Fuel 89 (2010) 1911–1918

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Co-pyrolysis of pine cone with synthetic polymers

Mihai Brebu a, Suat Ucar b, Cornelia Vasile a, Jale Yanik c,*
a
‘‘Petru Poni” Institute of Macromolecular Chemistry, Physical Chemistry of Polymers Laboratory, 700487 Iasi, Romania
b
Chemistry Program, Izmir Vocational School, Dokuz Eylül University, 35160 Buca-Izmir, Turkey
c
Ege University, Faculty of Science, Chemistry Department, 35100 Izmir, Turkey

articleinfo abstract

Article history: Biomass from pine cone (Pinus pinea L.) was co-pyrolyzed with synthetic polymers (PE, PP and PS) in order
Received 28 May 2009 to investigate the effect of biomass and plastic nature on the product yields and quality of pyrolysis oils and
Received in revised form 21 January 2010 chars. The pyrolysis temperature was of 500 °C and it was selected based on results from ther- mogravimetric
Accepted 26 January 2010 analysis of the studied samples. Co-pyrolysis products namely gases, aqueous and tar fraction coming from
Available online 21 February 2010 biomass, oils from synthetic polymers and residual char were collected and ana- lyzed. Due to the synergistic
effect in the pyrolysis of the biomass/polymer mixtures, higher amounts of liquid products were obtained
Keywords: compared to theoretical ones. To investigate the effect of biomass con- tent on the co-pyrolysis, the co-
Co-pyrolysis pyrolysis of pure cellulose as model natural polymer for biomass with polymer mixture was also carried out.
Biomass In the presence of cellulose, degradation reaction leading to more gas formation and less char yield was more
Cellulose
advanced than in the case of co-pyrolysis with pine cone. Co- pyrolysis gave polar oxygenated compounds
Polymer
distributed between tar and aqueous phase and hydrocar- bon oils with composition depending on the type
Pyrolysis oil
of synthetic polyolefin. Co-pyrolysis chars had higher calorific values compared to pyrolysis of biomass alone.

© 2010 Elsevier Ltd. All rights reserved.

1. Introduction Synthetic polymers could act as hydrogen source in thermal co-

Evaluation of municipal solid wastes (MSW) plays an important
role for utilization in energy production and the protection of
environment. The MSW in most European countries contains 65
wt.% or more lignocellulosic materials and lignocellulosic/cellu-
losic waste (paper, cardboard, vegetable and food residues) that are
commingled with synthetic polymer based materials (~15%) and
inorganic materials ( ~20%). In the last decades, lignocellulosic
materials such as wood flour and cellulosic fibers were increasingly
used for the production of polymeric composites [1–3]. In addition,
the lignocellulosic/plastics laminates are spreading in food indus-
try as aseptic packaging materials. Therefore the treatment and
valorization of biomass–plastic mixtures is both a necessity and a
great challenge. The upgrading of these waste materials to hydro-
carbon mixtures by co-pyrolysis or co-gasification techniques have
received much attention in recent years because these might allow
the reduction of the volume of waste, the recovery of chemicals and
the replacement of fossil fuels [4,5]. The thermal co-processing
treatment methods could be environmentally friendly ways for the
transformation of lignocellulosic and plastic waste into valuable
products such as chemicals or fuels.
* Corresponding author. Tel./fax: +90 232 38828264.
E-mail address: jale.yanik@ege.edu.tr (J. Yanik).
processing with organic natural materials with less hydrogen con-
tent such as coal or biomass [6]. The synergistic effects observed for
co-liquefaction of coal–plastic mixtures lead to an increase in oil
yields [7–9]. On the other hand, biomass has low C content of 47–51
wt.% and high O content of 42–46 wt.% giving highly oxy- genated
pyrolysis oils. However, synthetic polymeric materials such as waste
plastics or tires have very high C content of about 84 wt.% and low
O content of about 1.5 wt.% producing hydrocar- bon oils by
pyrolysis. Co-processing of synthetic polymers with biomass could
balance the C, O and H in the feedstock, with strong effects on the
properties of degradation products. Biomass has low- er thermal
stability compared to plastics and thus it could affect their radical
degradation mechanism by promoting the degrada- tion of synthetic
macromolecules [1]. In the co-pyrolysis, the yields and composition
of the products strongly depends on the treat- ment method,
processing conditions, type of biomass and of syn- thetic polymers.
In this study, co-pyrolysis of thermoplastics (PE, PP and PS) with
a lignocellulosic material and with cellulose was carried out to
investigate the effect of biomass and plastic origin on the product
yields. Pine cone was selected as lignocellulosic material because of
its’ low ash content. Thus, the catalytic effect of inorganic matter has
been minimized in comparison with the pyrolysis between cel-
lulose and complex lignocellulosic material. Chemical structures and
fuel properties of liquid products and chars were investigated.

0016-2361/$ - see front matter © 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2010.01.029
1912 M. Brebu et al. / Fuel 89 (2010) 1911–1918

Table 1 2.3. TG analysis

Properties of pine cone (Pc).

Proximate analysis, wt.% (as received) Thermogravimetric analysis of pine cone, PE, PP and PS was per-
Moisture 9.6 formed in a thermogravimetric analyzer (Perkin Elmer Diamond
Ash 0.9 TG/DTA) under N2 atmosphere. The sample amount (particle si- ze
Volatile 77.8
< 100 lm) was of about 10 mg for each TG run. The flow rate of
Elemental analysis, wt.% (on dry basis) purge gas (pure N 2, 99.99%) was kept at 200 ml min —1. The sam- ple
C 42.62
was heated from the ambient temperature up to 600 °C with heating
H 5.56
N 0.76
rate of 10 °C min—1.
S 0.05
O* 51.01
2.4. Product analysis
Main constituents, wt.% (on dry basis)
Lignin 24.9
Hemicellulose 37.6
The condensable pyrolysis products were separated into aqueous
Cellulose 32.7 fraction and tar/oils. The aqueous fraction was extracted with ethyl
Extractives 4.8 acetate that allows qualitative analysis of contained organic com-
* pounds. The degradation tars/oils and the ethyl acetate extracts from
Calculated by difference.
aqueous fractions were analyzed by gas chromatography coupled
with mass selective detector (GC–MSD), performed on an Agilent
6890N GC–5975 inert XL MSD instrument using a HP5-MS column
Condenser (cross-linked methyl siloxane: 30 m × 0.25 mm × 0.25 lm). The
following parameters were used: injector – temperature of 225 °C,
split ratio of 50:1, volume of injected sample of 0.2 ll; temperature
Glass reactor

(30 mm / 350 mm) Water program – initial temperature of 35 °C that was hold for 1 min, fol-
lowed by heating up to 50 °C by a heating rate of 5 °C min—1 then up
to 240 °C by a heating rate of 10 °C min—1 and finally hold at 240 °C
Furnace
for 7 min; flow rate program – initial flow rate of 0.5 ml min—1 that
(500 °C)
was hold for 4 min then increased to 1 ml min—1 that was main-
tained until the end of analysis. Identification of compounds was
Teflon bag performed according to library data.

Sample (15 g) Air trapWater trap Elemental analysis (C, H, S and N) of pine cone, oils/tars and res-
idues was determined with an elemental analyzer (LECO CHNS 932)
Graduated cylinder according to ASTM D5291-96. The gross calorific values of oils/tars
Thermocouple for liquid products and residues were determined using an IKA C-2000 Basic

Fig. 1. Schematic representation of experimental set-up for pyrolysis of pine cone

model analyzer according to ASTM D240-02. The amount of total
alone and mixed with synthetic polymers. phenols in aqueous fractions were determined by colorimetry
(reaction of phenols with 4-nitroaniline to a yellow complex) with
the photometer by Hach Lange-DR2800. Water amounts of oils/ tars
2. Materials and methods
and aqueous fractions were determined by coulometric or vol-
umetric Karl Fischer Titrator (Mettler Toledo DL 31).
2.1. Materials

The feedstock materials used in this study included pine cones of
Pinus pinea L. (Pc), cellulose (Cell), low density polyethylene (PE),
polypropylene (PP) and polystyrene (PS). The pine cones obtained
from forest in Izmir area were milled and sieved to a particle size of
less than 1 mm and dried in air for several days. Commercially
available cellulose was used as powder form. PE, PP, and PS were
commercial polymers which did not contain any stabilizers, fillers
and pigments. Some properties and composition of the pine cones
are given in Table 1.
2.2. Pyrolysis procedure
The pyrolysis experiments were performed in a glass reactor
under atmospheric pressure by semi-batch operation (Fig. 1). A 15
g amount of feedstock material was used for each experiment and
heated by 10 °C min—1 up to final decomposition temperature of 500
°C. The reactor has an internal diameter of 30 mm and a to- tal length
of 350 mm. The liquid products were condensed in a water-cooled
condenser and collected in a graduated cylinder. As aqueous fraction
was immiscible with tar and oil it could be easily separated by
density. Gaseous products were passed through a flask with water.
Experiments were performed on Pc alone or as binary mixtures with
PE, PP or PS in 1/1 weight ratio. Two mixtures consisted of
Pc/PE/PP/PS and Cell/PE/PP/PS in weight ratio of 3/4/2/ 1 were also
studied.
3. Results and discussion
3.1. TGA results
Fig. 2 shows the thermogravimetric (TG) and derivative ther-
mogravimetric (DTG) curves of pine cone, PE, PP and PS. It can be
seen that pine cone has the lowest thermal stability starting to
decompose around 200 °C while the synthetic polymers decompose
at higher temperatures of around 350 °C (PS and PP) or 400 °C (PE).
Following the loss of moisture that occurs below 150 °C, the DTG
curve for pine cone exhibits two peaks in the temperature range of
200–480 °C. The main decomposition step took place between 250
and 400 °C with maximum rate at 360 °C (Tmax), showing a large
DTG peak with a shoulder at 274 °C that is a sign of many
overlapping processes giving a mass loss of about 65 wt.% from the
initial sample The second decom- position step is much smaller in
both the temperature range (400–480 °C) and the mass loss ( 5.6
~ [10–13], it seems that the first
wt.%). Based on the litera- ture data
DTG peak is associated with the decomposition of hemicellulose
and cellulose and the second one mainly with decomposition of
lignin and of residual charcoal from cellulose and hemicellulose. As
seen from Fig. 2, the TG/DTG curves of PS, PP and PE have almost
the same trends; this indicates that they have similar pyrolysis
behavior due to the hydrocarbonated main chain. The TG and DTG
curves of polymers
 M. Brebu et al. / Fuel 89 (2010) 1911–1918 1913

100 Table 2
Product distributions from the pyrolysis of pine cone alone and copyrolysis of Pc/PE,
Pc/PP, Pc/PS, Pc/PE/PP/PS and Cell/PE/PP/PS at 500 °C, wt.%.
Pine cone
80
Sample mass , %

PE Feed Gas* Aqueous phase Tar/oil Char

PP Pc 15.9 38.6 8.9 36.6

60 Pc/PE (1/1) 16.5 18.9 45.0 19.6
PS
Pc/PP (1/1) 16.8 18.4 45.7 19.1
Pc/PS (1/1) 8.8 17.4 52.3 21.5
40
Pc/PE/PP/PS (3/4/2/1) 11.3 11.9 64.1 12.7
Cell/PE/PP/PS (3/4/2/1) 21.5 14.0 54.9 9.6
20 *
Calculated by difference.

0
50 150 250 350 450 550
Table 3
Product distributions from the pyrolysis of PE, PP and PS alone, wt.%.

29 Feed Gas* Oil Residue

PE 14.4 68.2 16.8

24 PP 12.7 72.6 14.7
PS 1.0 85.2 13.8
-DTG , a.u.

19 *
Calculated by difference.

14

9
4 co-pyrolysis of biomass/synthetic polymers. The product yield from
-1
50 150 250 350 450
Temperature, ºC
Fig. 2. TG (a) and DTG (b) curves of pine cone, PE, PP and PS.
recorded in this work are similar with those reported by other
authors [14–16].
In the case of synthetic polymers, there was no residue remain-
ing at the final temperature of TG measurements (650 °C) whereas
the residue for pine cone was of 15 wt.% from the initial sample
mass. This is related to the high content of ash and fixed carbon
in biomass, which was not decomposed at this temperature. From
TG/DTG curves, it can be concluded that the temperature of 500 °C
is the suitable pyrolysis temperature for the mixture of synthetic
polymers and pine cone. It should be noted that no synergetic ef-
fect was observed from the TG and DTG curves of polymer/pine
cone mixtures (not presented here). The temperatures correspond-
ing to the maximum rate of mass loss (Tmax) of each polymer were
the same when analyzed alone and in mixtures.
3.2. Pyrolysis yields
As known, pyrolysis yields depend on many parameters such as
temperature, particle size, heating rate and type of feedstock. Tem-
perature plays a major role in biomass pyrolysis. In this study, the
co-pyrolysis of biomass and synthetic polymer was carried out at 500
°C. The co-pyrolysis temperature was chosen based on the TGA
results.
Pyrolysis of pine cone alone and mixed with synthetic polymers
gave gaseous and condensed products accumulated in the graduate
cylinder, part of initial material remaining inside reactor as resi- due.
The condensed products consisted of an aqueous phase that contains
water-soluble organic compounds and an organic phase. The organic
phase was tar for pyrolysis of pine cone and a mixture of tar and oil
for pyrolysis of pine cone mixed with synthetic poly- mers. Although
these two fractions were separated for individual analyses, this
could not be done quantitatively. Therefore they
were considered together as ‘‘oil” in calculation of mass balance.
Table 2 shows the char, oil, aqueous fraction and gas yields from the
pyrolysis of pine cone alone was also presented in the same table.
For comparison purpose, the product yields from pyrolysis of
550 synthetic polymers (PE, PP, PS) [17] are given in Table 3.
Although the liquid product obtained from pyrolysis of pine cone
consisted mainly of aqueous phase, pyrolysis of polymers produced
oil as main product. By comparing the product yields from Tables 2
and 3, it is seen that the experimental yields from the co-pyrolysis
are different from the theoretical ones calculated based on the yields
from the pyrolysis of the individual compo- nents of the mixtures.
Adding PE, PP or PS to pine cone led to an increase in the yields of
gas and liquid pyrolysis products. It is known that because of the
high hydrogen content, polyolefinic plastics are excellent hydrogen
source. It has been suggested by other researchers that polyolefinic
polymers such as PE and PP could provide hydrogen during thermal
co-processing with wood biomass and can lead to an increase of
liquid production [18]. Sim- ilarly, Rutkowski et al. studied the co-
pyrolysis of cellulose with polystyrene and obtained bio-oils with
higher yields and better quality in comparison to those produced
from biomass alone [19]. Their results showed that the addition of
polystyrene to cel- lulose has a positive effect on the yield and basic
physical proper- ties of bio-oil. They concluded that during
pyrolysis, not only does decomposition of cellulose and polystyrene
simultaneously occurs, but also, reactions between the degradation
of products from cel- lulose and polystyrene take place. Moreover,
Sharypov et al. stud- ied the thermal behavior of wood biomass and
synthetic polymer mixtures in a rotating autoclave [20]. Beech wood,
pine wood, cel- lulose, hydrolytic lignin were used as wood biomass
and medium density polyethylene, isotactic and atactic
polypropylene were se- lected as polyolefinic materials. The
obtained results showed that there was a synergistic effect in the co-
pyrolysis of biomass–plastic mixtures in the form of enhanced oil
yields. Also, it was observed that the type of both biomass and
polymer plays an important role in the product distribution of co-
pyrolysis. Finally, they concluded that co-pyrolysis process could
have potential for utilization of lig- nocellulosic and plastic waste for
liquid production. In this study, the residue yields from the co-
pyrolysis process were lower than that of theoretical one for all
tested pine cone–polymer mixtures whereas their oil yields were
higher. The reason might be presence of hydrogen which was
provided by polyolefinic polymers in the
1914 M. Brebu et al. / Fuel 89 (2010) 1911–1918

Abundance
26
1.2e+07 Tar

1.0e+07
22

0.8e+07 29
34

0.6e+07 11
31

0.4e+07

16 30
13 17 19 21
0.2e+07 12 28 32
35
1 4 9 15 20 24 25
3 7 8 14 27 33
10 18 23
0 2 5 6

Abundance
ethylacetate 1: acetone 12: 2-furanmethanol 24: maltol
solvent 2: acetic acid methylester 13: xylene 25: 1,4-dimethoxybenzene
1.2e+07 Aqueous phase 3: 2,3-butanedione, 14: 3,4-dihydro-2H-pyran 26: 4-methyl-2-methoxyphenol (p-creosol)
2-butanone 5-methyl-2(3H)-furanone 27: 4,7-dimethylbenzofuran
2-methylfuran 15: -pinene 5-(hydroxymethyl)-2-furancarboxaldehyde
1.0e+07 4: acetic acid 16: 5-methyl,2-furancarboxyaldehyde 2,3-dimethoxytoluene
5: propanoic acid methylester 17: phenol 28: 3-methyl-1,2-benzenediol
6: 2-butenal 18: 3-carene 29: 4-ethyl-2-methoxyphenol (p-ethylguaiacol)
7: 1-hydroxy-2-propanone 19: 2-cyclopenten-1-one-2-hydroxy-3- 30: 4-methyl-1,2-benzenediol
0.8e+07 3-methyl-3-buten-2-one methyl (maple lactone) 31: thymol
8: 2,5-dimethylfuran 20: 2-methylphenol 32: 4-alylguaiacol (eugenol)
9: toluene 21: 3-methylphenol 33: vanillin
0.6e+07 10: 3-furaldehyde 22: 2-methoxyphenol (o-guaiacol) 34: isoeugenol
11: 2-furancarboxyaldehyde 23: 2-methylbenzofuran 35: acetovanillone

0.4e+07

0.2e+07

0
2 4 6
Time , min C C C 8 10 12 14 16 18 20
C C C C C C C
5 6 7 C8 9 10 11 12 C13 14 15 C16 17 C18

Fig. 3. GC–MSD chromatograms and identification of main compounds in tar and in ethyl acetate extract from aqueous fraction produced from the pyrolysis of pine cone.
with the lignin content of biomass [22]. The fact that a consider- able
difference in the gas yields was observed between the two mixtures might
co-pyrolysis reactions. Thus, the hydrogen partly inhibited the be due to the presence of lignin which degrades
recondensation reactions leading to formation of char. From Tables
2 and 3 it is clearly seen that the co-pyrolysis has no considerable
effect on the yields of gas and aqueous phase.
There was no difference in the product yields of mixtures con-
taining PE and PP while the one with PS gave higher amount of
oil and fewer gases. In fact, comparison of the PS gas yield with
PE and PP showed that gas yield is the lowest for PS (Table 3).
The distinctive difference between the pyrolysis product distribu-
tion between PS and the other polyolefins (PE and PP) is attributed
to the chemical structure and associated thermal behavior [16]. As
seen from the thermogravimetric results, evolution of degradation
products (weight loss) started at lower temperatures for PS com-
pared to PP and PE. The degradation of PS produces monomer, di-
mer, trimer and benzene derivatives which are the main
compounds in the liquid product. The free radicals formed during
pyrolysis of PS are more stable and could initiate other reactions.
When cellulose was mixed with synthetic polymers instead of
pine cone, the amount of gaseous products almost doubled and
that of aqueous phase slightly increased. Degradation was stronger
in this case, proved by the lower amount of residue. The reason
might be the lower amount of cellulose in the pine cone/polyolefin
mixtures because beside cellulose, pine cone also contains large
amounts of hemicellulose and lignin, as well as extractives. Be-
cause of its aromatic nature, lignin gives higher yields of char
and tar than cellulose [21]. Therefore, char formation increases
slowly and evolves low quantity of gas at the pyrolysis
tempera- ture used in our experiments [23].

3.3. Characterization of liquid products

Pyrolysis of pine cone gives polar oxygenated

compounds com- ing from its cellulose and lignin
components and these compounds were distributed
between tar and aqueous phase. Fig. 3 shows the GC–
MSD chromatograms of tar and of organic compounds
ex- tracted with ethyl acetate from the aqueous fraction
obtained from pyrolysis of pine cone. As seen from Fig. 3,
tar and aqueous phase show similar composition. The
compounds in bio-oil (tar) can be classified into two
groups; water soluble and water insoluble. Water
insoluble fraction is composed of lignin derived
degradation products (high molecular weight and low
molecular weight lignin materials) and extractives which
can not be eluted in GC [24]. It can be said that the
chromatogram of tar in Fig. 3 shows only the water
soluble compounds in tar. This explains the similar
compo- sition of tar and aqueous phase, as shown by
Fig. 3.
In contrast to tar obtained from pyrolysis of pine cone
alone, oils obtained from co-pyrolysis of tar and
polyolefins consisted mainly of hydrocarbons (Fig. 4).
The composition of oils varied with the type of polyolefin
used in co-pyrolysis. The composition of oils was
characterized by C-NP gram curves (Fig. 5). These curves
show the distribution of compounds (e.g. GC–MSD area
%) in a complex mixture versus the corresponding carbon
number of nor- mal paraffins (e.g. carbon number of n-
octane is 8) having equiva- lent boiling point range [25].
The equivalence with the normal paraffin was made by
comparing the retention times from GC anal-
 M. Brebu et al. / Fuel 89 (2010) 1911–1918 1915

Abundance

Tar/oils Pine cone

10e+06

5e+06

Pc/Pe
10e+06

5e+06

Pc/Pp
10e+06

5e+06

Pc/Ps
10e+06

5e+06

0
2 4
Time , min CC C 6 C 8 C 10 C 12 14 C 16 C 18 C 20 C 22 24 C 26 C 28 C 30
C8 C12 C13 14 C15 17 C18 C25
5 6 7 9 10 11 16 19 C20 C21 C22 23 24 26

Fig. 4. GC–MSD chromatograms of oils produced from pyrolysis of pine cone alone and mixed with PE, PP and PS.
from co-pyrolysis come from degradation of lignocellulosic mate- rial (pine
cone) because the pyrolysis of synthetic polymers gives non-polar
ysis using a non-polar column. In these conditions hydrocarbons hydrocarbons. This was clearly seen in the GC–MSD chromatograms of
appear in the order of their increasing boiling points. aqueous phases (Fig. 3) that show similar
The chromatogram of oil obtained from the mixture of pine cone
and PE showed the typical shape of homologues series of sat- urated
and unsaturated hydrocarbons coming from the degrada- tion of PE
that are uniformly distributed on a wide range of carbon numbers
in C-NP gram (Fig. 5). The oil from the mixture of pine cone and
PP showed numerous GC peaks corresponding to branched
hydrocarbons, the main ones being located at carbon number values
of 6, 9, 11, 14, 16 and 18 that are typical for propyl- ene oligomers
from dimers up to heptamers [26]. The mixture con- taining PS
showed a maximum at n-C9 in C-NP gram, corresponding to peaks
of styrene monomer and derivatives in the chromatogram and also
other maxima at n-C17, n-C18 and n- C25 corresponding to styrene
dimer and trimer structures.
To observe the effect of co-pyrolysis on composition of oils, the
experimental C-NP gram curves of pyrolysis oils from mixtures
were compared with the calculated ones based on the additive rule.
As seen in Fig. 5 the amount of low molecular weight com- pounds
in n-C5–n-C15 range is smaller and that of the compounds above n-
C16–n-C18 is greater in the co-pyrolysis oils compared to the
theoretical values (calculated C-NP curves). This result indi- cates
that lignocellulosic material inhibits the formation of light
compounds from degradation of PE, PP and PS by participating of
biomass-derived radicals in polymer radical terminations [27].
It is expected that the compounds in aqueous phases obtained
composition for pyrolysis of pine cone alone or mixed
with PE, PP and PS.
The main classes of compounds and the main
compounds in each class are listed in Table 4, their amount
being determined from the percent peak area in GC–MSD
chromatograms. By consid- ering the results in Table 4, it is
difficult to give an explanation on the synergistic effect of
biomass and plastic during co-pyrolysis. However,
differences had been observed in composition of aque- ous
phases from pyrolysis of synthetic polymers mixed with
pine cone and with cellulose. The non aromatic ketones,
guaiacols and catechols that are degradation products of
lignin were absent in the aqueous phase from pyrolysis of
mixture containing cellulose alone as component of
biomass. However, the relative amount of furans from the
pyrolysis of mixture containing cellulose instead of pine
cone was considerably higher than that of mixture contain-
ing pine cone, since furans are formed from decomposition
of cel- lulose. It should be also noted that the aqueous
phases consisted of water around 62–69 wt.%.
Overall, it can be mentioned that the composition of oils
ob- tained from co-pyrolysis depends on the type of
synthetic polymer in mixture whereas the type and amount
of organics in aqueous phase varied with the ratio of
holocellullose and lignin.

3.4. Fuel characteristics of the pyrolysis products

Pyrolysis of carbonaceous materials produces gas,

oil/tar and char which can be used as fuel as well as a
feedstock for petro- chemicals and other applications. The
pyrolysis tar obtained in this study from pine cone was
reddish brown in color with irritable odour, whereas the
oils obtained from co-pyrolysis were yellow
1916 M. Brebu et al. / Fuel 89 (2010) 1911–1918

Table 4
The main compounds in aqueous phases obtained from pyrolysis of Pc and copyrolysis of Pc/PE, Pc/PP, Pc/PS, Pc/PE/PP/PS and Cell/PE/PP/PS.

Compounds Rt (min) % Area

Pc Pc/PE Pc/PP Pc/PS Pc/PE/PP/PS Cell/PE/PP/PS

Alcohols 0.35 1.38 0.77 0.67 1.36 1.28

Acids 7.90 11.38 9.05 7.99 7.51 3.79
Formic acid 3.06 – 0.23 0.20 – 0.20 0.27
Acetic acid 3.71 5.06 8.80 7.05 6.07 5.46 –
Propanoic acid 4.70 1.47 0.88 0.73 0.70 0.69 1.98
2-Propenoic acid 4.80 0.30 0.86 0.73 0.57 1.17 0.19
Aldehydes 3.83 5.13 3.60 3.58 5.38 3.70
Acetaldehyde 2.40 2.13 3.26 2.42 1.94 3.30 0.97
Hydroxyacetaldehyde 3.17 0.51 0.63 0.60 0.62 0.64 1.52
2-Propenal, 2-methyl 4.01 0.41 0.72 0.57 0.40 0.74 0.41
2-Butenal, 2-methyl 5.64 0.18 – – – – 0.27
Propanol 5.73 0.39 0.52 0.42 0.40 0.45 0.52
Benzeneacetaldehyde 10.23 0.21 – 0.18 0.25 0.25 –
Non aromatic ketones 13.99 19.77 19.65 16.05 18.28 22.44
Furans 14.52 17.46 16.20 13.91 15.14 36.21
Furan, 2-methyl 5.32 0.11 0.09 0.09 0.08 0.09 0.10
2-Furaldehyde 6.24 0.23 0.23 0.22 0.16 0.17 0.17
2-Furancarboxaldehyde 6.56 6.80 8.17 7.32 6.45 7.27 15.35
2-Furfuryl alcohol 6.94 1.54 1.27 1.47 1.62 1.69 0.82
Furan, 2-ethyl 7.11 0.16 0.16 0.13 0.14 0.15
2-Acetylfuran 7.93 0.35 0.45 0.38 0.29 0.37 0.08
2(5H)-Furanone 7.98 0.90 1.20 1.01 0.91 1.19 0.70
2(5H)-Furanone, 5-methyl 8.50 0.37 0.45 0.40 0.24 0.47 1.09
5-Methylfurfural 8.84 1.86 2.25 2.02 1.69 1.86 6.07
Hydroxymethylfurfural 13.10 1.40 1.54 1.76 1.88 1.29 11.07
5-Acetoxymethyl-2-furaldehyde 14.24 0.25 0.25 0.31 0.37 0.35 0.49
Phenols 2.61 8.75 11.10 12.96 12.05 5.51
Phenol 9.12 1.08 1.31 1.25 0.84 1.31 –
Phenol, 2-methyl 10.37 0.28 0.43 0.31 0.16 0.22 0.29
Phenol, 3-methyl 10.70 0.67 0.97 0.97 0.48 0.69 0.35
Phenol, 2,4-dimethyl 11.87 0.30 0.50 0.40 0.16 0.32 –
Phenol, 2,3-dimethyl 12.18 0.27 0.25 0.37 – – –
Guaiacols 15.99 11.83 11.21 6.96 5.11 –
Guaiacol 10.98 3.39 4.00 3.43 2.74 2.58 –
Phenol, 2-methoxy-4-methyl 12.38 0.09 0.09 0.07 – – –
Phenol, 2-methoxy-4-methyl 12.60 7.33 4.52 3.49 – – –
Phenol, 4-ethyl-2-methoxy 13.86 1.22 1.31 1.30 1.05 0.77 –
Eugenol 14.95 0.30 0.25 0.27 0.33 0.17 –
Phenol, 2-methoxy-4-propyl 15.08 0.19 0.14 0.26 0.11 – –
Vanilin 15.54 0.90 0.70 0.92 1.13 0.87 –
Phenol, 2-methoxy-4-(1-propenyl) 15.63 0.23 0.18 0.24 0.24 – –
Phenol, 2-methoxy-4-(1-propenyl) 16.17 1.31 0.77 1.14 1.35 0.72 –
Catechols 4.84 5.04 8.68 7.91 10.41 –
1,2-Benzenediol, 3-methyl 13.55 0.78 1.27 1.96 1.19 1.76 –
1,2-Benzenediol, 3-methoxy 13.62 0.11 0.18 0.22 0.19 0.20 –
Hydroquinone 13.72 0.23 0.29 0.42 0.48 0.47 –
1,2-Benzenediol, 4-methyl 13.96 1.95 2.96 4.42 3.98 4.91 –
3,5-Dihydroxytoluene 14.03 0.09 0.34 0.09 0.19 – –
Hydroquinone, methyl 14.70 0.28 – 0.81 – – –
1,3-Benzenediol, 4,5-dimethyl 14.84 0.28 – 0.75 0.49 0.77 –
1,3-Benzenediol, 4-ethyl 15.25 1.12 – – 1.10 1.46 –
1,3-Benzenediol, 4-propyl 16.44 – – 0.27 0.29 0.22 –

Table 5
Properties of tar and oils produced from pyrolysis of Pc and copyrolysis of Pc/PE, Pc/PP, Pc/PS, Pc/PE/PP/PS and Cell/PE/PP/PS.

Sample name Pc Pc/PE Pc/PP Pc/PS Pc/PE/PP/PS Cell/PE/PP/PS

Elemental composition (wt.%)

C 23.55 81.00 84.65 80.49 81.56 80.59
H 7.68 12.94 13.17 12.53 7.94 12.09
N 0.84 0.43 0.57 0.40 0.64 0.48
S 0.14 0.02 0.06 0.04 0.05 0.02
Oa 67.79 5.61 1.55 6.54 9.81 6.82
Water amount (wt.%) 66.0 0.09 0.45 0.02 0.13 0.04
GCVb (MJ kg—1) n.d. 46.33 45.58 46.43 41.33 45.71
a
Calculated by difference.
b
Gross calorific value.

in color with typical petroleum hydrocarbons odour. The water the separation of the aqueous phase. Because of this, oxygen con-
content, elemental composition and calorific value of the oils are tent of tar is extremely high. On the other hand, oils from co-pyro-
given in Table 5. The tar contained high amount of water even after lysis consisted of hydrocarbons. The oxygen and trace amounts of
 M. Brebu et al. / Fuel 89 (2010) 1911–1918 1917

40
40
Oils Oils
b
GC-MSD area , %

GC-MSD area , %
30 Pc 30 Pc
PE PP

20 20

10 10

0 0
5 10 15 20 25 5 10 15 20 25
carbon number carbon number

PS: 73.78
40 40
Oils Oils
d

GC-MSD area , %
GC-MSD area , %

30 30

20 20

10 10

0 0
5 10 15 20 25 5 10 15 20 25
carbon number carbon number

Fig. 5. Experimental and calculated C-NP grams of oils produced from pyrolysis of pine cone mixed with PE, PP and PS.

Table 6
4. Conclusions
Physico-chemical properties of chars produced from pyrolysis of Pc and copyrolysis of
Pc/PE/PP/PS and Cell/PE/PP/PS. In this study, co-pyrolysis of pine cone with synthetic polymers
Sample name Pc Pc/PE/PP/PS Cell/PE/PP/PS
was carried out at 500 °C by semi-batch process. Ther- mal behavior
of each polymer and of pine cone was also inves- tigated by TGA.
Elemental composition (wt.%)
C 70.33 79.79 93.19
Thermogravimetric analysis of pine cone, PE, PP and PS showed that
H 3.98 3.60 3.45 decomposition starts around 200 °C with cellulose and
N 0.98 0.94 0.72 hemicellulose fraction of biomass while above 400 °C degradation
S 0.08 0.07 0.06
of lignin fraction overlaps with that of synthetic polyolefins. This
Oa 24.63 15.6 2.58
GCVb (MJ kg—1) 27.35 31.64 34.76
may lead to interactions between components of mixtures that
manifests by a synergistic effect in product yields. The
a
Calculated by difference. composition of co-pyrolysis oils depends on the type of synthetic
b
Gross calorific value.
polymer in mixture whereas the type and amount of organic
compounds in aqueous phase varied with the ratio of holocellullose
and lignin in biomass. The co-pyrolysis chars had high calorific
nitrogen and sulphur in oils show the presence of some tarry impu- values and ash content below 1 wt.% with very low sulphur
rities coming from pine cone degradation. concentration making them attractive for use as a solid fuel or as
The pyrolysis char could be used as a solid fuel or as raw mate- raw material for production of acti- vated carbon.
rial for activated carbon production. The potential use of chars as As a conclusion, the results obtained in this study showed that
fuel depends on their calorific value and ash content. All chars ob- co-pyrolysis of biomass and synthetic polymers could be an envi-
tained in this study from the pyrolysis of pine cone and co-pyroly- ronmentally friendly way for the transformation of commingled
sis of synthetic polymers mixed with pine cone or cellulose have ash lignocellulosic and plastic waste into valuable products such as
content lower than 1 wt.%. The elemental composition and gross chemicals or fuels.
calorific value of some of them are shown in Table 6. Due to the
higher content of oxygen, the char obtained from pyrolysis of pine
cone alone had lower calorific value than those obtained from co- Acknowledgement
pyrolysis. The difference in elemental composition of chars from
synthetic polymers mixed with pine cone and with cel- lulose may This work was done in the framework of an inter- academic
be linked to the presence of lignin in pine cone. The very low sulphur exchange between Romanian and Turkish Academies of Sciences.
content makes these chars attractive for use in incineration.
1918 M. Brebu et al. / Fuel 89 (2010) 1911–1918
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.fuel.2010.01.029.
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