Journal of the Energy Institute 92 (2019) 1270e1283

Contents lists available at ScienceDirect

Journal of the Energy Institute

journal homepage: http://www.journals.elsevier.com/journal-of-the-energy-
institute

Pyrolysis of chlorine contaminated municipal plastic waste: In-situ

upgrading of pyrolysis oils by Ni/ZSM-5, Ni/SAPO-11, red mud and
Ca(OH)2 containing catalysts
B. Fekhar, L. Gombor, N. Miskolczi*
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: This work is focussing to the thermo-catalytic batch pyrolysis of contaminated real municipal plastic
Received 10 September 2018 waste using different catalyst mixtures in their different ratios: Ni/ZSM-5, red mud, Ca(OH)2 and Ni/
Received in revised form SAPO-11, red mud, Ca(OH)2. The effect of the catalysts to the pyrolysis oil properties and the in-situ
11 October 2018
upgrading (especially the storage, transportation and corrosion stability) of pyrolysis oil was investi-
Accepted 17 October 2018
Available online 21 October 2018
gated. High concentration of Ni/ZSM-5 and Ni/SAPO-11 zeolites in catalyst mixtures can increase the
yield of gases and pyrolysis oil, the concentration of aromatics or the hydrogen content in gases; however
the presence of red mud in higher content can further increase the hydrogen concentration. ZSM-5 based
Keywords:
Catalyst mixtures catalysts showed higher efficiency in aromatization reactions. An accelerated aging test at 80
C till 1
Contaminated municipal plastic waste week was performed to investigate the storage and transportation stability of pyrolysis oils. Only slight
Aging increase was found in the density and viscosity, on the other hand there was a bit greater increase using
Corrosion SAPO-11 based catalysts than ZSM-5. The change in the olefin content was followed via bromine number
Isomerization and FTIR spectra of pyrolysis oil, which resulted ~3% and ~4% decreasing using Ni/ZSM-5 and Ni/SAPO-11
containing catalyst mixtures. Regarding acidic components, they significantly increased by aging time,
while the high red mud and/or Ca(OH)2 in catalyst mixtures had notable benefit, because they can
drastically decrease the concentration of chlorinated compounds, which led to less weight loss during
corrosion test using copper plate till 60 days at 20
C.
© 2018 The Authors. Published by Elsevier Ltd on behalf of Energy Institute. This is an open access article
under the CC BY license (http://creativecommons.org/licenses/by/4.0/).

1. Introduction

Due to the advantageous property and long lifetime, plastics are important materials in our society. The yearly plastics consumption is
around 300 million tonnes in worldwide and about 60 million tons in the EU [1]. Most of the waste polymers are landfilled (27%) and
valorised with energy recovery (41%) in Europe [1e3]. However, there is a great difference among the landfill rate of different countries;
some of them has less than 5%, while others have more than 70%. It is a positive tendency, that the amount of the collected, recycled and
energy recovered waste plastic are significantly increased; besides the amount of the landfilled plastic waste is decreased in the last ten
years [1]. Currently, on average, 30% of the plastic wastes are recycled, inside and outside of the EU by mechanically or chemically. Pyrolysis
(so called chemical recycling) may be an efficient option to resume the energy from waste polymers and to obtain valuable hydrocarbons
[3,4]. Gas, pyrolysis oil and coke should be the products of pyrolysis process. The arising oil can be used as fuel oil in furnaces or after further
upgrading as fuel in vehicles. Whereas different types of the plastics have variance in their chemical structure and physical nature, the yield
and composition of the pyrolysis products are significantly different [5e7].
It is also well known, that high quality, waste derived hydrocarbons could be obtained by the pyrolysis of polyolefin (high density
polyethylene (HDPE), low density polyethylene (LDPE) and polypropylene (PP)) and polystyrene (PS). On the other hand, contaminations

* Corresponding author. University of Pannonia, Chemical Engineering and Process Engineering Institute, MOL Department of Hydrocarbon and Coal Processing, Egyetem u.

m, H-8200, Hungary.
10, Veszpre
E-mail address: [email protected] (N. Miskolczi).

https://doi.org/10.1016/j.joei.2018.10.007
1743-9671/© 2018 The Authors. Published by Elsevier Ltd on behalf of Energy Institute. This is an open access article under the CC BY license (http://creativecommons.org/
licenses/by/4.0/).
 B. Fekhar et al. / Journal of the Energy Institute 92 (2019) 1270e1283 1271

and the presence of other polymers, such as polyvinyl chloride (PVC), polyamide (PA), paper, biomass or even additives for plastics, con-
taining different elements except for carbon and hydrogen, can significantly deteriorate the advance property of the pyrolysis products. The
problem can be eliminating by the efficient type selective collection of waste materials, but it needs relatively high installing and operating
costs. Regarding the undesired constituents, chlorine is one of the key components, because significant corrosion can be caused by chlo-
rinated components during storage, transportation, combustion, etc. Another problem is that the chlorinated components can poison the
catalysts not only during the pyrolysis, but also in further application of pyrolysis oil [8e13]. PVC has a key role in the plastics industry and
the occurrence of PVC in streams of municipal plastic wastes is very common. Approximately 10% of the plastic is PVC, used for building and
construction, packaging, households, automotive, electric and electronic, etc. sector [1].
During the thermal decomposition of PVC toxic and corrosive compounds are generated, especially vast amount of hydrogen chloride in
gaseous product and chlorinated organic compounds in pyrolysis oil [8,10,11]. On the other hand, the reduction of chlorinated compounds in
pyrolysis product obtained from PVC containing raw materials is an unsolved problem. For this intention the pyrolysis kinetic of both virgin
and waste PVC, each alone or mixed with other plastics, have been studied by many authors [10,11,14]. The presence of the other plastics and
the PVC concentration can significantly affect the dechlorination reactions [14].
The in-situ reduction in the concentration of chlorinated compounds can be divided into different groups: stepwise pyrolysis, catalytic
pyrolysis, pyrolysis with adsorbents added to the sample, or even hydrothermal carbonisation are used [3,4,15e23]. In stepwise pyrolysis, a
prior low temperature step (up to 350
C) is used for the sake of eliminating the chlorine from the original sample in the form of HCl, which
leaves the reactor system as gas; then the temperature is elevated and the sample is pyrolyzed in a conventional run between 400 and 800
C
[4,12,17e19]. In general, the co-pyrolysis of PVC with other plastics and biomass are investigated by stepwise process. E.g. H. Kuramochi et al.
concluded that the HCl emission could significantly reduce due to the presence of wood, because of the hemicellulose as a strong Cl absorbent
[18]. Stepwise pyrolysis often applying different or separated reactor vessels with different temperatures, because more than 95% of the
dehydrochlorination reactions take place in the first unit at low temperature (300e350
C), while the chlorine content of the products from
the following reactors were less (<0.025%) [19]. By biomass-PVC co-pyrolysis also the reaction kinetic parameter should be modified [20].
Regarding hydrothermal carbonisation, the high temperature favoured to the aromatic hydrocarbons [21]. Nowadays, more and more
researcher investigates the co-pyrolysis of plastic waste and different types of biomass. In this case, the initial characterization of feedstock
has a great significance to know the suitability of raw material to carry out further experimental sets, because all the biomass could not be
suitable, economic, qualitative and high yield bio-oil producer. Thermogravimetric analysis is appropriate to characterize the feedstock. B.B.
Uzun and E. Yaman studied the pyrolysis kinetics of walnut shell and waste polyolefins using thermogravimetric analysis. The results provide
valuable information on pyrolysis mechanism and based on them, walnut shell have considerable potential for pyrolysis. However, the
heating rate has a significant effect on the pyrolysis process [22]. Akancha et al. investigated the co-pyrolysis of waste polypropylene and rice
bran wax to produce biofuel. The physical properties of the pyrolysis oil were fairly comparable to Diesel and gasoline [23].
In catalytic pyrolysis, some catalysts with metal content have been studied in order to demonstrate their positive properties. In general,
the used catalysts are metals on inorganic supporter, such as synthetic zeolites, therefore, they have double role, as pyrolysis catalysts and
inhibitors for HCl formation [3,18e21,24e26]. Not only single catalysts, but also metal loaded catalyst and catalyst mixtures/composites are
used. E.g. fluid catalytic cracking, hydrocracking catalysts or ZSM-5 and iron oxide composite catalyst can efficiency used for reducing the
chlorine content of products of vacuum gas oil and PVC pyrolysis [16].
Regarding the adsorbents, especially the HCl emission can be decreased, however, the reduction in chlorinated compounds in pyrolysis
oils would be also advantageous. Numerous materials as biomass constituents, petrochemical residues and alkaline adsorbents (NaHCO3,
CaO, CaCO3, Na2CO3, Ca(OH)2) have been used as HCl adsorbents [4,16,25,27].
Another option for quality improving of the chlorinated pyrolysis products is the upgrading. A. Lopez-Urionabarrenechea et al. reported,
that chlorinated oils from waste plastic pyrolysis could be upgraded by red mud, because it can promote the cracking and dechlorination
reactions [27]. Andrei Veksha et al. can upgrade the non-condensable pyrolysis gases using CaCO3 supported catalytic sorbent containing 5%
NiO during high temperature (700
C) process [28]. S. Kumagai et al. investigated the effect of calcium oxide and calcium hydroxide catalysts
on the product distribution of decomposition at 600
C of individual and mixed plastics under a steam atmosphere. CaO increased gas and
liquid production from the plastic mixture, which was further enhanced in the presence of Ca(OH)2 [29].
It is worth to say, that owing to the reaction scheme of decomposition reactions, the high olefin content is the characteristic of the
pyrolysis products, however it is changing wide range. Generally pyrolysis oils have 30e70% unsaturated hydrocarbons, depending on the
reaction parameters [30e36]. Not only the before mentioned chlorinated compounds in pyrolysis oil, but also the unsaturated hydrocarbons
can occur problems during the long term utilization. As it is known, the reactivity of the unsaturated compounds is higher than saturated
hydrocarbons due to the distorted electron cloud. The consequence of this fact is that C]C bonds can easily react with another C]C bond,
which lead to oligomerization and polymerization e.g. during long term storage. The high temperature or sunlight radiation redounds to
those reactions [30e36]. More information is available about the aging of biomass sourced pyrolysis oils (hardwood, softwood, sewage
sludge, wheat straw, chicken manure, etc.), but only few result is published regarding the aging of pyrolysis oil obtained by contaminated or
PVC containing plastic waste [37e39]. Regarding the aging test, an accelerated test at 80
C for 24 h is the mostly used.
In this work, the thermo-catalytic pyrolysis of real waste plastics containing PVC was performed for in-situ improving of pyrolysis oil and
the long term utilization of pyrolysis oil was investigated via accelerated aging and corrosion tests.

2. Experimental

2.1. Materials

Mixtures of polyolefin rich real municipal waste plastics contained PVC was used as raw material in our current work: 35% LDPE, 32%
HDPE, 24% PP, 4% PVC, 3% ethylene-propylene dimer and 2% polystyrene. Raw material was supplied by household collection and contained
1.5% chlorine, while the ash content was 4.7%. Waste plastics had been shredded and then crashed by laboratory device (Dipre).
Mixtures of Ni/ZSM-5, Ni/SAPO-11 catalysts, Ca(OH)2 (supplied by VWR) and red mud from Bayer process for alumina production were
added to the raw materials for the in-situ product improving. Red mud contains Fe2O3 (74.8%), Al2O3 (9.8%), CaO (4.6%), TiO2 (3.2%), SiO2
1272 B. Fekhar et al. / Journal of the Energy Institute 92 (2019) 1270e1283

(2.2%), MnO (1.2%), Na2O (0.9%), V2O5 (0.4%), SrO2 (0.2%) and 2.6% others. The BET surface of the Ca(OH)2 and red mud was 28.4 and 35.1 m2/g,
respectively. Table 1 summarizes the composition of catalyst mixtures.
The ZSM-5 ([Nan(H2O)16][AlnSi96-nO192]) catalyst supporter is MFI-type 10 membered ring channel synthetic zeolite with 5.3  5.6 Å
channels, while AEL-type, crystalline silicoaluminophosphate (SAPO-11) catalyst ([Nan][Al20SinP20-nO80]) supporter is a one-dimensional
also 10-membered, but elliptical pore channel synthetic zeolite with 6.3  3.9 Å pore size.
Both the ZSM-5 and SAPO-11 catalysts were loaded by nickel using the following procedure. Catalysts were continuously stirred in 1 M
Ni(NO3)2$6H2O (supplied by VWR) at 80
C for 5 h, then they were washed by deionized water, filtered and dried for 10 h at 110
C. In the
final step, each catalyst was conditioned at 500
C for 5 h in air.
Ni/ZSM-5 had 15.1 Si/Al ratio, 324 m2/g BET surface and 1.55 nm average pore diameter. Contrary, Ni/SAPO-11 catalyst had 0.25 Si/Al ratio,
211 m2/g BET surface and 2.11 nm average pore diameter. The micro, meso and total pore volumes were 0.081, 0.018 and 0.099 cm3/g
regarding Ni/ZSM-5 and 0.052, 0.063 and 0.15 cm3/g in case of Ni/SAPO-11, respectively. The nickel content of catalysts was 9%, since the
catalyst supporters were able to bind this amount of nickel during the impregnation of catalysts. This amount of nickel content is appro-
priate according to literature references [40e42].

2.2. Pyrolysis process

Waste plastics were pyrolyzed in a one stage stainless steel batch reactor at 510e520
C in nitrogen atmosphere (Fig. 1). The heating rate
was 15
C/min. The nitrogen flow was 5 dm3/h [43]. The reactor external wall was fitted with electric heating system and the temperature
was controlled by PID controller. Firstly, 50 g of the raw material together with 2.5 g of catalyst was placed in the reactor, then, after the
assembling of the rig, the temperature was elevated to the set value.
Volatiles from the decomposed hydrocarbons were driven though a heat exchanger, where condensable from hydrocarbon gases had
been transformed into liquid product, then the fractions were separated in phase separator into pyrolysis oil and hydrocarbon gases. Hy-
drocarbon gases were bubbled through a scrubber filled with sodium hydroxide solution. The yields of products were calculated based on
the mass balance. The weight of pyrolysis oil and residue were measured after the experiment. Gas yield was calculated in the knowledge of
pyrolysis oil and solid residue (Y(gas) ¼ 100-Y(pyrolysis oil)-Y(residue)).

2.3. Methods

A DANI type GC instrument was used fitted with programmed injector, flame ionized detector for analysis of hydrocarbon composition of
gases: Rtx PONA column (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).
Sample analysis was taken using isotherm conditions (T ¼ 30
C). The temperature of injector and detector were 240
C.
Hydrogen content of the gas products was measured by a Shimadzu GC-2010 gas chromatograph (TCD detector, Carboxen™ 1006 PLOT
column (30 m  0.53 mm)). The temperature was increased from 35
C (hold time 2 min) to 250
C at 40
C/min heating rate, then the final
temperature was hold till 5 min.
Pyrolysis oil was analysed by DANI type GC (Rtx 1 dimetil-polysiloxan capillary (30 m  0.53 mm, thickens of 0.25 mm)) using the
following temperature program: 40
C for 5 min, then the temperature was elevated by 10
C/min till 350
C and it was kept at 350
C till
20 min. Both the injector and detector temperature was 350
C. Components were identified based on their retention time, while the
pyrolysis oil composition was evaluated via peak areas belong to the components.
The chlorine content of products was measured by x-ray instruments (PHILIPS MiniPal PW 4025/02 non-polarized EDXRFS). The
spectrometer was powered by PW 4051 MiniPal/MiniMate Software V 2.0A, equipped with a rhodium-side window tube anode and Si-PIN
detector. The fluorescent x-ray was detected by a Si-PIN detector with a beryllium window. The analysis was taken in helium medium.
The long term application of the pyrolysis oils was followed by accelerated aging and corrosion test. Samples were stored in a sample
holder at 80
C till 7 days. The density (EN ISO 12185) and the viscosity (EN 16896) were measured at 25
C, moreover the Total Acid Number
(TAN) (ISO 6618) and Jodine Number (MSZ 19971-1983) were followed at 0, 1, 3, 5 and 7 days of the test. To investigate the corrosion
property, a copper plate was stored in pyrolysis oil at 25
C till 60 days and the weight loss of the copper plate was calculated by the
following equation:
mi mf
mi $100
weight loss ¼ (1)
A
where mi and mf are the initial and final weights of the metal plate, A is the surface area of the plate.
The pyrolysis oils were also investigated by Fourier Transformed Infrared spectroscopy (TENSPR 27 FTIR instrument with ATR unit). The
resolution was 3 cm1, the illumination was SiC Globar light, a RT-DLaTGS type detector was used. The change of the olefin content was
followed by the integrated peak areas at 890, 910, 950 and 990 cm1 using the following equation:

Table 1
The composition of the catalysts, %.

111-Z 112-Z 121-Z 211-Z 111-S 112-S 121-S 211-S

Ni/ZSM-5 33.3 50.0 25.0 25.0 0.0 0.0 0.0 0.0

Ni/SAPO-11 0.0 0.0 0.0 0.0 33.3 50.0 25.0 25.0
Ca(OH)2 33.3 25.0 25.0 50.0 33.3 25.0 25.0 50.0
Red mud 33.3 25.0 50.0 25.0 33.3 25.0 50.0 25.0
 B. Fekhar et al. / Journal of the Energy Institute 92 (2019) 1270e1283 1273

Fig. 1. The batch process for pyrolysis.

IAðxÞ0  IAðxÞi
DðIAÞ ¼ $100 (2)
IAðxÞ0
where IA(x)0 is the integrated peak area at x ¼ 890, 910, 950 and 990 cm1 without aging, and IA(x)i is the integrated peak area at x ¼ 890,
910, 950 and 990 cm1 after i ¼ 1,3,5,7 days.
The oligomers and polymers formed by the aging test was separated from the by pyrolysis oil by filtration using VWR (514-0066) filer,
Nylon, 0.2 mm, D 25 mm type device. Then the amount of the separated fraction had been weighted and the polymerized ratio was calculated
as following:

mi  m0
PR ¼ $100 (3)
m0
where mi is the weight of the separated oligomers-polymers i ¼ 1,3,5,7 days and m0 is the weight of the tested sample.

3. Results and discussion

3.1. Product yields

The yields of pyrolysis products are summarized in Fig. 2. Pyrolysis was taken till no volatiles could evaporate from the reactor. In general,
higher yield of gaseous products (18.8e26.2%) was observed over ZSM-5 based catalyst mixtures; while more pyrolysis oil was obtain using
Ni/SAPO-11:Ca(OH)2:red mud catalyst mixtures (64.2e71.9%). As it was before discussed, Ni/ZSM-5 catalysts had larger BET surface area, than
Ni/SAPO-11 catalysts, furthermore the micropore volume of Ni/ZSM-5 catalysts were also higher than Ni/SAPO-11. For higher yields of gases
especially the larger micropore volume could be blamed. It is also well established that the CeC bond cracking properties of Ni/ZSM-5 with a
high Si/Al ratio were higher than that of the Ni/SAPO-11 catalyst. This was particularly significant for 1:1:2 red mud:Ca(OH)2:Ni/ZSM-5

100

80

Gases
60
Yields, %

Light oil
Residue
40

20

0
111-Z

112-Z

121-Z

211-Z

111-S

112-S

121-S

211-S
No-catalyst

Fig. 2. Product yields and the time needed for total pyrolysis.
1274 B. Fekhar et al. / Journal of the Energy Institute 92 (2019) 1270e1283

catalysts. It is important to mention, that the ratio of pyrolysis oil and gases was higher using SAPO-11 based catalysts, than that of ZSM-5
based. During the pyrolysis, the hydrocarbon macromolecules enter the pores of the catalyst, where they further cracked. Due to the pore
size of the catalysts, the decomposed polymer macromolecules could escape from the smaller pore size ZSM-5 supported catalysts only after a
larger degradation. The SAPO-11 has a bit larger average pore diameter than ZSM-5; for this reason, the larger molecules can also come out
from the pores of the catalyst without further cracking. When these longer carbon-chain molecules reach the active centres of the catalyst
they undergo cyclization and polycyclization [44e46]. Due to these reactions, coke formation is initiated which leads to deactivation of
catalyst. The more coke deposition on the catalyst, the larger coke agglomerates are formed on its surface.
Regarding the residue, a bit more solid phase decomposed products was obtained over SAPO-11 based catalysts, than ZSM-5. Residue was
investigated by SEM instrument. It was concluded, that catalysts, inorganic content of the plastic and the coke agglomerated into larger
particles in case of Ni/SAPO-11 based catalyst mixtures (Fig. 3). Whereas, the catalyst grain were well separated from each other and did not
covered by thick and hard coke layer.

3.2. Gaseous products

Gases contained hydrogen and C1eC5 hydrocarbons, dominantly C2, C3 and C4; n-olefin, n-paraffin, branched olefin and branched
paraffin. The compositions of hydrocarbon gases are summarized in Table 2.

Fig. 3. SEM microgram of residue obtained by thermo-catalytic pyrolysis of waste plastic using 112-Z (a) and 112-S (b) catalyst mixtures.

Table 2
The composition of gases.

No-catalyst 111-Z 112-Z 121-Z 211-Z 111-S 112-S 121-S 211-S

a
n-Olefin, area % 38.5 23.4 23.5 26.7 26.4 22.4 21.3 26.9 24.0
Branched olefin, area %a 12.3 37.4 38.5 33.8 32.2 44.8 47.7 40.1 42.2
n-Paraffin, area %a 41.2 21.8 22.0 25.6 23.0 22.0 20.1 25.4 22.1
Branched paraffin, area %a 8.0 17.4 16.1 13.9 18.5 10.7 10.9 7.6 11.8
n-Olefin/n-paraffin 0.93 1.08 1.07 1.04 1.15 1.02 1.06 1.06 0.57
Branched olefin/branched paraffin 1.55 2.15 2.40 2.43 1.74 4.17 4.38 5.26 3.58
Non-branched/branched 3.93 0.83 0.83 1.09 0.98 0.80 0.71 1.09 0.85
Hydrogenb, % 0.5 1.7 3.9 4.5 1.1 2.2 4.4 5.9 1.5
a
By GC-FID.
b
By GC-TCD.
 B. Fekhar et al. / Journal of the Energy Institute 92 (2019) 1270e1283 1275

Without catalyst, the n-olefin (38.5%) and the n-paraffin (41.2%) hydrocarbons were the main products. However, owing to the isom-
erization effect of the catalysts, the concentrations of branched hydrocarbons can significantly increase during thermo-catalytic pyrolysis,
such as isobutane, isobutene, trans-but-2-ene, cisz-but-2-ene, isopentane, 2,2 dimethyl-butane, methyl-pentane. Both the Ni/ZSM-5 and Ni/
SAPO-11 containing catalyst mixtures occurred notable increasing in branched hydrocarbons. Without catalyst the concentrations of non-
branched and branched hydrocarbons was 80.5 and 19.5%, respectively. Contrary, the summarized concentration of branched hydrocarbons
was 51.2e56.1% in pyrolysis oil by Ni/ZSM-5 catalyst mixtures and 47.7e58.6% by mixtures of Ni/SAPO-11:Ca(OH)2:red mud catalysts. It is
worth to note, that the isomerization effect could only slightly decreased by the adding of Ca(OH)2 and red mud to the catalyst mixture.
The n-olefin/n-paraffin ratio was between 0.57 and 1.15 by catalysts. The thermal and catalytic degradation of hydrocarbons occurs
primarily by b-scission, resulting approximately 1:1 ratio of n-olefin and n-paraffin. As it is shown by the results, the amount of olefins can
be increased by the using of catalysts. For the isomerization of hydrocarbons obtained by the degradation of the longer molecules, the
catalyst must have sufficient acidity for the rearrangement of the hydrocarbon skeletal and dehydrogenation/hydrogenation function.
Results well shown, that significantly more isomers of hydrocarbons were obtained using high concentration of both Ni/ZSM-5 (112-Z) and
Ni/SAPO-11 (112-S) catalysts. Results show, that the ratio of non-branched/branched hydrocarbons decreased from 3.93 to 0.71e1.09 by the
use of catalysts; but there were no trend-like, significant differences among the catalysts. However, the using of catalyst mixtures with 50%
Ni/ZSM-5 and Ni/SAPO-11 catalysts the highest branched and lowest non-branched hydrocarbons were resulted.
It is worth to investigate the ratio of saturated and unsaturated hydrocarbons within the branched molecules. Less branched olefin and
more branched paraffin were obtained by ZSM-5 catalysts (111-Z, 112-Z, 121-Z, 211-Z) than SAPO-11 catalysts (111-S, 112-S, 121-S, 211-S).
Comparing the effects of the two catalysts to the formation of branched unsaturated hydrocarbons, it can be concluded, that the higher
surface areas and Si/Al ratios were the cause for elevated olefin content regarding ZSM-5 catalysts. For example, the ratio of branched olefin/
branched paraffin ranged between 1.74 and 2.43 for ZSM-5 catalysts or 3.58e5.26 for SAPO-11 catalysts. In both cases, the highest value was
achieved by 121-Z and 121-S catalyst, while the lowest by 2:1:1 ratios. The SAPO-11 catalyst is particularly beneficial for the formation of
isobutene, trans-but-2-en, cis-but-2-en and isopentene. It is also observed, that more multi-branched isomers was obtained over SAPO-11
catalysts.
It is right, that the used pyrolysis temperature was low for significant hydrogen production over transition metal loaded catalysts [47].
The hydrogen content of the gas products was 0.5% without catalysts, which could be increased to 1.1e4.5% and 1.5e5.9% using Ni/ZSM-5
and Ni/SAPO-11 containing catalyst mixtures, respectively. That result was also supports the higher isoolefin content. The reason for this
may be the following. Firstly, the n-paraffin adsorbed and dehydrogenated on the metallic active centres of the catalyst resulting n-olefins,
and then n-olefin transformed to carbenium ion at the acidic sites of the zeolite. That non-branched carbenium ion rearrange to branched
olefin beside proton loss. It is also known, that the branched olefin is hydrogenated to paraffin and leaves the catalyst using suitable zeolites.
The metallic sites are required to maintain the proper olefin concentration and to maintain the propagation reactions. On the SAPO-11
catalysts, in the first step, hydrogen and carbonium ions are formed, which is also isomerised, but the final hydrogenation of the
branched olefin into branched paraffin was slightly occurred, which led to higher hydrogen content in gases. In both cases, the high Ni ion-
exchanged catalyst (112-Z and 112-S) could mostly increase the hydrogen concentration, while red mud mixed into the catalysts had

pez et al. demonstrated that less than
synergic effect. The relatively low hydrogen content was also supported by previous results. E.g. A. Lo
1.2% hydrogen was obtained from stepwise pyrolysis of the mixtures of PE, PP, PS, PET and PVC, while the gas fraction contained mainly C2, C3
and C4 hydrocarbons [4].

3.3. Pyrolysis oil

The pyrolysis oils were analysed by GC-FID. Results are shown in Fig. 4. Based on result, pyrolysis oils were the mixtures of C5eC30
hydrocarbons: n-olefin, n-paraffin, branched hydrocarbons and aromatics.
Firstly, the catalysts can also affect the concentrations of different compounds in pyrolysis oils. The concentrations of n-paraffin, n-olefin,
branched hydrocarbons (both saturated and unsaturated) and aromatic were 30.8%, 27.0%, 40.3% and 1.9% without catalyst. It is well shown,
that mostly the concentrations of aromatics and branched hydrocarbons can increase with the addition of catalysts.
Each of the catalysts showed high activity in isomerization reactions which led to the increasing in branched hydrocarbons, however,
aromatization reactions was occurred rather on Ni/ZSM-5 containing catalysts. Regarding aromatic compounds in pyrolysis oil from catalyst

211-S

121-S

112-S

111-S
n-paraffin
211-Z
n-olefin
121-Z
branched
112-Z aroma cs
111-Z

No-catalyst

0 25 50 75 100
ComposiƟon, %

Fig. 4. The composition of pyrolysis oil.

1276 B. Fekhar et al. / Journal of the Energy Institute 92 (2019) 1270e1283

free experiment, the polystyrene in raw material was their source. Contrary, the aromatic content was 11.4e17.6% over Ni/ZSM-5 containing
catalysts, while 8.1e11.0% using Ni/SAPO-11 containing catalysts; mostly benzene, toluene, xylenes and other short-chain substituted aro-
matic hydrocarbons. It is important to remark, that owing to the difference in catalyst channels, the concentration of short-chain substituted
aromatic hydrocarbons was higher when Ni/SAPO-11 containing catalysts were used, than that of Ni/ZSM-5 containing. One dimension of Ni/
SAPO-11 catalyst was larger, than Ni/ZSM-5 catalyst; therefore the larger hydrocarbons (e.g. short alkyl chain substituted aromatics) can leave
the catalyst surface without decomposition. It is also well shown, that Ni/SAPO-11 catalysts had a bit favourable effect for production of n-
paraffin, however the concentration of branched hydrocarbons were tendency-like less, than that of using Ni/ZSM-5 catalysts.
The n-paraffin/n-olefin ratio were 1.09e1.18 using Ni/ZSM-5 containing catalysts, while 1.31e1.43 over Ni/SAPO-11 catalysts. The ratio of
branched and non-branched aliphatic hydrocarbons in the pyrolysis oil was 0.70 for cracking without catalysts, which increased to 1.31e2.17
by Ni/ZSM-5 catalysts and 0.97e1.75 using Ni/SAPO-11 catalysts.
The ratio of branched and non-branched aliphatic hydrocarbons increased in the order of 211, 121, 111 and 112 signed catalysts using both
ZSM-5 and SAPO-11 supporters. This was due to the catalyst skeleton rearranging property. However, more n-paraffin and less n-olefin
hydrocarbons were produced over SAPO-11 catalyst. This is due to local hydrogenation reactions. During the decomposition of polymer
waste, the source of hydrogen is primarily the cyclization and aromatization reactions of aliphatic hydrocarbons and the forms of isom-
erization reactions when non-branched hydrocarbons transformed to branched unsaturated hydrocarbons. It is also important to remark,
that the hydrogen content of the gas products correlates with the ratio of n-parafin/n-olefin in pyrolysis oils in case of SAPO-11 catalysts.
Regarding the amount of hydrogen, for catalysts, primarily the aromatization reactions can be blamed while regarding the SAPO-11 catalysts
the dehydrogenation isomerization reactions resulting in unsaturated branched hydrocarbons should be also caused according to the
following reaction scheme (Fig. 5).
The olefin content of pyrolysis oils was followed via their Jodine number (Fig. 8). According to the result, the total olefin content of the
products was higher with Ni/SAPO-11 based catalysts than on Ni/ZSM-5 based regarding each sample. Considering, that the n-olefin content
of products is decreased in the presence of catalysts and the fact that the n-olefin content of the products was lower using SAPO-11 sup-
ported catalysts than that of the ZSM-5, it is easy to see that more branched olefins can be obtained over SAPO-11 catalysts with accordance
the before mentioned reaction scheme.

3.4. Chlorine content and corrosion properties

The chlorine content of pyrolysis products is important for their future utilization, which is summarized in Fig. 6. Catalysts can signif-
icantly affect the chlorine content of the products. It is well known that the decomposition of PVC is taken at relatively low temperature
(300e350
C), which is lower than the temperature needed to the cracking of the polyethylene CeC bonds (400e420
C) [4]. The
dechlorination efficiency is increase by the increase of the temperature and pyrolysis time [13]. However higher temperature needs more
energy and due to the recombination reaction, pyrolysis oils contain higher concentration of chlorinated compounds. During the pyrolysis of
PVC, the CeCl bond with high dipole moment begins to break, resulting in chlorine and alkyl radicals. Hydrogen may be also generated by
further reactions from the alkyl radicals, which should recombine with chlorine to produce HCl. This will primarily appear in gas products.
However, the chlorine radical may also be recombined with alkyl radicals, resulting in organic chlorine compounds which will initially
appear in the pyrolysis oil and the residual product of pyrolysis. The problem is mainly with organic chlorine compounds in pyrolysis oil
because their removals are difficult and significantly deteriorate the long-term utilization and stability of the products. Inorganic chlorine in
the gas product, mostly HCl, can be easily removed with various sorption processes.
Regarding pyrolysis products, 102202 ppm chlorine was in the gases, 4364 ppm was in the pyrolysis oil and 1950 ppm was in the residue
without catalyst. These values were significantly changed by the using of catalysts. The distribution of chlorine among the different products
and the high chlorine content in gases was confirmed by others [27]. Generally, catalysts reduced the amount of chlorine in gas products and
pyrolysis oil, while the amount of chlorine in the residue fraction increased. When analysing data, it is also worth considering that chlorine is
generated in the first half of the decomposition reactions, that is why, the longer takes the pyrolysis, or the higher the yield of the given
fraction, their diluent effect will prevail.
Comparing the two zeolites, the chlorine content of the gas products was lower, and that of the pyrolysis oil were higher in all cases
produced on the mixtures of Ni/ZSM-5 catalysts containing catalyst, than that of over Ni/SAPO-11 catalysts. This was the consequence

-H2

+H2

+H2

-H2

R -H2

-H2

R
Polyaromatic, Coke

Fig. 5. Reaction scheme of the dehydrogenation isomerization reactions.

 B. Fekhar et al. / Journal of the Energy Institute 92 (2019) 1270e1283 1277

120000

100000

Chlorine content, ppm

80000

60000
Gases
40000 Pyrolysis oil
Residue
20000

112-S
111-S

121-S

211-S
No-catalyst

111-Z

112-Z

121-Z

211-Z
Fig. 6. Chlorine content of the products.

probably the fact that, owing to the higher hydrogen content of the product mixture over SAPO-11 catalysts, the chlorine radicals were easily
able to combine to HCl and reduce the concentration of organic chlorine compounds in hydrocarbons. This assumption is also supported by
the fact that the chlorine content of the gas products correlates with the hydrogen content. It was confirmed by others, who concluded that
the chlorine from PVC correlates with hydrogen to generate hydrochloric acid (HCl) at a lower temperature using metal oxide catalysts [14].
It is also worth note that the presence of red mud and Ca(OH)2 was highly preferred in the reduction of the chlorine content of pyrolysis oil.
This was observed for both ZSM-5 and SAPO-11 supported catalysts. The advanced property of the red mud for chlorine reducing in gases
and pyrolysis oil was also reported by A. Lopez-Urionabarrenechea et al. They demonstrated that vast amount of chlorine moved to the solid
phase during the catalytic post treating of pyrolysis oil [27].
The reason for this was that due to the alkali character of both substances, chlorine-containing compounds could be chemically react
with additional compounds of catalysts, resulting in a significant increase in the residual chlorine content, while the chlorine content of the
gas products and pyrolysis oils was significantly reduced. The chlorine content of the pyrolysis oil decreased from 4364 ppm to 284 ppm
while the chlorine content of gases changed from 81762 ppm to 48128 ppm using 211-Z, while 228 ppm chlorine was measured in pyrolysis
oil using 211-S catalyst.
Fig. 7 shows the appearances of the pyrolysis oil after 60 days treating and summarize the result of corrosion test. A copper plate was put
into the pyrolysis oil at 20
C till 60 days. The change in weight of the copper plate was registers in each 5th day. According to results,
increasing tendencies were found in case of both catalyst free and catalyst supported pyrolysis. The change in the weight of copper plate was
0.458%/mm2 without catalysts, which value could be significantly decreased by catalysts. It is also well shown, that lower weight loss was
found in case of pyrolysis oils obtained by the using of SAPO-11 supported catalysts. Especially the presence of Ca(OH)2 and red mud rich
catalysts showed high efficiency in better corrosion properties. E.g. the weight loss of copper plate was 0.055%/mm2 (121-Z) and 0.039%/mm2
(211-Z) or 0.039%/mm2 (121-S) or 0.025%/mm2 (211-S). These results are supported by the chlorine content of pyrolysis oils shown in Fig. 6.
The lower the chlorine content of pyrolysis oil, the less the weight loss of the copper plate. Regarding the appearances of the pyrolysis oil, they
were dark after the treating excluded the using of 121-Z, 211-Z, 121-S and 211-S catalysts. In those cases the colours of the oil only slightly
become darker, and they kept yellowish transparent liquid.
That result was confirmed also by TAN during the aging accelerated test (Fig. 8). The TAN of pyrolysis oil obtained by catalyst free py-
rolysis was 5.9 mg KOH/mg sample. However pyrolysis oil had less acidic components by the using of catalysts, especially SAPO-11 based;
2.7e4.3 mg KOH/mg sample in case of ZSM-5 based catalysts, while 2.1e4.2 mg KOH/mg sample using SAPO-11 catalysts. On the other hand
the TAN increased in less degree when catalyst was used for pyrolysis, especially with high Ca(OH)2 and red mud concentration. Without
catalyst the change in TAN was 70% (from 5.9 mg KOH/g to 19.4mgKOH/g). The increasing in TAN was less using catalysts, especially in case of
SAPO-11, because the TAN increased with 36e57% and 29e48% using Ni/ZSM-5 and Ni/SAPO-11 containing catalysts, respectively. Pre-
sumably acidic chlorine containing compounds are transformed from the chlorinated organic components during the aging, which can be
neutralized by KOH.

3.5. Aging test

The change in the main properties of the pyrolysis oil as function of time is key property for their long term application. An accelerated
aging test was performed to investigate the longer term utilization of pyrolysis oils and the effect of the catalysts to the properties. Results
are summarized in Fig. 8.
Regarding the density and viscosity slight increasing tendencies were found both without and with catalysts. However, catalysts had
advantageous effect to both properties. The density and viscosity of the pyrolysis oil was 0.851 g/cm3 and 1.905 mm2/s without catalysts,
respectively. The density could be increased by 1.99%, while the viscosity by 5.49% without catalysts. It is clear, that the catalysts can increase
both the density and viscosity increasing of pyrolysis oil at the end of treating. It is also important to note, that lower density and viscosity of
pyrolysis oils was measured by the using of catalysts. The density of pyrolysis oil obtained by absence of catalysts increased to 0.868 g/cm3 at
7th day of the treating at 80
C. Comparing, when catalysts were used, the pyrolysis oil density was 0.773e796 g/cm3 without treating,
which increased to 0.791e0.817 g/cm3 during the accelerated aging. It means, that the density can increased by 2.03e2.68% using Ni/ZSM-5
catalysts, while 2.57e3.06% using Ni/SAPO-11 catalysts. Similar phenomena was concluded regarding the viscosity, however the increasing
ratio was higher: 5.95e9.32% in case of Ni/ZSM-5 catalyst mixtures and 9.15e11.44% by Ni/SAPO-11 based catalysts. It is important to
remark, that same order of catalysts was found regarding the density and viscosity increasing in case of both Ni/ZSM-5 and Ni/SAPO-11
1278 B. Fekhar et al. / Journal of the Energy Institute 92 (2019) 1270e1283

Fig. 7. Samples after 60 days storage (a) (A ¼ no catalyst, B ¼ 111-Z, C ¼ 112-Z, D ¼ 121-Z, E ¼ 211-Z, F ¼ 111-S, G ¼ 112-S, H ¼ 121-S, I ¼ 211-S) and weight loss of copper samples
during corrosion test (b-ZSM-5 supported catalyst, b-SAPO-11 based catalysts).

catalysts: 121, 211, 111 and 211. That order is the same, as it was earlier mentioned for increasing in the concentrations of unsaturated
hydrocarbons. The higher concentration of unsaturated hydrocarbons is the cause for higher increasing in both density and viscosity using of
SAPO-11 catalysts.
The change in olefin content was also followed via the FTIR spectra of the products at 990, 955, 910 and 890 cm1 wavenumbers. Py-
rolysis oils show typical hydrocarbon FTIR spectra (Fig. 9). There were infrared activity between 2800 and 3000 cm1 (eCH2e, eCH3
symmetric and asymmetric vibration bands), between 1250 and 1500 cm1 (asymmetric and symmetric deformation stretching of eCH3
groups). Peaks with low intensity at 1615 cm1 was attributed to the aromatic hydrocarbons (C]C streching vibration), while around 610
and 690 cm1 refer to the chlorinated hydrocarbons CeCl streching vibration, which was the less in case of catalyst mixtures with high red
mud and Ca(OH)2 content. Bands in the range of 850e1000 cm1 refer to the olefins and mowing vibration at 720 cm1 was caused by
eCH2e group. In our current work the 850-1000 cm1 range was investigated. There are four peaks in that range: at 890 cm1 (vinylidene),
at 910 and 990 cm1 (vinyl) or 950 cm1 (vinylene). In general, the infrared signal at 910 and 990 cm1 decreased, while at 950 cm1
increased by the using of catalysts, compared to catalyst free case, which refers to the rearrangement of hydrocarbon skeletal.
Fig. 9 summarizes the change in peak areas during the accelerated aging. As it seems, the peak areas of the FTIR spectra of pyrolysis oils
only slightly decreased (less than 5%), which is similar result as it was demonstrated regarding density or viscosity. It is important to note,
that the change of vinyl type olefins was higher than that of the other two types, furthermore the catalyst use during the pyrolysis can also
 B. Fekhar et al. / Journal of the Energy Institute 92 (2019) 1270e1283 1279

Fig. 8. Results of the aging tests (a, b-density, c, d-viscosity, e, f-TAN, g,h-Jodine number, i, j-peak intensity).
1280 B. Fekhar et al. / Journal of the Energy Institute 92 (2019) 1270e1283

Fig. 9. FTIR spectra of pyrolysis oils obtained from pyrolysis using Ni/ZSM-5 (a) and Ni/SAPO-11 (b) containing catalyst mixtures.

decrease the change of the integrated peak areas. Results refers, that vinyl type olefins had greater role during the aging than the other two.
Glancing the result it can be also concluded, that the relative change in integrated peak areas was typically between 5 and 7 days using
catalyst mixture with Ni/ZSM-5, whereas between 1 and 3 days in case of SAPO-11 supported catalysts. It means that the aging of pyrolysis
oils obtained by ZSM-5 supported catalyst takes later than that of SAPO-11 catalysts.
The concentration of unsaturated hydrocarbons during the aging was followed via Jodine number, which refers to the amount of the
Jodine needed for the saturation of C]C bonds in mass unit of the sample. It is important observation, that pyrolysis oils by higher un-
saturated branched hydrocarbons resulted faster aging. However it is also worth to note, that only slight and not significant decreased was
found, which compliant result with changing in density or viscosity is. Jodine numbers are slightly decreased as function of treating days.
E.g. it changed from 149 to 144 regarding pyrolysis oil obtained from catalyst free pyrolysis, which means 3.6% decreasing after the 7th day.
Ni/ZSM-5 based catalysts could not affected the Jodine number of pyrolysis oils (3.3e3.9% decreasing), however the concentration of un-
saturated hydrocarbons decreased a bit greater extent using Ni/SAPO-11 based catalysts (4.3e6.1%). Results well demonstrate that the
highest decreasing in unsaturated hydrocarbons was found by the using of 1:1:2 catalyst ratio both in case of Ni/ZSM-5 and Ni/SAPO-11
catalysts.
 B. Fekhar et al. / Journal of the Energy Institute 92 (2019) 1270e1283 1281

Fig. 10. The pyrolysis oils after 7th day aging test at 80
C (a, b) and the result of polymers residue test (A ¼ no catalyst, B ¼ 111-Z, C ¼ 112-Z, D ¼ 121-Z, E ¼ 211-Z, F ¼ 111-S,
G ¼ 112-S, H ¼ 121-S, I ¼ 211-S).

Fig. 10 summarized the oligomer-polymer phase separated from the pyrolysis oils during the aging test, which well supported the
infrared results. Without catalyst nearly linear relationship was found regarding the polymerized olefins as function of treating days. At the
7th day 0.15% of the pyrolysis oil could be separated by filtration. That value was significantly lower by the using of catalysts: 0.05e0.69% in
case of Ni/ZSM-5 based catalysts, and 0.06e0.078% using Ni/SAPO-11 based catalysts. It means that the catalysts can reduced the amount of
the separated fraction. Presumably, it could be explained by the difference in the distribution of the hydrocarbon structure of unsaturated
compounds. In accordance with the FTIR result, in case of pyrolysis oils by ZSM-5 catalyst showed faster change during the end of the
treating time (after 4th days), while the polymerization reactions took place rather during the first half of the accelerated aging (before 3rd
day). It is important to remark, that the polymerized fraction is accumulated in the bottom of sample holder, and the pyrolysis oil kept
transparent above that part.

4. Conclusion

In this work the thermo-catalytic pyrolysis of real municipal plastic waste, the longer term stability and corrosion properties of pyrolysis
products were investigated. It was found, that the PVC containing raw material could be converted mainly into pyrolysis oil, however the
composition of catalysts had a notable effect to the gas:pyrolysis oil ratio. High synthetic zeolite containing catalyst mixtures can drastically
increase the gas yield. Comparing the Ni/ZSM-5 and Ni/SAPO-11 catalyst mixtures, due to the larger pore areas and higher Si/Al ratio, the
ZSM-5 containing compositions resulted higher yield in gases, than SAPO-11. SEM result well demonstrated that larger agglomerates were
found in residues obtained from thermo-catalytic pyrolysis using SAPO-11 based catalyst, than ZSM-5. Regarding gases, catalysts can
isomerize the main carbon frame (especially using catalysts with high concentration of Ni/ZSM-5 and Ni/SAPO-11), and promote the
production of unsaturated hydrocarbons; however the n-olefin and n-paraffin ratio slightly increased. The synergetic property of Ni ion-
exchanged catalyst and red mud to hydrogen production was also demonstrated. High concentration of red mud led to the highest pro-
portion of hydrogen in gases: 121-Z and 121-S; furthermore more hydrogen was obtained using SAPO-11 based catalysts. In accordance with
hydrogen content, the concentration of unsaturated branched hydrocarbons, especially isobutene, trans-but-2-en and cis-but-2-en were
also high in case of SAPO-11 containing catalyst. Pyrolysis oils contain C5eC30 hydrocarbons, while the aromatic, branched and unsaturated
hydrocarbon content increased by the use of catalysts. ZSM-5 based catalysts show high efficiency in aromatization reaction. For conclusion
the stability tests, the density and viscosity are only slightly increased, while the olefin content (especially vinyl type) slightly decreased
during the accelerated aging at 80
C till 7 days, demonstrating, that the high vinylene olefin content of given fractions is not crucial
regarding the stability. Catalysts can decrease the ratios of changing comparing to the catalyst free thermal pyrolysis. However, the aging of
pyrolysis oils obtained by Ni/ZSM-5 containing catalyst takes later than that of Ni/SAPO-11. Contrary, acidic components can cause more
significant change in both TAN or even during the corrosion test. Both the TAN and relative change in copper plate weight loss during the
corrosion test were lower using catalysts during the pyrolysis, especially SAPO-11 based. Regarding the chlorinated compounds, however a
single step and not stepwise process was used, the chlorine could be transformed mainly into gaseous products and the chlorine con-
centration in pyrolysis oils can further decreased by the using of catalysts. Especially the presence of red mud and Ca(OH)2 was highly
1282 B. Fekhar et al. / Journal of the Energy Institute 92 (2019) 1270e1283

preferred for the reduction of the chlorine content of pyrolysis oil, and catalyst mixtures with Ni/SAPO-11 showed better properties for
chlorine reduction than Ni/ZSM-5 based.

Acknowledgement

The authors acknowledge the Horizon 2020, Marie Curie Research and Innovation Staff Exchange (RISE) (MSCA-RISE-2014 (Flexi-pyrocat,

chenyi 2020 under the EFOP-3.6.1-16-2016-00015 and Economic
No.: 643322)). The authors also acknowledge the financial support of Sze
Development and Innovation Operative Program of Hungary, GINOP-2.3.2-15-2016-00053: Development of liquid fuels having high
hydrogen content in the molecule (contribution to sustainable mobility).

References

[1] Home: PlasticsEurope, Building and Construction, PlasticsEurope, 25 May 2017. www.plasticseurope.org/pdf.
[2] Towards a Circular Economy e Waste Management in the EU, 2017, p. 140. Directorate for Impact Assessment and European Added Value Directorate-General for
Parliamentary Research Services European Parliament, Rue Wiertz 60, B-1047 Brussels. E-mail: [email protected] and [email protected].
[3] S.L. Wong, N. Ngadi, T.A.T. Abdullah, I.M. Inuwa, Current state and future prospects of plastic waste as source of fuel: a review, Renew. Sustain. Energy Rev. 50 (2015)
1167e1180, https://doi.org/10.1016/j.rser.2015.04.063.
[4] A. Lo
pez, I. de Marco, B.M. Caballero, M.F. Laresgoiti, A. Adrados, Dechlorination of fuels in pyrolysis of PVC containing plastic wastes, Fuel Process. Technol. 92 (2011)
253e260, https://doi.org/10.1016/j.fuproc.2010.05.008.
[5] I.M. Gandidi, M.D. Susila, A. Mustofa, N.A. Pambudi, Thermal-catalytic cracking of real MSW into bio-crude oil, J. Energy Inst. 91 (2018) 304e310, https://doi.org/10.1016/
j.joei.2016.11.005.
[6] A. Lo
pez, I. de Marco, B.M. Caballero, M.F. Laresgoiti, A. Adrados, Pyrolysis of municipal plastic wastes: influence of raw material composition, Waste Manag. 30 (2010)
620e627, https://doi.org/10.1016/j.wasman.2009.10.014.
[7] E.D. Owen, Chemical Aspects of PVC Stabilisation, Degradation and Stabilisation of PVC, 1984, pp. 197e252, https://doi.org/10.1007/978-94-009-5618-6_5.
[8] J. Leadbitter, PVC and sustainability, Prog. Polym. Sci. 27 (2002) 2197e2226, https://doi.org/10.1016/s0079-6700(02)00038-2.
[9] W.H. Starnes, Structural and mechanistic aspects of the thermal degradation of poly(vinyl chloride), Prog. Polym. Sci. 27 (2002) 2133e2170, https://doi.org/10.1016/
s0079-6700(02)00063-1.
€ Çepeliog
[10] O. ullar, A.E. Pütün, Products characterization study of a slow pyrolysis of biomass-plastic mixtures in a fixed-bed reactor, J. Anal. Appl. Pyrol. 110 (2014)
363e374, https://doi.org/10.1016/j.jaap.2014.10.002.
[11] H. Bockhorn, A. Hornung, U. Hornung, P. Jakobstro € er, M. Kraus, Dehydrochlorination of plastic mixtures, J. Anal. Appl. Pyrol. 49 (1999) 97e106, https://doi.org/10.1016/
s0165-2370(98)00124-7.
[12] M. Grabda, S. Oleszek, E. Shibata, T. Nakamura, Study on simultaneous recycling of EAF dust and plastic waste containing TBBPA, J. Hazard Mater. 278 (2014) 97e106,
https://doi.org/10.1016/j.jhazmat.2014.05.084.
[13] G. Yuan, D. Chen, L. Yin, Z. Wang, L. Zhao, J.Y. Wang, High efficiency chlorine removal from polyvinyl chloride (PVC) pyrolysis with a gaseliquid fluidized bed reactor,
Waste Manag. 34 (2014) 1045e1050, https://doi.org/10.1016/j.wasman.2013.08.021.
[14] Q. Cao, G. Yuan, L. Yin, D. Chen, P. He, H. Wang, Morphological characteristics of polyvinyl chloride (PVC) dechlorination during pyrolysis process: influence of PVC
content and heating rate, Waste Manag. 58 (2016) 241e249, https://doi.org/10.1016/j.wasman.2016.08.031.
[15] D. Czajczyn
ska, T. Nannou, L. Anguilano, R. Krzyzy_ n
ska, H. Ghazal, N. Spencer, H. Jouhara, Potentials of pyrolysis processes in the waste management sector, Energy
Procedia 123 (2017) 387e394, https://doi.org/10.1016/j.egypro.2017.07.275.
[16] M.F. Ali, M.N. Siddiqui, Thermal and catalytic decomposition behavior of PVC mixed plastic waste with petroleum residue, J. Anal. Appl. Pyrol. 74 (2005) 282e289,
https://doi.org/10.1016/j.jaap.2004.12.010.
[17] M. Blazso
, E. Jakab, Effect of metals, metal oxides, and carboxylates on the thermal decomposition processes of poly(vinyl chloride), J. Anal. Appl. Pyrol. 49 (1999)
125e143, https://doi.org/10.1016/s0165-2370(98)00123-5.
[18] H. Kuramochi, D. Nakajima, S. Goto, K. Sugita, W. Wu, K. Kawamoto, HCl emission during co-pyrolysis of demolition wood with a small amount of PVC film and the effect
of wood constituents on HCl emission reduction, Fuel 87 (2008) 3155e3157, https://doi.org/10.1016/j.fuel.2008.03.021.
[19] H. Bockhorn, J. Hentschel, A. Hornung, U. Hornung, Environmental engineering: stepwise pyrolysis of plastic waste, Chem. Eng. Sci. 54 (1999) 3043e3051, https://
doi.org/10.1016/s0009-2509(98)00385-6.
€
[20] S. Uçar, A.R. Ozkan, €z, Co-pyrolysis of waste polyolefins with waste motor oil, J. Anal. Appl. Pyrol. 119 (2016) 233e241, https://doi.org/10.1016/j.jaap.2016.01.013.
S. Karago
[21] C. Santella, L. Cafiero, D. De Angelis, F. La Marca, R. Tuffi, S.V. Ciprioti, Thermal and catalytic pyrolysis of a mixture of plastics from small waste electrical and electronic
equipment (WEEE), Waste Manag. 54 (2016) 143e152, https://doi.org/10.1016/j.wasman.2016.05.005.
[22] B.B. Uzun, E. Yaman, Pyrolysis kinetics of walnut shell and waste polyolefins using thermogravimetric analysis, J. Energy Inst. 90 (2017) 825e837, https://doi.org/10.1016/
j.joei.2016.09.001.
[23] Akancha, N. Kumari, R.K. Singh, Co-pyrolysis of waste polypropylene and rice bran wax e production of biofuel and its characterization, J. Energy Inst. 92 (2019)
933e946.
[24] S.M. Al-Salem, A. Antelava, A. Constantinou, G. Manos, A. Dutta, A review on thermal and catalytic pyrolysis of plastic solid waste (PSW), J. Environ. Manag. 197 (2017)
177e198, https://doi.org/10.1016/j.jenvman.2017.03.084.
[25] P. Laurent, C. Kestemont, C. Braekman-Danheux, A. Fontana, Municipal waste pyrolysis (1). The behaviour of chlorine with cellulose and lignin, Erdol ErdGas Kohle 116
(2000) 89e92.
[26] Z. Yao, X. Ma, A new approach to transforming PVC waste into energy via combined hydrothermal carbonization and fast pyrolysis, Energy 141 (2017) 1156e1165,
https://doi.org/10.1016/j.energy.2017.10.008.
[27] A. Lopez-Urionabarrenechea, I. de Marco, B.M. Caballero, M.F. Laresgoiti, A. Adrados, Upgrading of chlorinated oils coming from pyrolysis of plastic waste, Fuel Process.
Technol. 137 (2015) 229e239, https://doi.org/10.1016/j.fuproc.2015.04.015.
[28] A. Veksha, A. Giannis, W.-D. Oh, V.W.-C. Chang, G. Lisak, Upgrading of non-condensable pyrolysis gas from mixed plastics through catalytic decomposition and
dechlorination, Fuel Process. Technol. 170 (2018) 13e20, https://doi.org/10.1016/j.fuproc.2017.10.019.
[29] S. Kumagai, I. Hasegawa, G. Grause, T. Kameda, T. Yoshioka, Thermal decomposition of individual and mixed plastics in the presence of CaO and Ca(OH)2, J. Anal. Appl.
Pyrol. 113 (2015) 584e590, https://doi.org/10.1016/j.jaap.2015.04.004.
[30] A. Fontana, Ph. Laurent, C.G. Jung, J. Gehrmann, M. Beckmann, Municipal waste pyrolysis (2): chlorine capture by addition of calcium and sodium-based sorbents, Erdol
ErdGas Kohle 117 (2001) 362e365.
[31] S.D.A. Sharuddin, F. Abnisa, W.M.A.W. Daud, M.K. Aroua, A review on pyrolysis of plastic wastes, Energy Convers. Manag. 115 (2016) 308e326, https://doi.org/10.1016/
j.enconman.2016.02.037.
[32] R. Miandad, M.A. Barakat, A.S. Aburiazaiza, M. Rehan, A.S. Nizami, Catalytic pyrolysis of plastic waste: a review, Process Saf. Environ. Protect. 102 (2016) 822e838,
https://doi.org/10.1016/j.psep.2016.06.022.
[33] B. Kunwar, H.N. Cheng, S. R Chandrashekaran, B. K Sharma, Plastics to fuel: a review, Renew. Sustain. Energy Rev. 54 (2016) 421e428, https://doi.org/10.1016/
j.rser.2015.10.015.
[34] K. Ragaert, L. Delva, K. Van Geem, Mechanical and chemical recycling of solid plastic waste, Waste Manag. 69 (2017) 24e58, https://doi.org/10.1016/
j.wasman.2017.07.044.
[35] F. Ates, U.T. Un, Production of char from hornbeam sawdust and its performance evaluation in the dye removal, J. Anal. Appl. Pyrol. 103 (2013) 159e166, https://doi.org/
10.1016/j.jaap.2013.01.021.
[36] D.K. Ratnasari, M.A. Nahil, P.T. Williams, Catalytic pyrolysis of waste plastics using staged catalysis for production of gasoline range hydrocarbon oils, J. Anal. Appl. Pyrol.
124 (2017) 631e637, https://doi.org/10.1016/j.jaap.2016.12.027.
 B. Fekhar et al. / Journal of the Energy Institute 92 (2019) 1270e1283 1283

[37] S. Jitkarnka, B. Chusaksri, P. Supaphol, R. Magaraphan, Influences of thermal aging on properties and pyrolysis products of tire tread compound, J. Anal. Appl. Pyrol. 80
(2007) 269e276, https://doi.org/10.1016/j.jaap.2006.07.008.
[38] J.V. Ortega, A.M. Renehan, M.W. Liberatore, A.M. Herring, Physical and chemical characteristics of aging pyrolysis oils produced from hardwood and softwood feedstocks,
J. Anal. Appl. Pyrol. 91 (2011) 190e198, https://doi.org/10.1016/j.jaap.2011.02.007.
[39] L. Jampolski, M.T. Morgano, H. Seifert, T. Kolb, N. Willenbacher, Flow behavior and aging of pyrolysis oils from different feedstocks, Energy Fuel. 31 (2017) 5165e5173,
https://doi.org/10.1021/acs.energyfuels.7b00196.
[40] C. Wu, P.T. Williams, Ni/CeO2/ZSM-5 catalysts for the production of hydrogen from the pyrolysis-gasification of polypropylene, Int. J. Hydrogen Energy 34 (2009)
6242e6252, https://doi.org/10.1016/j.ijhydene.2009.05.121.
[41] P.H. Blanco, C. Wu, J.A. Onwudili, P.T. Williams, Characterization and evaluation of Ni/SiO2 catalysts for hydrogen production and tar reduction from catalytic steam
pyrolysis-reforming of refuse derived fuel, Appl. Catal. B Environ. 134e135 (2013) 238e250, https://doi.org/10.1016/j.apcatb.2013.01.016.
[42] I.F. Elbaba, C. Wu, P.T. Williams, Hydrogen production from the pyrolysis-gasification of waste tyres with a nickel/cerium catalyst, Int. J. Hydrogen Energy 36 (2011)
6628e6637, https://doi.org/10.1016/j.ijhydene.2011.02.135.

ja, E. Tulok, Thermo-catalytic two-step pyrolysis of real waste plastics from end of life vehicle, J. Anal. Appl. Pyrol. 128 (2017) 1e12, https://doi.org/
[43] N. Miskolczi, J. So
10.1016/j.jaap.2017.11.008.
[44] J. Jae, G.A. Tompsett, A.J. Foster, K.D. Hammond, S.M. Auerbach, R.F. Lobo, G.W. Huber, Investigation into the shape selectivity of zeolite catalysts for biomass conversion,
J. Catal. 279 (2011) 257e268, https://doi.org/10.1016/j.jcat.2011.01.019.
[45] W. Li, C. Huang, D. Li, P. Huo, M. Wang, L. Han, G. Chen, H. Li, X. Li, Y. Wang, M. Wang, Derived oil production by catalytic pyrolysis of scrap tires, Chin. J. Catal. 37 (2016)
526e532, https://doi.org/10.1016/S1872-2067(15)60998-6.
[46] M. Shahinuzzaman, Z. Yaakob, Y. Ahmed, Non-sulphide zeolite catalyst for bio-jet-fuel conversion, Renew. Sustain. Energy Rev. 77 (2017) 1375e1384, https://doi.org/
10.1016/j.rser.2017.01.162.
[47] J.M. Saad, M.A. Nahil, P.T. Williams, Influence of process conditions on syngas production from the thermal processing of waste high density polyethylene, J. Anal. Appl.
Pyrol. 113 (2015) 35e40, https://doi.org/10.1016/j.jaap.2014.09.027.