Bioresource Technology 133 (2013) 443–454

Contents lists available at SciVerse ScienceDirect

Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech

Comparision of real waste (MSW and MPW) pyrolysis in batch reactor

over different catalysts. Part I: Product yields, gas and pyrolysis oil
properties
Funda Atesß b, Norbert Miskolczi a,⇑, Nikolett Borsodi a
a
MOL Department of Hydrocarbon and Coal Processing, University of Pannonia, 10 Egyetem u., 8200 Veszprém, Hungary
b
Department of Chemical Engineering, Faculty of Engineering, Iki Eylul Campus, Anadolu University, 26555 Eskisßehir, Turkey

h i g h l i g h t s

" Pyrolysis of MSW and MPW was investigated in absence and presence of catalysts.
" The n-olefin/n-paraffin ratio has decreased as function of temperature.
" Aromatic and cyclic compounds predominantly formed in the presence of catalysts.
" Aromatic carbon joined to hydroxyl and ether oxygen resonances both were not observed.
" The catalytic effect was more significant in case of MPW pyrolysis.

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

Article history: Pyrolysis of municipal solid waste (MSW) and municipal plastic waste (MPW) have been investigated in
Received 12 November 2012 batch reactor at 500, 550 and 600 °C both in absence and presence of catalysts (Y-zeolite, b-zeolite, equi-
Received in revised form 14 January 2013 librium FCC, MoO3, Ni–Mo-catalyst, HZSM-5 and Al(OH)3). The effect of the parameters on the product
Accepted 17 January 2013
properties was investigated. Products were characterized using gas-chromatography, GC/MS, 13C NMR.
Available online 8 February 2013
Yields of volatile fractions increased, while reaction time necessity for the total cracking decreased in
the presence of catalysts. Catalysts have productivity and selectivity in converting aliphatic hydrocarbons
Keywords:
to aromatic and cyclic compounds in oil products. Gases from MSW consisted of hydrogen CO, CO2, while
Pyrolysis
Carbon distributions
exclusively hydrogen and hydrocarbons were detected from MPW. Catalyst efficiency was higher using
NMR MPW than MSW. Pyrolysis oils contained aliphatic hydrocarbons, aromatics, cyclic compounds and less
Catalysts ketones, alcohols, acids or esters depending on the raw materials.
Ó 2013 Elsevier Ltd. All rights reserved.

1. Introduction ble to collect separately therefore it is easy and more economical to

Pyrolysis is one of the mostly investigated ways for municipal
waste (municipal solid waste (MSW) and municipal plastic waste
(MPW)) recycling, which is suitable for production of gas, liquid
and solid hydrocarbons or other valuable products. During the
pyrolysis the large molecules of the raw material are degraded into
smaller ones at temperatures of 350–1000 °C under atmospheric
pressure using inert atmosphere. Basically polymers, like plastics
or biomass could be processed by this way. The major area of the
utilization of pyrolysis products is both the petroleum and petro-
chemical industry: they could be used as blending components
for fuels or precursors of production of valuable chemicals. How-
ever the composition of products is strongly depending on the
raw materials. Quite often plastics and organic wastes are impossi-
⇑ Corresponding author.
E-mail address: mnorbert@almos.uni-pannon.hu (N. Miskolczi).
dispose them together. That is why lot of co-pyrolysis studies were
carried out, which were aimed to widen the possible range of raw
materials. If biomass is pyrolized in itself, liquid products contain
significant amount of water and other organic chemicals such as
organic acids, alcohols, aldehydes, ketones, phenols and ethers that
is unfavorable in terms of their utilization (Sharypov et al., 2002).
Therefore most of the studies focus on biochar, the solid, residual
product of biomass pyrolysis, which could be used for energy pro-
duction like coal or for production of adsorbents (Bernardo et al.,
2012). The predominant compounds in the pyrolysis-oils obtained
from fluidized pyrolysis of waste square timber and waste ordinary
plywood were methyl acetate, acids, hydroxyacetone, furfural,
non-aromatic ketones, levoglucosan and phenolic compounds
(Jung et al., 2012). The composition of the pyrolysis oils is depend-
ing on the raw materials and experimental parameters; higher
plastic ratio in raw materials increases the oil yields and decreases
the water content. Polymers that contain more hydrogen than bio-

0960-8524/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.biortech.2013.01.112
444 F. Atesß et al. / Bioresource Technology 133 (2013) 443–454

mass could provide hydrogen during co-processing (Miskolczi Table 1a

et al., 2011; Sharypov et al., 2002; Cornelissen et al., 2008). Shary- Main properties of the raw materials (MSW and MPW).

pov et al. (2002) studied the co-pyrolysis of wood biomass and Properties MSW MPW
synthetic polymers. They found that 400 °C was the optimum tem- Proximate analysis
perature for biomass/plastic mixture degradation which corre- Moisture (%) 5.2 0.9
sponded to the maximum light liquid product yield. Congruent Ash (%) 4.7 1.4
results were obtained by Cornelissen et al. (2008), who pyrolized Combustibles (%) 91.1 97.7

biomass together with polylactic acid and investigated the bio-oil Ultimate analysis
yield and heating values. Flash co-pyrolysis of willow and PLA re- C (%) 59.3 85.9
H (%) 21.2 14.1
sulted in an enhanced bio-oil yield with lower water content and O (%) 19.5 0.0
a higher calorific value. Synergistic effects were observed to addi- S 648 135
tion of PLA: an increase of 28% in bio-oil yield and a decrease of Cl 11196 2689
37% in water content. The potential synergistic activities between Zn 4953 1310
Ca 6218 1504
tar sand and walnut shell during co-pyrolysis was also investigated
Br 9105 2316
and concluded that the bio-oil yield could be increased, it had more Sb 1299 749
aliphatic and aromatic contents, and the alkane content was higher K 226
in the bio-oil from co-pyrolysis (Kar, 2011). On the other hand, the P 967
thermal decomposition of ‘‘model compounds’’ and not a real Fe 8349
Cr 2344
waste have been widely investigated. Product yields and composi-
Pb 992
tions obtained from from co-prolysis were not comparable to the
Heating value (MJ/kg) 27.1 42.2
cases when the plastic and biomass were pyrolized separately.
The products of the co-pyrolysis should be generally further up-
graded to their utilization. In the literature no studies could be
finding about catalysts during co-pyrolysis in order to improve b-scission. Previous researchers found that metals (Ni, Mo, Fe, Al,
the quality of the pyrolysis products. etc.) exert a significant effect, especially to the product quality
In present study pyrolysis of real municipal solid waste (MSW) (Sharypov et al., 2002). E.g. the olefin and aromatic content or even
and municipal plastic waste (MPW) obtained from landfill, was hydrogen in gases could be changed in the presence of Ni or other
carried out in a batch reactor at 500, 550 and 600 °C in absence noble metals catalysts and their small amount is sufficient to
and presence of catalysts (Y-zeolite, b-zeolite, equilibrium FCC, affect the product property to a large extent. In this work Y-zeolite,
MoO3, Ni–Mo-catalyst, HZSM-5 and Al(OH)3). The effect of the b-zeolite, equilibrium FCC, MoO3, Ni–Mo-catalyst, HZSM-5,
pyrolysis parameters on the properties of products was investi- Al(OH)3 were used in order to achieve more intensive degradation
gated. Products were characterized using gas-chromatography, of raw materials and modification of pyrolysis product structure.
GC/MS, 13C NMR. Table 1b shows the main properties of the catalysts. The highest
Si/Al ratio was found in case of FCC catalyst (23.2). Regarding
BET surfaces the following order was found: Y-zeolite (379.5 m2/
2. Methods g) > HZSM-5 (366.9 m2/g) > b-zeolite (349.2 m2/g) > Ni–Mo-cata-
lyst (218.3 m2/g) > FCC (192.2 m2/g) > Al(OH)3 (109.5 m2/
2.1. Raw materials g) > MoO3 (84.9 m2/g). The microporous surface areas of catalysts
were between 49.5 and 161.4 m2/g, while the average pore size
In this work real municipal solid waste (MSW) has been used as was in the range of 14.8 and 238.2 lm. Due to porous structure
raw material obtained from Hungarian waste recycling plant. and cationic balance; Y-zeolite and HZSM-5 were the most acid
Waste materials were collected mainly from households and it is catalysts.
consisted of plastics, paper, metals, textile, organic waste, etc. Then
plastic particles were separated from the other constituents of 2.2. Pyrolysis process
MSW and called as municipal plastic waste (MPW). Before the
pyrolysis experiments both MSW and MPW were shredded and A small laboratory scale batch reactor was used for pyrolysis at
scraped into particles with up to 10 mm size and then they were 500, 550 and 600 °C under nitrogen blanket using atmospheric
analyzed. Results are summarized in Table 1a. Based on visually pressure. Fig. 1 demonstrates the layout of the process. In each case
observation and Fourier transformed infrared spectroscopy by par- 50 g of raw materials were put into the reactor and 10% catalyst
ticles to particles, MSW had 58.4% plastics, 27.5% papers, 8.1% was used in thermo-catalytic pyrolysis. 500 °C temperature was
other organic wastes (wood, thin foil, vegetable garbage, etc.), used for thermo-catalytic experiments. Right before the experi-
4.8% textile/synthetic fibres and 0.9% metals, while MPW had poly- mental runs raw materials were crashed into particles with less
ethylene (59.1%), polypropylene (25.0%), polystyrene (7.2%) and than 10 mm in main dimension. The temperature of the reactor
others (PET, PVC, PA, ABS) (8.7%). In consequence of the high paper vessel has been measured by thermocouple and controlled by
and organic waste content in MSW, its heating value was relatively PID controller. Volatile products from the degraded polymer melts
low (27.1 MJ/kg), while MPW has considerable higher value have been run via water cooled condenser, where pyrolytic oil and
(42.2 MJ/kg). The moisture and ash content was 5.2% and 4.7% in water were transformed to liquid phase. The condensed fraction
MSW, respectively, while MPW had 0.9% moisture and 1.4% ash. (pyrolytic oil and water together) has been separated from gases
Ultimate analysis showed that MPW had higher carbon and lower and then it was further divided into pyrolytic oil and water based
hydrogen content than MSW. Oxygen was measured only in MSW on their density difference in another separation unit. Pyrolytic oils
(19.5%). Regarding other elements, MPW had less and significantly have been collected in a sample holder and then analyzed by GC/
lower amount of contaminants. Based on 3 parallel measurements MS, 13C NMR. Residue oil and char was taken away from the
the deviation in reproducibility of the ultimate, proximate and reactor. Gas product was collected in a gas bag and analyzed by
contaminants analysis was 2.1%, 3.0%, and 2.2%, respectively. gas-chromatograph. Product yields were calculated based on their
Zeolite structures have efficient catalytic properties to cracking weight. The amount of pyrolytic oil, water and residue was mea-
of the polymer skeletal and their activity is responsible for that via sured by laboratory scale, while gas yield was calculated based
 F. Atesß et al. / Bioresource Technology 133 (2013) 443–454 445

on volume measured by gas flow meter and their composition ob- reported in ppm using solvent as an internal standard (CDCl3 at
tained from GC analysis. 77.15 ppm).

3. Results and discussion

2.3. Product analysis
Compositions of gases were analyzed by gas chromatography.
Carlo Erba Vega Series GC 6000 GC fitted with 50 m  0.32 mm
fused silica column with Al2O3/KCl coating has been used for hydro-
carbon analysis under isothermal conditions, while the GC have
been equipped with thermal conductivity detector (2 m length by
2 mm diameter column, packed with 80–100 mesh molecular
sieve) using isothermal conditions in case of CO and CO2 measure-
ments. The heating value of gases was calculated based on their
composition and individual heating value of components.
The oil products were analyzed by GC/MS using a Hewlett–Pack-
ard HP 7890 gas chromatograph coupled to a HP 5975 quadrupole
detector. The gas chromatograph was equipped with a 30 m 
0.25 mm capillary column coated with a 0.25 lm thick film of 5%
phenyl-methylpolysiloxane (HP-5). Helium was employed as a car-
rier gas at a constant flow rate of 1.2 ml/min. The initial oven tem-
perature was 45 °C held for 2 min and then programmed from 45 to
290 °C at 5 °C/min with an isothermal held for 10 min. Splitless
injection was applied at 290 °C. The ion source and transfer line
temperatures were 230 and 300 °C, respectively. Data were ac-
quired in the full-scan mode between m/z 33–533 and a solvent de-
lay of 3 min was used. Chromatographic peaks were identified by
means of WILEY mass spectral data library and from their retention
times using standard compound when available. The percentages of
the peaks were calculated from the TIC (total ion chromatogram)
peak area.
The 13C NMR spectra of oils were then recorded at a frequency
of 500 MHz using a Bruker Avancell 500 MHz instrument and are
3.1. Product yields
Product yields obtained from pyrolysis are summarized in
Fig. 2. As data well shows pyrolysis oil, gases, water phase and hea-
vy oil + char have been obtained from MSW pyrolysis, while prod-
ucts were apart from any water in case of MPW destruction. Data
represents the product quantities after 3000 s reaction time, but
the triangle symbols refer to the time necessity of fully pyrolysis;
it means that only solid char was remained in the reaction vessel
after that time and no more volatile yields could be obtained from
that. After that time the yields of gases, pyrolytic oil and water did
not changed, they have shown constant values. Considerable dif-
ference was found for fully pyrolysis time necessity. E.g. 5239 s
has needed for MSW pyrolysis in absence of catalyst at 500 °C,
while that of was in the range of 4331–5110 s using catalysts.
The least pyrolysis time was required when municipal solid waste
had been degraded over Y-zeolite catalyst, because it could be de-
creased by 908 s (17.33%) related to the pure thermal case. It is also
clear that the fully decomposition of MPW pyrolysis have higher
time necessity than MSW without catalyst; 6652 s at 500 °C,
5299 s at 550 °C and 4187 s at 600 °C. It is well known that paper
and organic wastes pyrolysis resulted in higher proportion of vol-
atiles using same reaction conditions and start to decompose at
lower temperature than conventional plastics (Sharypov et al.,
2002; Bernardo et al., 2012; Cornelissen et al., 2008). Results dem-
onstrate that less reaction time is needed for full pyrolysis of MPW
in the presence of catalysts, than it was found in MSW degradation
using same temperature and catalysts. E.g. 4331, 4546, 4529 and

Table 1b
Main properties of catalysts.

Y-zeolite b-zeolite FCC MoO3 Ni–Mo HZSM-5 Al(OH)3

BET surface (m2/g) 379.5 349.2 192.2 89.4 218.3 366.9 109.5
Micropores (m2/g) 78.6 127.7 94.2 – 49.5 161.4 –
Diameter (lm) 35.3 22.2 54.1 192.5 Structural 14.8 238.2
Si/Al 6.5 17.1 23.2 – 7.9 12.6 –
Acidity (meqv. of NH3/g) 0.61 0.47 0.51 – 0.26 0.55 –

Waste collection

Waste Metals, paper, organic

separation waste, etc

Shredding

999.99

Crushing Gases
3
PT
6

TT
4 5
7 2 Pyrolysis oil
TC

TZ

1 4

Char
Water

Layout of the pyrolysis process

(1. Gas bottle, 2. Reactor, 3. Cooling, 4. Separation, 5. Water trap, 6. Gas flow meter, 7. Rotameter)

Fig. 1. Layout of the pyrolysis process.

446 F. Atesß et al. / Bioresource Technology 133 (2013) 443–454
4359 s was needed for full MSW decomposition in case of Y-zeolite
catalyst, b-zeolite, FCC and HZSM-5 catalyst, respectively. Follow-
ing the previous order of catalysts only 3681, 3702, 3884 and
3493 s was required for full MPW pyrolysis. Presumably the cata-
lyst poisoning was the cause for their less activity in MSW pyroly-
sis. It is important to remark that others demonstrated enhanced
efficiency of catalysts in the presence of water during MSW or bio-
mass pyrolysis (Kargöz et al., 2003). Yang et al. investigated the
influence of mineral material on biomass pyrolysis. They found
that dry addition of KCl, Na2CO3, Al2O3, Fe2O3 did not influence
the decomposition. However water washing pre-treatment of min-
eral materials significantly influenced the yields and product dis-
tribution. In current work the effect of the catalyst poisoning was
more significant than the favourable effect of the water presence.
The moisture content was 5.2% and 0.9% in MSW and MPW, respec-
tively. Owing to the oxygen content of MSW (19.5%), water was
also obtained from each MSW pyrolysis; it was changed between
16.8% and 23.2% (both water from humidity and reaction water).
This was the consequence of the cellulose destruction. Water
should be used to an upgrade of the gases toward e.g. hydrogen
over special noble metal catalysts, but the energy cost of this oper-
ation is high because of the high pressure necessity of the reac-
tions. On the other hand one phase water free oil fraction was
the product from MPW pyrolysis. Results were confirmed by
experimental work of others. E.g. Sharypov et al. (2002) have
Fig. 2. Yields of products obtained from MSW (A) and MPW (B) pyrolysis (3000 s) and the time necessity for fully pyrolysis.
investigated the co-pyrolysis of biomass and synthetic polymer
mixtures. Synergetic interaction was found between the biomass
particles and synthetic polymers, furthermore higher yields of vol-
atiles was found in case of biomass and synthetic polymer mixture
co-pyrolysis than using exclusively synthetic polymers. In the first
stage of co-pyrolysis paper and organic waste start to decompose
at lower temperature resulting radicals, than radicals from organic
wastes were responsible for further decomposition of synthetic
polymer chains, e.g. by b-scission. The further transformation of
radicals gave different alkanes, carbonyl and hydroxyl groups or
even aromatics. Furthermore biomass-derived radicals can
combined with polymer-derived radicals in termination step to
stabilize their structure. The most water was given in the presence
of Ni–Mo-catalyst in case of MSW pyrolysis, while the least in
HZSM-5 catalyst application. The most significant effect of the cat-
alysts presence was that the yields of the heaviest fractions (char
and heavy oil) have decreased. Especially the pyrolysis oil and
the gas yields could be increased in thermo-catalytic pyrolysis, re-
lated to the catalyst free case. It is important to remark that the
volatile yield increasing efficiency of catalysts was significantly
higher in case of MPW pyrolysis. Pyrolysis oil yields increase was
between 14.87% (Al(OH)3) and 105.13% (FCC catalyst) in case of
MSW raw material related to the catalyst free pure thermal
experiment at 500 °C, while that was 293.85 (Al(OH)3)–394.44%
(FCC catalyst) using MPW. Regarding gas increasing efficiency,
 F. Atesß et al. / Bioresource Technology 133 (2013) 443–454 447

the Y-zeolite (48.28%) was the most efficient catalyst in MSW pyro-
lysis and HZSM-5 (138.62%) catalyst in MPW pyrolysis. The cata-
lyst efficiency in gas and pyrolysis oil yield increasing could be
explained with their pore surface. Owing to the variant ratios of
catalysts micropre/macropore surface areas, different activity in
production of hydrocarbons in gas and/or pyrolysis oil was found.
That is the reason why e.g. the HZSM-5 catalyst could increased
rather the gas yield, than pyrolysis oil yield. Gas formation is taken
in the micropore surface with higher probability, than on macrop-
ores. Due to the temperature dependence of C–C bond thermal sta-
bility the yields of gases and pyrolysis oils have increased as
function of temperature. E.g. 22.4% gas, 26.5% water phase and
30.9% pyrolysis oil yield was found in case of MSW pyrolysis using
3000 s reaction time at 600 °C. Moreover higher increasing in pyro-
lysis oil yield could be observed if the temperature moved from
500 to 550 °C, than in case of the temperature switching from
550 to 600 °C. If the temperature was moved from 500 to 550 °C,
the pyrolysis oil yield could be increased by 98.9% and 80.7% in
case of MSW and MPW pyrolysis, respectively. On the other hand
only 59.3% and 43.8% increasing in case of MSW and MPW pyroly-
sis was found by the temperature increasing from 550 to 600 °C,
respectively. Regarding gas yield increasing 40.0% (500 °C ? 550
°C) and 10.3% increasing (550 °C ? 600 °C) was calculated using
MSW raw material; while 35.4% (500 °C ? 550 °C) and 30.6%
(550 °C ? 600 °C) in case of MPW pyrolysis absence of catalysts.
It is important to remark that according to Selective Refuse Collec-
tion model the product properties may largely vary during the ini-
tial diffusion and its becomes more stable once the model is
assessed; this phenomenon may affect the results.
3.2. Gases
The compositions of gas products are summarized in Table 2.
Based on the GC analysis gases consisted of hydrogen CO, CO2
and hydrocarbons with carbon atoms up to pentene in case of
MSW destruction, while exclusively hydrogen and hydrocarbons
were in gases using MPW. The concentrations of CO and CO2 were
20.43% and 41.52% in case of pure thermal pyrolysis of MSW at
500 °C and catalysts were able to decrease the CO content parallel
with the increasing in CO2 concentration. Basically the cellulose
content of paper and other natural sourced materials could be
blamed for carbon-oxides formation. This result was confirmed
by earlier works, who reported that vast amount of carbon-monox-
ide and carbon dioxide were produced in the presence of waste pa-
per (Sharypov et al., 2002; Duangchan and Samart, 2008). Water-
shift reaction (CO + H2O M H2 + CO2) and Boudavard reaction
(CO2 + C M CO + CO) are responsible for CO decreasing and
increasing in both hydrogen and CO2 concentrations. MoO3 and
Ni–Mo-catalysts showed the highest decreasing in water yield, fur-
thermore that two catalysts could result the highest increasing in
both hydrogen and CO2 content. Rouppolo et al. investigated the
biomass pyrolysis without catalyst at 400–600 °C in fluidized bed
system (Ruoppolo et al., 2012), and reported that higher water/
raw material ratio was favourable for more shift gas reaction.
During the co-pyrolysis of biomass and petroleum based polymers
Ni–Al2O3 complex synthetic catalysts composed Ni and Mg oxides,
dolomite and other Ni-based had the greatest influence on the gas
composition (Ruoppolo et al., 2012; Onderwater et al., 2001; Xiao
et al., 2010). Especially the carbon-oxides/hydrocarbons ratio could
be affected by those catalysts. In current work the (CO + CO2)/
hydrocarbons ratio was 1.628 in absence of catalysts and that of
was in the range of 1.359 (HZSM-5) and 1.704 (Al(OH)3) in ther-
mo-catalytic pyrolysis at 500 °C. That ratio was 1.192 at 600 °C
without catalysts. The most significant effects of the catalysts pres-
ence were: increase in hydrogen concentration and isomerisation
of carbon frame (increasing in i-butane concentration). E.g. 0.97%
hydrogen and 0.54% i-butane content was measured in pure ther-
mal pyrolysis of MSW at 500 °C, while 1.45% hydrogen and 4.04% i-
butane was formed using MPW raw material. Whereas the hydro-
gen content was between 1.98% (FCC) and 6.53% (MoO3), or 1.33%
(MoO3)–9.67% (HZSM-5) i-butane content was measured in gases
obtained from thermo-catalytic pyrolysis of MSW. Furthermore

Table 2
Gas composition (in %) and heating values (in MJ/kg) obtained from MSW and MPW pyrolysis.

Thermal pyrolysis without catalyst Thermo-catalystic pyrolysis in the presence of catalyst at 500 °C
500 °C 550 °C 600 °C Y-zeolite b-zeolite FCC MoO3 Ni–Mo HZSM-5 Al(OH)3
MSW pyrolysis H2 (%) 0.97 1.21 1.42 1.28 1.57 1.18 6.53 2.73 0.98 1.00
CO (%) 20.43 17.64 15.14 14.89 16.11 17.55 16.15 16.48 16.85 20.41
CO2 (%) 41.52 42.71 39.63 43.72 42.05 42.41 44.48 43.89 42.76 42.59
CH4 (%) 5.41 5.76 7.03 7.34 6.69 6.57 4.65 5.24 6.17 4.98
C2H4 (%) 4.87 5.01 6.05 4.47 4.71 4.63 4.98 5.35 5.11 4.54
C2H6 (%) 4.54 4.74 7.21 5.85 5.13 5.27 5.07 5.57 5.00 4.43
C3H6 (%) 4.64 4.76 4.69 4.26 4.08 3.66 4.20 4.04 3.91 4.98
C3H8 (%) 4.11 5.04 5.56 3.30 3.35 3.55 3.43 3.60 3.26 4.98
C4H8 (%) 3.68 4.56 4.49 2.23 1.99 2.15 1.99 1.86 1.46 3.77
C4H10 (%) 3.89 3.91 4.57 2.02 2.30 2.69 2.77 2.62 1.46 4.54
i-C4H10 (%) 0.54 0.49 0.11 7.34 8.16 6.57 1.33 4.91 9.67 0.89
C5H10 (%) 3.03 2.23 2.13 2.02 1.88 2.26 2.43 2.51 2.17 2.33
C5H12 (%) 2.38 1.95 1.96 1.28 1.99 1.51 1.99 1.20 1.20 0.55
Heating value. MJ/kg 18.41 19.37 22.18 20.25 20.63 19.52 23.13 20.46 20.47 17.96
MPW pyrolysis H2 (%) 1.45 2.62 3.99 2.30 2.50 2.92 7.96 5.93 1.97 1.38
CO (%) 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
CO2 (%) 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
CH4 (%) 10.57 11.94 11.96 13.40 12.87 11.56 10.84 10.32 9.72 10.31
C2H4 (%) 10.45 10.68 10.77 9.40 9.88 9.45 10.50 9.77 9.52 10.69
C2H6 (%) 11.16 11.62 11.57 11.50 10.88 11.26 11.42 11.53 10.76 11.82
C3H6 (%) 11.99 11.41 11.07 9.50 9.78 9.55 11.07 10.32 9.90 11.57
C3H8 (%) 12.94 12.46 12.16 9.90 10.18 11.56 11.42 11.53 10.76 13.21
C4H8 (%) 12.35 12.46 11.37 9.40 10.48 9.45 10.84 10.54 10.03 12.20
C4H10 (%) 11.64 10.16 11.96 10.50 10.48 10.72 10.84 10.76 10.45 13.08
i-C4H10 (%) 4.04 3.14 1.99 15.20 14.57 15.28 6.23 10.76 18.83 4.28
C5H10 (%) 7.24 6.39 6.38 5.40 4.49 4.83 4.84 5.16 4.34 6.29
C5H12 (%) 6.17 7.12 6.78 3.50 3.89 3.42 4.04 3.40 3.72 5.16
Heating value. (MJ/kg) 47.36 48.30 49.32 48.07 48.21 48.47 52.26 50.69 47.65 47.33
Table 3

448
Identified aliphatic compounds in oils obtained from the pyrolysis of MSW and MPW with (500 °C) or without catalyst (500; 550 or 600 °C).

Retention time Compound name MSW MPW

500 °C 550 °C Y-zeolite b-zeolite Ni–Mo HZSM-5 500 °C 550 °C 600 °C Y-zeolite b-zeolite Ni–Mo HZSM-5
4.03 Heptane, 3-methylene – – – – 0.45 – – 0.48 – 0.74 0.45 – –
4.19 4-Octene – 0.41 – 0.52 1.06 1.13 0.99 – 1.57 2.86 0.71 0.6 8.14
4.68 Heptane, 2.4-dimethyl- – – – – – – 0.47 – – 0.6 0.44 0.22 –
5.11 2,4-Dimethyl-1-heptene 5.99 3.35 9.09 1.53 8.9 3.07 4.28 0.68 – 0.64 – – –
6.47 4-Nonene – – – – 2.2 1.14 2.49 – 1.29 – – 1.86 –
6.55 Nonane 0.88 – – 1 0.82 – 0.71 – 1.21 0.25 0.93 0.72 –
8.16 3-Nonane, 2-methyl- – – – – – – – – – – 1.21 – 1.99
8.55 Octane, 3,6-dimethyl- – – – – – – 1.31 1.71 2.2 – 0.92 1.31 –
9.12 1-Decene 0.55 2.22 1.81 0.24 0.81 0.8 1 2.09 2.79 0.63 0.58 0.52 –
9.42 Decane 1.07 1.52 1.34 1.04 1.38 2.31 1.85 1.61 1.13 1.86 0.69 0.99 1.48
9.7 Nonane, 2,6-dimethyl- 0.93 0.65 1.05 – 4.06 1.35 – 0.85 3.01 3.47 1.37 1.5 –
9.82 Decane. 4-methyl- 1.18 1.15 1.53 0.37 – 1.42 1.55 – – 2.44 – 1.25 –
11.9 4-Decene, 3-methyl- – – – – – 3 – – – – – – –
12.16 1-Undecene 0.73 1.66 0.91 1.02 1.12 1.47 1.17 1.83 2.36 0.9 0.56 0.99 0.9
12.41 Undecane 0.77 1.17 0.94 1.21 0.77 1.51 1.05 1.64 1.74 0.9 0.74 0.84 1.05

F. Atesß et al. / Bioresource Technology 133 (2013) 443–454

12.59 5-Undecene, 4-methyl- – – – – – 1.4 – – – – – – –
13.23 1-Undecene, 7-methyl- 0.47 0.67 0.56 – – – 0.58 – – – 0.71 – –
13.94 Heptane, 4-methylene – – – – 1.07 0.84 – – – – – – –
15.09 1-Dodecene 1.02 1.73 0.95 1.05 1.21 1.36 1.58 1.96 2.4 1.04 0.67 0.92 1.03
15.33 Dodecane 1.24 1.09 1.17 1.29 1.54 1.18 1.4 1.93 2.2 1.37 0.6 1.02 1.12
16.4 Dodecane, 4,6-dimethyl- – – 1.51 – 1.89 – 0.59 – – 0.46 – 0.36 –
17.88 1-Tridecene 1.21 2.41 1.62 1.02 1.67 0.81 2.5 2.33 2.36 1.37 0.41 1.64 0.92
18.12 Tridecane 1.21 – 2.5 1.47 2.18 0.87 3.3 2.03 1.79 1.49 0.48 1.53 0.98
18.81 Undecane, 2,4-dimethyl- – – – – – – 1.85 0.97 – – – – –
19.51 2,3-Dimethyl-3-heptene – – – – – – 1.23 0.5 – – – – –
19.8 Tridecane, 2-methyl 1.65 – – 0.43 – – – – – – – – –
20.52 1-Tetradecene 1.07 1.39 0.71 1.21 0.76 – 1.19 2.12 2.86 0.97 0.55 1.13 1.24
20.73 Tetradecane 1.19 0.99 0.95 1.23 0.88 0.74 1.32 1.64 2.3 1.27 0.55 0.86 1.05
23.03 1-Pentadecene 1.59 1.89 1.33 0.94 0.98 – 1.68 2.36 1.91 1.07 0.3 1.56 1.01
23.22 Pentadecane 1.42 1.12 1.1 1.39 0.83 0.74 1.78 1.76 2.03 1.57 0.63 1.14 1.24
23.85 6-Tridecene, 7-methyl- – – – – – – 0.75 0.27 – – – – –
25.4 1-Hexadecene 1.18 1.34 0.43 0.83 0.53 – 1.28 1.6 1.78 0.53 – 1.11 0.72
25.58 Hexadecane 1.55 1.2 0.98 1.73 0.68 0.63 1.52 1.69 1.97 1.47 0.85 1.2 1.3
27.64 1-Heptadecene 1.11 0.87 0.37 0.91 0.28 – 0.91 1.77 1.87 0.54 0.23 1 0.82
27.82 Heptadecane 1.59 0.85 1.05 1.59 0.58 0.51 1.46 1.7 2.18 1.38 0.48 1.26 1.39
29.79 1-Octadecene 1.25 0.69 0.27 0.71 – – 2.02 0.93 1.59 0.45 – 1.18 0.73
29.95 Octadecane 2.03 1.13 0.87 1.46 0.59 0.48 1.45 1.02 2.06 1.01 0.39 1.55 1.36
31.82 1-Nonadecene 1.01 0.63 – 0.76 – – 0.79 1.56 1.16 0.34 – 0.88 0.66
31.97 Nonadecane 1.53 1.02 0.83 1.7 0.4 – 1.28 1.52 2.75 0.87 0.36 1.39 1.33
33.77 1-Eicosene 1.38 0.96 0.4 0.62 – – 0.96 1.66 1.44 0.54 – 1.03 0.85
33.9 Eicosane 1.98 0.82 0.88 1.57 0.33 – 1.28 1.66 2.23 0.8 0.38 1.28 1.44
35.61 1-Heneicosene 0.97 0.51 – 0.68 – – 0.63 0.94 1.06 – – 0.6 0.61
35.74 Heneicosane 1.4 0.81 0.7 2.21 0.35 – 1.07 2.33 2.08 0.61 0.39 1.16 1.27
37.38 1-Docosene 1.58 – – 0.45 – – 0.62 – 1.08 – – – 0.55
37.52 Docosane 1.66 0.82 0.68 1.92 0.26 – 0.85 2.96 2.11 0.51 0.51 1.41 1.21
39.09 1-Tricosene 0.44 0.33 – – – – – – 0.7 – – 0.46 –
39.2 Tricosane 1.22 0.66 0.64 1.95 – – 0.7 2.32 2.03 0.43 0.49 1.33 1.13
40.73 1-Tetracosene 0.53 0.3 – – – – – – – – – – –
40.84 Tetracosane 1.03 0.73 0.53 1.52 0.56 – 0.56 2.4 1.89 0.47 0.45 1.27 1.06
42.39 Pentacosane 1.2 0.82 0.55 1.14 – – 0.61 2.22 1.61 0.46 0.33 1.47 1.12
43.89 Hexacosane 1.01 0.5 0.38 1 – – 0.49 1.93 1.86 0.43 0.27 1.72 0.92
45.34 Heptacosane 0.78 0.66 0.47 0.64 – – – 1.92 1.24 0.4 – 1.03 0.75
46.74 Octacosane 0.71 0.49 0.4 0.47 – – – 1.63 2.02 0.42 – 0.83 0.77
 F. Atesß et al. / Bioresource Technology 133 (2013) 443–454 449

both the hydrogen and i-butane production was more significant if

catalysts were used in MPW instead of MSW, because 7.96%
0.71
0.61

(MoO3) hydrogen concentration or even 18.73% (HZSM-5) i-butane

–
–
–
–
–
content could be reached. It is interesting that the most efficient
catalyst in main carbon frame isomerisation (HZSM-5) showed
the less efficiency in hydrogen formation in case of MPW pyrolysis,
0.69
0.61
0.71
0.44

vice versa. This phenomenon could be attributing to the dehydro-

–
–
–

genation characteristic of Mo atom and the low surface area of

MoO3. That is why the reforming catalysts in refinery operations
are containing Mo. It was demonstrated by earlier works that the
HZSM-5 catalyst is showed quite high selectivity in the formation
–
–
–
–
–
–
–

of paraffins, olefins and branched hydrocarbons, while the yield of

gases was also high (Kargöz et al., 2003; Onderwater et al., 2001;
Xiao et al., 2010). The hydrogen/CO ratio could be also increased
from 0.047 (without catalyst) to 0.643 (MoO3) at 500 °C using
MSW. Regarding catalysts Al(OH)3 was the less efficient for
–
–
–
–
–
–
–

hydrogen formation (and water shift reaction), because the hydro-

gen/CO ratio was only 0.049. In case of MPW pyrolysis both MoO3
1.52

and Ni–Mo-catalysts have shown the most significant effect to the

–
–
–
–
–
–

hydrogen formation. The demonstrated result refers that hydrogen

has found not only via water shift reaction, but also dehydrogena-
tion of synthetic polymer-derived radicals, too. Relation to the
1.45
1.34
1.16
0.97

0.67
0.51
0.8

temperature dependence it is clear that both the CO

(20.43% ? 15.03%) and CO2 (41.52% ? 39.35%) concentrations, fur-
thermore i-butane (0.54% ? 0.11%) have decreased as function of
pyrolysis temperature in the range of 500 and 600 °C pyrolysing
–
–
–
–
–
–
–

MSW. However, the hydrogen content looks rather similar with

very slight increasing (0.97% ? 1.42%). If MPW was pyrolyzed,
decreasing in hydrogen and i-butane concentrations and slight
increasing in methane content had been concluded. Slight decreas-
–
–
–
–
–
–
–

ing in n-olefin/n-paraffin ratio was found in case of both MSW

(from 0.797 to 0.660) and MPW (from 0.801 to 0.727) pyrolysis
as function of temperature, which refers to the greater possibility
of saturation reaction at higher temperature (e.g. by intermolecular
–
–
–
–
–
–
–

hydrogen transfer). Nevertheless the concentration of iso-paraffins

and olefins decreased with temperature, because the further
degradation of branched hydrocarbons is greater, than that of
non-branched with increasing temperature (Kargöz et al., 2003;
0.35
–
–
–
–
–
–

Onderwater et al., 2001; Xiao et al., 2010).

3.3. Pyrolysis oils

0.37

3.3.1. GC/MS analysis of oils

–
–
–
–
–
–

In this study, oil compositions obtained from MSW and MPW

pyrolysis with or without a catalyst have been evaluated by GC/
0.44
0.52

0.39
0.34

MS. The detailed component analysis, including retention time,

0.7

–
–

compound name, and peak area for oils are shown in Tables 3
and 4. The distribution of compounds in the oils was determined
using a semiquantitative study by means of the percentage area
of chromatographic peaks. As shown in the Tables, because the
–
–
–
–
–
–
–

MSW and MPW oils consist mainly of aliphatic and aromatic and
cyclic hydrocarbons, we have focused on these compounds. Certain
part oils obtained from MSW and MPW pyrolysis at 600 °C and
over FCC catalysts could not be recovered in solution form and they
Pentatriacontane
Tetratriacontane

were therefore not analyzed by GC/MS. Because higher tempera-

Hentriacontane
Dotriacontane
Tritriacontane

tures may induce side-reactions or promote deactivation of the

Nonacosane
Triacontane

catalyst, the temperature range studied was determined at be-

tween 500 and 550 or 600 °C in thermal procedure and 500 °C
for the catalytic procedure.
Due to its structure, the polymer degradation range is wider
than the lignocellulosic biomass. The primary pyrolysis reactions
of the MPW raw materials continued up to 600 °C, but these reac-
tions were completed at 550 °C for the other material, which also
have lignocellulosic structure. A high resemblance was determined
55.39
57.53
50.9
48.1
49.3

53.6

as a result of the comparison of aliphatics of the MSW and MPW

52

oils with standard diesel in the GC. The largest straight-chain al-
Table 4

450
Identified aromatic and cyclic compounds in oils obtained from the pyrolysis of MSW and MPW with (500 °C) or without catalyst (500; 550 or 600 °C).

Retention time Compound name MSW MPW

500 °C 550 °C Y-zeolite b-zeolite Ni–Mo HZSM-5 500 °C 550 °C 600 °C Y-zeolite b-zeolite Ni–Mo HZSM-5
3.65 Toluene 0.24 – 2.12 1.38 1.38 2.64 0.57 1.02 0.31 1.11 1.21 0.18 1.12
4.86 Cyclohexane. 1,3,5-trimethyl – – – – 0.7 – – – –– – – – –
4.98 Cyclohexane. propyl- – – – – 2.31 2.4 – – – 0.46 1.2 – -
5.14 Cyclopentane. 1,3-dimethyl- – – – – – – –– – – – – 0.66 –
5.41 1,2,3-Trimethylcyclohexane – – – – – – 0.93 – – 0.86 0.72 – –
5.61 Benzene, ethyl- 4.1 2.63 5.29 7.7 4.57 11.25 1.61 0.64 0.24 1.97 2.03 1.94 2.95
5.81 o-Xylene 1.23 1.48 5.97 2.4 1.59 4.78 – – – – – – –
5.81 p-Xylene – – – – – – 0.6 1.15 0.97 1.35 4.54 4.86 4.08
6.41 Styrene 3.01 5.13 14.49 2.52 3.29 4 – 4 0.91 0.6 0.62 0.88 1.67
6.58 Cyclopropane, 1-butyl-2-pentyl – – – – – – – – – – 0.93 – –
7.27 Benzene, (1-methylethyl)- 1.61 0.18 1.93 1.82 0.93 2.49 – 0.33 – – 0.91 – –
8.11 Benzene, propyl- – – – 0.58 – 0.4 – – – – – – –
8.36 Benzene, 1-ethyl-2-methyl- – – – 2.5 1.01 3.19 – – – 1.41 3.34 0.25 2.6
8.56 Benzene, 1,3,5-trimethyl- – 1.79 – 1.25 0.91 1.16 – – – – 2.36 – 6.4
8.65 Cyclopentane, 1-ethyl-3-methyl- – – – – – – – – 2.2 8.61 – – 1.53

F. Atesß et al. / Bioresource Technology 133 (2013) 443–454

8.92 Alpha-methylstyrene 2.1 1.61 3.63 0.7 0.96 1.85 – 1.22 – – – – –
9.29 Benzene, 1,2,3-trimethyl- – – – 1.82 1.52 2.56 – – – 1.33 2.79 1.01 2.16
10.18 Benzene, 1-methyl-2-(1-methylethyl) – 0.29 – 1.7 1.42 1.05 – – – 0.33 1.69 – –
10.31 DL-Limonene – 0.77 – 1.01 1.82 0.92 – – – – – – –
10.48 1H-Indene, 2,3-dihydro– – – 0.69 1.96 – 1.19 0.52 0.17 – 0.51 1.24 – 0.72
10.88 1H-Indene – – - 1.26 – – – – – – – – –
10.99 Benzene, 1-methyl-3-propyl- – – – – – – – – – – 1.63 0.38
11.22 Benzene, 1.2-diethyl- – 0.75 – – – – – – – – 2.63 – –
11.26 Benzene, 4-ethyl-1.2-dimethyl- – – – 1.79 – 2.09 – – – – – –– –
11.3 Cyclohexane, hexyl- – 1.28 – – – 1.36 – – – – – – –
11.39 Cyclohexane, decyl- – – 0.86 0.59 – 1.98 0.84 – – – – – –
11.83 Benzene, 1-ethyl-2.4-dimethyl- – – – 1.36 – – – – – 0.51 1.34 – 0.89
12.01 1-Methyl-2-penylcyclopropane – 2.34 – – – 2.07 – – – 0.65 1.54 – 1.32
12.36 1-Ethyl-2,2,6-trimethylcyclohexane – – – – – 1 – – – – – – –
12.6 Benzene, methyl(1-methylethyl)- – – – 1.75 – – – – – – – – –
12.89 Benzene, 1-methyl-4-(1-methylethyl) – – – – – 0.65 – - – 0.4 0.82 – 0.94
13.04 Benzene, 1,2,3,5-tetramethyl- – – – 0.73 – – – – – – 3.04 –– 0.94
13.8 Benzene, 2-ethenyl-1.4-dimethyl- – – – 2.85 0.34 0.8 – – – – 1.54 – –
14.02 1H-Indene, 2-methyl – – 1.13 – 0.38 – – – – – – – ––
14.1 Cyclohexane, 1,1,3,5-tetramethyl-trans – 1.21 – – – – – – – – – – –
14.9 Naphthalene – 0.31 – 1.34 0.37 0.96 – 0.56 – 0.76 1.52 – 0.91
14.98 1H-Indene, 2,3-dihydro-4,7-dimethyl- – – – – – 1.91 – – – –– – – –
15.3 Benzene, 1,3-dimethyl-5-(1-methyle – – – 0.73 – – 0.46 – – – 2.24 – –
17.6 Benzene, pentamethyl- – 1.29 – 0.93 – – – – – – – – –
17.98 Naphthalene, 1-methyl- – – – 1.19 – 0.86 – – – 0.63 2.91 – 1.14
18.33 Cyclohexane, 1,2,4-trimethyl- – – – – – – 1.12 – – – 3.65 – –
18.43 Napthalene, 2-methyl- 1.43 1.19 4.42 1.54 8.49 1.26 – 0.98 – 0.43 1.2 – 0.41
18.51 Cyclopentane, 1-pentyl-2-propyl- – – – – – – – 0.43 – 0.46 – – –
19. 47 Cyclohexane, (2-bromoethyl)- – – 0.85 – – – – – – – – – –
21.3 1,3-Dimethyl Naphthalene – – – 2.47 – – – – – – 3.14 – 0.97
23.04 Cyclohexane. eicosyl – – – – – 0.54 – – – – – – –
23.79 Cyclohexane, 1-ethyl-1-propyl- 1.22 1.03 0.49 – 0.59 – – – – – – 0.98 –
24.3 Naphthalene, 2,3,6-trimethyl- – – – 1.19 – – – – – – 2.49 – –
24.5 Cyclohexane, 1-ethyl-2-propyl- 2.15 – – – 0.32 – – – – – – - -
26.78 Benzene, 1, 10 -(1.3-propanediyl) 0.87 0.48 1.72 1.2 0.3 – – 0.71 – – 0.26 – –
29.56 Phenanthrene 1.13 – – – – – 0.94 – – 0.46 – – –
30.19 Cyclohexane, 1-ethyl-1. 4-dimeth 0.47 – – – – – – – – – – – –
33.5 Cyclohexane, 1,1,3.5-tetramethylcis 0.56 – – – – – – – – – – – –
37.82 Phenanthrene, 1-methyl-7-(1-met 0.52 0.39 – – – – – – – – – – –
 F. Atesß et al. / Bioresource Technology 133 (2013) 443–454 451

kenes and alkanes were determined from C10 to C33 and from C10 to
C35 at a pyrolysis temperature of 550 °C for the MSW and the MPW
pyrolytic oils without catalyst, respectively (Tables 3 and 4). Be-
cause the MPW consists only of polimer, such as PE, PP, PS, PVC,
the range of alkenes and alkanes are wider than that of the MSW
oils. For a similar reason, the yield of the total aliphatic hydrocar-
bons obtained from the MPW pyrolysis without a catalyst is higher
than that of the MSW oils for all temperatures. The ratio of n-par-
affines/n-olefines in the MPW oils is higher than that of the MSW
oils at 550 °C in particular. Polymer contains more hydrogen than
lignocellulosic material. Saturation of the olefins with the hydro-
gen formed during the decomposition of the MPW is predominant.
In addition, the total yield of olefines and paraffines was deter-
mined to be higher in the MPW oils for all temperatures. The n-
paraffines was higher than the n-olefines both with and without
a catalyst procedure for all oils (Fig. 3C and D). This result reflects
that neither the MSW nor the MPW oils have not needed an exter-
nal additional saturation by hydrogenation during pyrolysis, espe-
cially in the thermal procedure where the yields of aliphatics is
much higher.
Pyrolysis liquids obtained from agricultural waste products
contain a wide variety of oxygenated products: lignin-derived
phenolics, acids, aldehydes, ketones, furfural and levoglucosan.
Among these compounds, phenols are predominant in bio-oils ow-
ing to their lignocellulosic structure (Bu et al., 2011; Arcladas,
1991; Ku and Mun, 2006; Atesß and Isikdag, 2008). Only a small
concentration of phenol and derivatives was determined in the
MSW oils, while these components were not detected in the
MPW oils because of the raw material’s structure. This is an ex-
pected result. MPW consists only of plastic particles. However, be-
sides of plastics, MSW also consists of paper, organic waste and
textiles. These substances are responsible for the lignocellulosic
structure of MSW. Ketones are the third most abundant compound
in MSW oils, and MSW oil has more ketonic compound compared
MPW oil (Fig. 3A and B). MPW does not consist of any oxygen con-
tent, but MSW has 19.5% (see in Table 1a). Most of the oxygen in

Fig. 3. Oil composition obtained from MSW (A) and MPW (B) pyrolysis with or without catalyst, the distribution of aliphatic hydrocarbons obtained from MSW (C) and MPW
(D) pyrolysis with or without catalyst and the distribution of aromatic and cyclic hydrocarbons obtained from MSW (E) and MPW (F) pyrolysis with or without catalyst.
452 F. Atesß et al. / Bioresource Technology 133 (2013) 443–454
MSW undertakes the reaction to form ketones. The transformation
of ketones occurs mainly through decarboxylation and, to a lesser
degree, dehydration. Above 400 °C, this transformation produced
aliphatics and aromatics according to a reaction scheme (Gayubo
et al., 2004). Therefore, aliphatic and aromatic hydrocarbons
quickly formed. Because there is no activated medium, such as
an acidic, the aromatic and cyclic compounds remained at limited
levels in the thermal procedure. The pyrolysis oils contain mostly
aliphatic hydrocarbons and aromatic and cyclic compounds, and
less ketones, alcohols, acids and esters in the thermal procedure
without a catalyst. When using different catalysts, the aromatic
and cyclic compounds formed predominantly when compared to
the thermal pyrolysis. The reaction mechanisms are speculated
as follows: aliphatic compounds undergo dehydroaromatization
to form aromatic and cyclic compounds over catalysts.
Depending on certain properties, all catalysts have shown pro-
ductivity and selectivity in converting aliphatic hydrocarbons to
aromatic and cyclic compounds. The different characteristics of
the catalysts (i.e. different pore sizes, pore structure and acidity)
show the uniqueness of each catalyst. In fact, the aromatic
selectivity was HZSM-5 > b-zeolite > Y-zeolite > AlOH3 > MoO3 >
NiMo and b-zeolite > HZSM-5 > Y-zeolite > NiMo > AlOH3 > MoO3
for the MSW and MPW oils, respectively (Fig. 3E and F).
Zeolites are often used as catalysts to improve the product qual-
ity in pyrolysis. Comparing HZSM-5 and b-zeolite with other cata-
lysts, the combined yield and selectivity for aromatic hydrocarbons
and cyclic compounds is exceptionally high. Aromatic and cyclic
hydrocarbons were produced in lower quantities with other cata-
lysts apart from the zeolite catalysts. The low aromatic hydrocar-
bon production may be linked to the absence of shape selectivity
properties and there is no acidic medium for the other catalyst (Ta-
ble 1b).
Zeolites can be characterized by the Si/Al ratio. This ratio may
vary widely in the catalyst composition according to the aim of
the study. The Si/Al ratio is preferably from about 8 to 500. The
highest yield of aromatic and cyclic compounds was obtained as
55% in the case of HZSM-5 zeolite (Si/Al = 12.6) and 48% in the
case of b-zeolite (Si/Al = 17.1) for MSW and MPW oils, respec-
tively. Brønsted acid sites play an important role for the produc-
tion of aromatics. The production of aromatic and cyclic
compounds depends mostly on the active sites of the catalyst.
HZSM-5 was identified as an effective catalyst in the converting
of aliphatics to aromatics for MSW oils, while the b-zeolite cata-
lyst was identified for MPW oils. Thus, the nature of the oils al-
tered the effectiveness of zeolite catalysts to convert them to
hydrocarbons. Pore sizes are also important for catalysts. Pore
sizes higher than 300 m2/g enhanced the selectivities for aromatic
hydrocarbons (Table 1b).
Secondly, when comparing zeolites and other catalysts it can be
seen that the presence of acid sites in the zeolite structure play a
major role in aromatic and cyclic hydrocarbon formation. MoO3
and Al(OH)3 have no acidic sites. Therefore, aromatic and cyclic
compounds stayed limited levels. The catalytic properties of zeo-
lites strongly depend on both strong acid sites and a three-dimen-
sional system of intersecting channels and near circular zig-zag
channels (Adjaye and Bakshi, 1995). Some olefins produced from
light organics undergo cyclization to form cyclic compounds, while
the remaining undergo aromatization reactions to form aromatic
hydrocarbons. Bridgwater (1994), points out that an important
step in the reactions of hydrocarbons over zeolites is aromatiza-
tion. Huber et al. (2006) show that aromatization reactions may
proceed via the Diels–Alder reaction where olefins obtained by
cracking combine with each other to form cyclic and aromatic
compounds.
Aromatic hydrocarbons, such as benzene, toluene and xylenes,
together often referred to as BTX, are important in the petrochem-
ical industry. If ethylbenzene is included, the mixture is sometimes
referred to as EBTX. This can be produced by refining of petroleum.
Because of the depletion in fossil fuels, alternative production of
these compounds should be developed. Ethylbenzene, toluene
and xylene isomers (EBTX) were produced in this study. The yield
of ethylbenzene was increased (Table 4) and ethylene decreased
using catalysts in the pyrolysis. Ethylbenzene is produced by
combining formed benzene and ethylene in a catalyzed chemical
reaction during pyrolysis. Toluene is also a valuable petrochemical
for use as a solvent and intermediary in chemical manufactur-
ing processes. Moreover, toluene increased using a catalyst. Ben-
zene derivatives were considerably increased over the b-zeolite
and HZSM-5 catalysts. The use of zeolite catalysts has a positive ef-
fect in this regard (Table 4).
It is well known that PAHs are formed in large quantities as a
result of secondary thermo-chemical reactions at temperatures
over 700 °C (Ledesma et al., 2002). While the content of polyaro-
matic hydrocarbons in the pyrolysis oils was in a range between
0.3–0.4 mass% (Pakdel and Roy, 1991), the tars from biomass gas-
ification obtained at temperatures over 700 °C showed concentra-
tions of these compounds as high as 85 mass%. These compounds
are almost never produced in pyrolytic oils at neither moderate
temperatures nor when using catalysts in this study. This is an
advantage for oils, since high yields of these compounds are unde-
sirable because they are not useful as chemical feedstock (Bulush-
eva and Ross, 2011). Styrene and derivatives, DL-Limonene,
naphthalene and derivatives and 1H-indene and derivatives are
the other compounds produced during the MSW pyrolysis. DL-Lim-
onene and 1H-indene and derivatives were not detected in the
MPW pyrolysis.
3.3.2. 13C NMR analysis of oils
13
C NMR spectrometry gives direct structural information relat-
ing to the carbon groups present (Snape et al., 1979). The number
of signals tells us how many different carbons or sets of equivalent
carbons are in the 13C NMR. This method provides the percentages
of carbons in different chemical functional groups based on chem-
ical shift (Mullen et al., 2009).
Data obtained from the 13C NMR spectra of the oils is given in
Table 5. The data on the chemical shifts has been obtained from
references (Mullen et al., 2009; Ben and Ragauskas, 2011).
Carbonyl resonances (170–210 ppm) and aromatic carbon
joined to hydroxyl and ether oxygen resonances (148–168 ppm)
either were not observed or were observed with negligible small
peaks in the 13C NMR spectra. There is good agreement with the
GC/MS results. In addition, regarding the GC/MS results, the car-
bonyl groups have stayed minimum levels and aromatic carbon
joined to any oxygen was not observed. The region between
110–148 ppm contains the resonances of aromatic carbons. Com-
patible with the GC/MS results, aromatic carbons increased with
temperature and especially when using zeolite catalysts for oils ob-
tained from MSW and MPW pyrolysis.
The chemical shifts of the aliphatic groups are methyl, methy-
lene, or methine. The methyl groups have a chemical shift range
of 12–32 ppm, methylene groups of 22.5–44 ppm (for one adjacent
methine group), and methine groups of 27–57 ppm for no adjacent
methine groups (Snape et al., 1979). The region between 27.5–
37 ppm contains the resonances of the methylene groups in dis-
tinct compounds: CH2 not adjacent to CH in alkyl groups, CH2 al-
pha and CH2 adjacent to terminal CH3 in alkyl substituents with
more than four carbons, CH2 in ring joining ethylene groups and
some CH2 naphthenic. As shown from in Table 5, the carbon distri-
bution of this region is more dominant in the MPW oil, as expected.
Because of their structure, MPW oils have more aliphatic than
MSW oils.
 F. Atesß et al. / Bioresource Technology 133 (2013) 443–454 453

Table 5
Carbon distributions (% of total carbon) of oils obtained from MSW and MPW pyrolysis based on literature compounds (Snape et al., 1979; Ben and Ragauskas, 2011).

Chemical shift, 500 °C 550 °C Y- b- MoO3 Ni– HZSM- Al(OH)3

ppm zeolite zeolite Mo 5
MSW Carbonyl 170–210 – – – – – – – –
pyrolysis Aromatic C–O 148–168 – – – – – – – –
Aromatic C–C 129.5–148 2.5 3.7 3.9 4.1 2.6 2 3.2 4.1
Aromatic C–H 110–129.5 9.9 12.1 17.9 25.3 14.8 12.3 20.3 15.8
Ring joining methylene. CH in alkyl groups and naphtenic rings 37–60 8.2 12.0 11 9.1 9.4 13.9 4.8 13.8
CH2 in alkyl groups not adjacent to CH. CH2 in ring joining ethylene 27.5–37 47.2 38.4 35.2 33 28.5 21.9 26.2 23.9
groups
Naphthenic CH2. 24–27.5 2 2.2 4.9 1.9 6.6 7.3 5.8 4
CH2adjacent to terminal CH3 in alkyl groups>C4 22.5–24 4.9 6.8 6.8 4.6 5.4 2.6 5.8 4.6
a-CH3 not shielded by any adjacent rings or groups 21.5–22.5 7 4.2 2.3 2.8 4.6 –– 2.5 3.4
Methyl-aromatic 19.1–21.5 9.7 9.5 9.7 8.4 10.1 9.9 8.5 15.8
b-CH3 in ethyl groups 15–18 0.05 – 0.8 1.5 8.4 20.4 9.5 1.5
CH3 c or further from an aromatic ring + a-CH3 shielded by 2 adjacent 11–15 8.8 11 7.3 9.2 9.2 9.7 13.7 13.1
rings or groups
MPW Carbonyl 170–210 – – – – – – – –
pyrolysis Aromatic C–O 148–168 – – – – – – – –
Aromatic C–C 129.5–148 0.4 2.6 3.4 4.5 3.2 2.4 3.7 2.9
Aromatic C–H 110–129.5 6.2 9.4 11.9 14.7 4.4 4.5 11.9 7.5
Ring joining methylene. CH in alkyl groups and naphtenic rings 37–60 2.6 4.0 6.0 5.5 8.7 9.2 4.0 12.0
CH2 in alkyl groups not adjacent to CH. CH2 in ring joining ethylene 27.5–37 57.4 65.3 44.1 31.2 45.0 50.3 42.4 36.0
groups
Naphthenic CH2. 24–27.5 1.8 0.9 3.1 5.2 2.6 2.8 3.8 3.6
CH2 adjacent to terminal CH3 in alkyl groups > C4 22.5–24 12.2 7.5 11.1 9.3 9.6 8.0 17.0 8.5
a-CH3 not shielded by any adjacent rings or groups 21.5–22.5 – – – – 2.7 2.6 – 4.8
Methyl-aromatic 19.1–21.5 5.9 0.9 5.8 9.1 9.2 6.1 3.5 10.8
b-CH3in ethyl groups 15–18 1.9 0.7 0.6 1.4 0.8 3.9 1.1 0.8
CH3 c or further from an aromatic ring + a-CH3 shielded by 2 adjacent 11–15 10.9 7.7 14.0 13.6 13.7 10.1 12.9 13.5
rings or groups

The most distinguished signal in this region is a sharp peak at
29.5–29.8 ppm, which is attributed to methylene a or further
from the end of the chain, and c or further from an aromatic ring
in alkyl chains at least 8 carbon atoms long. Polymers formed by
a straightforward linking together of monomer units. Thermo-
plastic polymers, similar to those used in this study, consists of
long and mostly straight hydrocarbon chains. The degradation
of polymers to form smaller molecules may proceed by random
scission or specific scission. Polymer decomposition occurs
during breakage of the bonds that hold the atoms of the polymer
together. When heated above 450 °C, polymers such as polyeth-
ylene and polypropylene degrade to form a mixture of hydrocar-
bons. Other polymers undergo a specific chain scission with
breakage occurring only at the ends. The physical properties of
a polymer are strongly dependent on the size or length of the
polymer chain. Many polymeric materials having chain-like
structures similar to polyethylene are known. The ingredient
or monomer of polyethylene is ethylene. It has the formula
C2H4, and consists of a pair of CH2 groups connected by a double
bond. The second observed dominant carbon in the aliphatic
groups, after CH2 in alkyl groups not adjacent to CH and CH2
in ring joining ethylene groups, is the CH3 c or further from an
aromatic ring + a-CH3 shielded by 2 adjacent rings or groups.
Furthermore, the peak between 31.7–31.9 ppm is attributed to
methylene in the c position from the end of an alkyl side chain
(Snape et al., 1979). The peaks between 55.2–60.8 and 60.8–95.8
attributed to methoxylaromatic and aliphatic C–O, respectively,
were either not observed or were observed with a negligible
peak in the 13C NMR spectra. Other carbons were also detected
in the 13C NMR spectra, representing only a small percentage.
4. Conclusion
In this work pyrolysis of real MSW and MPW was investigated
in a batch reactor. It was concluded that:
 volatile product yields increased in the presence of catalyst,
while the fully pyrolysis time necessity decreased,
 using Ni–Mo-catalyst resulted the highest water, while HZSM-5
the least in case of MSW pyrolysis,
 gases contained hydrogen and hydrocarbons; CO, CO2 was
obtained only from MSW,
 aromatic and cyclic compounds predominantly formed in the
presence of catalysts,
 catalyst pore size and Si/Al ratio had main role to their
efficiency,
 the catalytic effect was more significant using MPW.
Acknowledgements
This work was supported by the European Union and co-fi-
nanced by the European Social Fund in the frame of TAMOP-
4.2.2/B-10/1-2010-0025 project. Also, the authors thank to the
AUBIBAM, for 13C NMR analysis.
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