.4 10.7 10.3 11.9 11.7
n-olefin 10.2 14.8 14.0 14.5 12.2 13.3 13.5
single ring aromatic 7.6 13.9 12.0 15.8 13.7 13.1 16.1
multiring aromatic 12.0 8.9 8.3 10.2 9.2 11.9 11.6
Biphenil 2.7 2.1 2.8 2.6 2.9 2.7 1.1
Ketone 2.3 2.0 1.8 2.1 2.9 2.9 2.6
Aldehyde 2.3 2.6 2.3 2.7 2.9 2.7 2.6
Phenol 6.1 2.0 2.5 2.3 1.8 2.7 2.6
methyl terephthalate 1.8 3.6 4.4 2.1 1.5 1.2 1.4
Benzoic acid 14.4 9.8 10.9 10.4 12.0 8.7 8.7
Terephtalic acid 15.2 13.4 9.4 11.9 11.1 10.9 9.5
di-n-oktil-phthalate 0.9 2.1 1.8 1.0 0.9 1.1 1.7
Other 12.6 14.2 17.4 13.7 18.5 16.9 16.8
90% N2 and 10% O2, T ¼ 550
C n-paraffin 11.9 12.1 9.0 11.5 9.4 9.2 11.2
n-olefin 14.2 18.0 15.3 17.8 17.5 17.9 16.2
single ring aromatic 7.4 10.9 20.1 10.2 10.8 11.2 12.0
multiring aromatic 8.9 14.7 15.2 14.1 17.6 15.6 18.2
Biphenil 0.9 0.6 0.9 0.8 0.8 0.5 0.9
Ketone 0.9 0.7 0.8 0.4 0.5 0.6 0.4
Aldehyde 1.3 2.3 2.5 2.7 2.5 2.3 2.4
Phenol 3.0 2.0 2.1 2.1 1.1 1.6 1.8
methyl terephthalate 1.0 0.8 0.6 0.8 0.8 0.9 0.6
Benzoic acid 11.6 7.7 6.5 7.0 7.3 6.1 8.3
Terephtalic acid 16.4 7.4 8.5 10.3 9.7 10.5 9.3
di-n-oktil-phthalate 1.0 1.6 0.9 1.2 1.5 1.1 0.8
Other 21.4 21.3 17.7 21.1 20.5 22.5 17.8
90% N2 and 10% O2, T ¼ 850
C n-paraffin 14.7 13.7 12.8 13.3 13.8 12.6 12.0
n-olefin 12.0 11.2 9.0 9.2 10.6 8.4 10.6
single ring aromatic 5.5 10.4 11.1 12.1 12.5 11.1 13.3
multiring aromatic 20.4 20.8 20.7 21.1 18.1 17.4 19.3
Biphenil 0.9 0.7 0.4 0.7 0.6 0.5 1.0
Ketone 1.1 1.0 0.9 0.4 1.0 0.8 1.1
Aldehyde 1.6 1.8 1.3 0.9 1.3 1.6 1.4
Phenol 3.1 1.2 1.6 1.8 1.4 1.8 1.3
methyl terephthalate 0.8 1.0 0.9 0.7 1.0 0.9 0.8
Benzoic acid 9.7 4.7 5.2 3.9 5.1 4.8 4.3
Terephtalic acid 9.2 9.4 9.0 7.5 7.6 7.9 8.5
di-n-oktil-phthalate 0.7 0.7 0.8 0.5 0.9 0.6 0.8
Other 20.1 23.3 26.5 27.7 26.1 31.5 25.6

yield of multi ring aromatic was obtained at high temperature
(850
C) for the process without catalyst using 95%N2 and 5%O2
atmosphere. The concentration of multi ring aromatic increased as
the reaction temperature was raised from 550
C to 850
C, but no
significant changes was found for the concentration of single ring
aromatic using 95%N2 and 5%O2 atmosphere. At the same time,
higher temperature and O2 concentration was favourable to the
formation of multi-ring aromatic hydrocarbons, resulting signifi-
cant decreasing in the ratio of single ring and multi ring aromatics
(Fig. 6 (b)). This ratio was affected also by the conversion of single
ring compounds to gas components. Due to the formation of single
ring aromatics the ratio was above 1.0 at each temperature using 5%
oxygen, which value decreased below 0.5 at 850
C using 10% O2 in
the carrier gas. The catalysts can also promote the production of
single ring aromatics especially in case of 5% O2 concentration.
Regarding to the oxygenated compounds, Ce/Ni/ZSM-5 catalyst
produced the highest phenol concentration (6.0%) at 550
C, while
Ca/Ni/ZSM-5 and Mn/Ni/ZSM-5 catalyst the lowest (3.7%) using 95%
N2 and 5%O2 atmosphere. High concentration of benzoic acid and
terephthalic acid was obtained in the absence of catalyst for the
various temperatures. The phenol concentration was significantly
higher using 95%N2 and 5%O2 atmosphere without catalysts, and
did not changed significantly using 90%N2 and 10%O2 pyrolysis-
gasification atmosphere. It is important observation, that the
presence of catalysts can reduce the concentration of phenolic
compounds at both temperatures using 90%N2 and 10%O2 atmo-
sphere. However the concentration of phenolic compounds did not
changed at 550
C in case of 95%N2 and 5%O2. The higher oxygen
concentration in the carrier gas can reduce the formation of
phenolic compounds in the presence of Ni containing catalysts, but
the promoters had no significant effect to their efficiency. The La/
Ni/ZSM-5 catalyst had the lowest yield of phenolic compounds in
 M. Al-asadi et al. / Journal of Cleaner Production 271 (2020) 122186
Fig. 6. The components in the pyrolysis oil fraction ((a) n-paraffin/n-olefin ratio; (b) single ring aromatics/multiring aromatics ratio; (c) phenol; (d) compounds containing oxygen).
95%/5% N2/O2 atmosphere at 850
C and at 550
C.
The concentration of compounds containing oxygen was the
highest at 850
C using 5% O2 in each case regardless the applica-
tion of catalyst. However, the catalysts e especially with promoters
e can reduce the quantity of these compounds (Fig. 6 (d)). The
catalyst efficiency was higher at 550
C, than at 850
C. Increasing
the quantity of the oxygen in the carrier gas can reduce significantly
the concentration of compounds containing oxygen in the pyrolysis
oil. However, the lowest concentration of compounds containing
oxygen was found in case of Ce/Ni/ZSM-5 catalyst at 850
C (14.0%)
using 90%/10% N2/O2 atmosphere. It was also concluded that the
ratio of n-paraffin/n-olefin increased well using Ce/Ni/ZSM-5 and
La/Ni/ZSM-5 catalysts at 850
C e especially under 90%/10% N2/O2
atmosphere. Parallel with this ratio, the concentration of multiring
aromatics, phenol and other compounds containing oxygen in the
pyrolysis oil decreased significantly. These changes were occurred
by the hydrogenation of the unsaturated compounds and molec-
ulse containing heteroatoms. The hydrogenation took place domi-
nantly using the Ce/Ni/ZSM-5 and La/Ni/ZSM-5 catalysts because
these catalysts provided the highest hydrogen concentration (Fig. 6
(a)).
4. Conclusion
In this study, the pyrolysis of waste plastic mixture was carried
out using one stage reactor with various temperatures, atmo-
spheres and catalyst. Significant effects were found on the product
yields and compositions (gases and oil) by changing the reaction
temperature, ratio of N2/O2 and catalyst type. The results showed
that rising in ratio of oxygen has positive effects on the gas and
liquid products at 850
C, while the yields were slightly increased in
case of all types of catalyst. The gases consist of mainly CH4, H2, CO,
linear and branched hydrocarbons up to C5. Results also demon-
strated that using of O2 as carrier gas can enhancing the production
of syngas due to the increasing reaction rate of partial oxidation.
9
The syngas production (H2 and CO) can be improved by the addi-
tion of Me/Ni/ZSM-5 catalysts or using more oxygen in N2/O2
mixture. Catalyst of La/Ni/ZSM-5 produced the maximum syngas at
temperature of 850
C, but the concentration of CO was signifi-
cantly less than hydrogen at both temperatures in all cases. Higher
oxygen content in the carrier gas can increased the CO2 concen-
tration at 550
C and decreased at 850
C. Furthermore, the Bou-
douard reaction was shifted toward the formation of CO in case of
higher partial CO2 content of the reaction mixture resulted more
CO in the gas product. Increasing in both the temperature and ox-
ygen concentration contributed to the formation of n-paraffin. Due
to the in-situ hydrogenation, the concentration of multiring aro-
matics, phenol and other compounds containing oxygen in the
pyrolysis oil decreased significantly by Ce/Ni/ZSM-5 and La/Ni/
ZSM-5 catalysts.
CRediT authorship contribution statement
M. Al-asadi: Investigation, Validation, Writing - original draft,
Writing - review & editing. N. Miskolczi: Investigation, Conceptu-
alization, Validation, Writing - original draft, Writing - review &
editing, Supervision. Z. Eller: Investigation, Writing - original draft,
Writing - review & editing.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
Acknowledgments
The authors acknowledge the financial support of the project

chenyi 2020 under the EFOP-3.6.1-16-2016-00015.
Sze
10 M. Al-asadi et al. / Journal of Cleaner Production 271 (2020) 122186

References 187e197. https://doi.org/10.1016/S0961-9534(00)00031-3.

Saad, J.M., Williams, P.T., 2016. Catalytic dry reforming of waste plastics from
different waste treatment plants for production of synthesis gases. Waste
Al-asadi, M., Miskolczi, N., Gombor, L., 2019. Dry reforming of waste polymers in
Manag. 58, 214e220. https://doi.org/10.1016/j.wasman.2016.09.011.
horizontal reactor to syngas production. Chemical Engineering Transaction 76,
Saad, J.M., Williams, P.T., 2017. Pyrolysis-catalytic dry (CO2) reforming of waste
1429e1434. https://doi.org/10.3303/CET1976239.
plastics for syngas production: influence of process parameters. Fuel 193, 7e14.
Al-asadi, M., Miskolczi, N., 2020. High temperature pyrolysis of municipal plastic
https://doi.org/10.1016/j.fuel.2016.12.014.
waste using Me/Ni/ZSM-5 catalysts: the effect of metal/nickel ratio. Energies 13
Sharifi, M., Haghighi, M., Rahmani, F., Karimipour, S., 2014. Syngas production via
(5), 1284. https://doi.org/10.3390/en13051284, 2020.
dry reforming of CH4 over Co- and Cu-promoted Ni/Al2O3eZrO2 nanocatalysts
Anuar Sharuddin, S.D., Abnisa, F., Wan Daud, W.M.A., Aroua, M.K., 2016. A review on
synthesized via sequential impregnation and solegel methods. J. Nat. Gas Sci.
pyrolysis of plastic wastes. Energ. Convers. Manage. 115, 308e326. https://
Eng. 21, 993e1004. https://doi.org/10.1016/j.jngse.2014.10.030.
doi.org/10.1016/j.enconman.2016.02.037.
Sogancioglu, M., Yel, E., Ahmetli, G., 2017. Pyrolysis of waste high density poly-
Bulgariu, L., Cojocariu, B., Mocanu, A., Nacu, G., 2018. Possible utilization of PET
ethylene (HDPE) and low density polyethylene (LDPE) plastics and production
waste as adsorbent for Orange G dye removal from aqueous media. Desalina-
of epoxy composites with their pyrolysis chars. J. Clean. Prod. 165, 369e381.
tion Water Treat 104, 338e345. https://doi.org/10.5004/dwt.2018.21909.
https://doi.org/10.1016/j.jclepro.2017.07.157.
Hartulistiyoso, E., Sigiro, F.A.P.A.G., Yulianto, M., 2015. Temperature distribution of
Sriningsih, W., Saerodji, M.G., Trisunaryanti, W., Triyono, R. Armunanto, Falah, I.I.,
the plastics pyrolysis process to produce fuel at 450
C. Procedia Environ. Sci. 28,
2014. Fuel production from LDPE plastic waste over natural zeolite supported
234e241. https://doi.org/10.1016/j.proenv.2015.07.030.
Ni, Ni-Mo, Co and Co-Mo metals. Procedia Environ. Sci. 20, 215e224. https://
Hu, Z., Jiang, E., Ma, X., 2019. The effect of oxygen carrier content and temperature
doi.org/10.1016/j.proenv.2014.03.028.
on chemical looping gasification of microalgae for syngas production. J. Energy
Sun, L.-z., Tan, Y.-s., Zhang, Q.-d., Xie, H.-j., Han, Y.-z., 2012. Tri-reforming of coal bed
Inst. 92 (3), 474e487. https://doi.org/10.1016/j.joei.2018.05.001. https://www.
methane to syngas over the Ni-Mg-ZrO2 catalyst. J. Fuel Chem. Technol. 40 (7),
plasticseurope.org/application/files/9715/7129/9584/FINAL_web_version_
831e837. https://doi.org/10.1016/S1872-5813(12)60032-2.
Plastics_the_facts2019_14102019.pdf.
Verma, R., Vinoda, K.S., Papireddy, M., Gowda, A.N.S., 2016. Toxic pollutants from
Iliopoulou, E.F., Stefanidis, S.D., Kalogiannis, K.G., Delimitis, A., Lappas, A.A.,
plastic waste- A review. Procedia Environ. Sci. 35, 701e708. https://doi.org/
Triantafyllidis, K.S., 2012. Catalytic upgrading of biomass pyrolysis vapors using
10.1016/j.proenv.2016.07.069.
transition metal-modified ZSM-5 zeolite. Appl. Catal., B 127, 281e290. https://
Wang, C., Zhang, J., Qin, G., Wang, L., Zuidema, E., Yang, Q., Dang, S., Yang, C., Xiao, J.,
doi.org/10.1016/j.apcatb.2012.08.030.
Meng, X., Mesters, C., Xiao, F.-S., 2020. Direct conversion of syngas to ethanol
Lopez, G., Artetxe, M., Amutio, M., Alvarez, J., Bilbao, J., Olazar, M., 2018. Recent
within zeolite crystals. Inside Chem. 6 (3), 646e657. https://doi.org/10.1016/
advances in the gasification of waste plastics. A critical overview. Renew. Sust.
j.chempr.2019.12.007.
Energ. Rev. 82, 576e596. https://doi.org/10.1016/j.rser.2017.09.032.
Wu, C., Williams, P.T., 2009. Hydrogen production from the PyrolysisGasification
Loy, A.C.M., Yusup, S., Lam, M.K., Chin, B.L.F., Shahbaz, M., Yamamoto, A., Acda, M.N.,
of polypropylene: influence of steam flow rate, carrier gas flow rate and gasi-
2018. The effect of industrial waste coal bottom ash as catalyst in catalytic
fication temperature. Energ. Fuel. 23 (10), 5055e5061. https://pubs.acs.org/doi/
pyrolysis of rice husk for syngas production. Energy Convers. Manag. 165,
10.1021/ef900278w.
541e554. https://doi.org/10.1016/j.enconman.2018.03.063.

, M., 2018. Fossil fuel energy consumption in Wu, T., Zhang, Q., Cai, W., Zhang, P., Song, X., Sun, Z., Gao, L., 2015. Phyllosilicate
Martins, F., Felgueiras, C., Smitkova
evolved hierarchical Ni- and CueNi/SiO2 nanocomposites for methane dry
European countries. Energy Procedia 153, 107e111. https://doi.org/10.1016/
reforming catalysis. Appl. Catal., A. 503, 94e102. https://doi.org/10.1016/
j.egypro.2018.10.050.
j.apcata.2015.07.012.
Mahoney, E.G., Pusel, J.M., Stagg-Williams, S.M., Faraji, S., 2014. The effects of Pt
Xue, Y., Johnston, P., Bai, X., 2017. Effect of catalyst contact mode and gas atmo-
addition to supported Ni catalysts on dry (CO2) reforming of methane to syn-
sphere during catalytic pyrolysis of waste plastics. Energ. Convers. Manage. 142,
gas. J. CO2 Util. 6, 40e44. https://doi.org/10.1016/j.jcou.2014.01.003.
441e451. https://doi.org/10.1016/j.enconman.2017.03.071.
Ng, Q.H., Chin, B.L.F., Yusup, S., Loy, A.C.M., Chong, K.Y.Y., 2018. Modeling of the co-
Yao, D., Yang, H., Chen, H., Williams, P.T., 2018. Investigation of nickel-impregnated
pyrolysis of rubber residual and HDPE waste using the distributed activation
zeolite catalysts for hydrogen/syngas production from the catalytic reforming of
energy model (DAEM). Appl. Therm. Eng. 138, 336e345. https://doi.org/10.1016/
waste polyethylene. Appl. Catal., B 227, 477e487. https://doi.org/10.1016/
j.applthermaleng.2018.04.069.
€ j.apcatb.2018.01.050.
Ozsin, G., Pütün, A.E., 2018. A comparative study on co-pyrolysis of lignocellulosic
Yao, D., Wu, C., Yang, H., Zhang, Y., Nahil, M.A., Chen, Y., Williams, P.T., Chen, H., 2017.
biomass with polyethylene terephthalate, polystyrene, and polyvinyl chloride:
Co-production of hydrogen and carbon nanotubes from catalytic pyrolysis of
synergistic effects and product characteristics. J. Clean. Prod. 205, 1127e1138.
waste plastics on Ni-Fe bimetallic catalyst. Energ. Convers. Manage. 148,
https://doi.org/10.1016/j.jclepro.2018.09.134.
, S., Jand, N., Kiennemann, A., Foscolo, P.U., 2000. Steam-gasification of 692e700. https://doi.org/10.1016/j.enconman.2017.06.012.
Rapagna
biomass in a fluidised-bed of olivine particles. Biomass Bioenerg 19 (3),