Bunga Ferula
Bunga Ferula
Bunga Ferula
Energy
journal homepage: www.elsevier.com/locate/energy
a r t i c l e i n f o a b s t r a c t
Article history: Slow pyrolysis of eastern giant fennel (Ferula orientalis L.) stalks has been performed in a fixed-bed
Received 29 June 2013 tubular reactor with (ZnO, Al2O3) and without catalyst at six different temperatures ranging from
Received in revised form 350 C to 600 C with heating rates of 15, 30, 50 C/min. The amounts of bio-char, bio-oil and gas
7 October 2013
produced, as well as the compositions of the resulting bio-oils were determined by FT-IR and GCeMS.
Accepted 19 November 2013
The effects of pyrolysis parameters such as temperature, catalyst and ratio of catalyst, particle size (Dp)
Available online 16 December 2013
and sweeping gas flow rate on product yields were investigated. According to results, temperature and
catalyst seem to be the main factors effecting the conversion of F. orientalis L. into solid, liquid and
Keywords:
Energy
gaseous products. The highest liquid yield (45.22%) including water was obtained with 15% zinc oxide
Biomass catalyst at 500 C temperature at a heating rate of 50 C/min when 0.224 > Dp > 0.150 mm particle size
Pyrolysis raw material and 100 cm3/min of sweeping gas flow rate were used.
Bio-oil Ó 2013 Elsevier Ltd. All rights reserved.
Giant fennel
Ferula orientalis L.
0360-5442/$ e see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.energy.2013.11.053
T. Aysu, M.M. Küçük / Energy 64 (2014) 1002e1025 1003
numbers between 4000 and 650 cm1. The aim of the analysis was thermogravimetric (TG) and differential thermal analysis (DTA).
to identify the functional groups of raw material and then The thermogravimetric weight loss and the corresponding deriva-
compare any structural changes after the liquefaction experi- tive curves are given in Fig. 2. When TG curve is examined, 6%
ments. The bands in the spectra of raw F. orientalis L. indicate that weight loss until 160 C indicates the amount of moisture content
it is mainly composed of lignin, cellulose and hemicelluloses [12e of raw material which is very close to the value given in Table 1.
15]. The band at 3335 cm1 is caused by OH of lignin in F. ori- Hemicellulose and cellulose of the raw material, the main compo-
entalis L. The absorption at wave number of 1736 cm1 is the nents of biomass start to decompose at 225 C. The temperature at
characteristic of xylans of hemicellulose. The absorption peaks at which the maximum decomposition occurs is determined as
about 3362, 2900,1365 and 1143 cm1 are the characteristics of 304 C. All of the components (hemicellulose, cellulose and lignin)
cellulose. Generally, similar absorption peaks are observed in the of the raw material decompose very rapidly at this temperature
spectrum of lignin. The absorptions at 2900, 1600e1500, 1416, reaching a maximum weight loss. At 382 C, rate of decomposition
1314, and 830e750 cm1 represent the lignin [12e14]. The char- gradually decreases and gets a minimum approximately at 435 C.
acteristic absorption peaks of raw F. orientalis L. prove the presence After 435 C, difference in weight loss gets smaller and becomes
of lignin, cellulose and hemicelluloses. zero at 600 C [16,17]. The amount of matter left behind after 600 C
Before performing the pyrolysis experiments, thermal behav- is the percentage of ash which is calculated as 4.90% by weight from
iour of the raw material (F. orientalis L.) was also investigated by TG curve.
Fig. 4. The effect of pyrolysis temperature and heating rate on the products yields.
1006 T. Aysu, M.M. Küçük / Energy 64 (2014) 1002e1025
separating funnel and separated from each other by decantation. The last group of experiments was performed to determine the
Pyrolytic oil or bio-oil is dried with anhydrous sodium sulphate and effect of sweeping gas (nitrogen) flow rate on the product yields,
recovered by evaporating the solvent in a rotary evaporator at specifically liquid product yield. Pyrolysis experiments in this group
temperature of 313 K and reduced pressure of 11 kPa and its yield were conducted with five different sweeping gas flow rates of 100,
(liquid) were calculated. After cooling the pyrolysis reactor, the 150, 200, 250 and 300 cm3/min by using the optimum conditions of
amount of solid (bio-char) left behind was removed and weighed. 500 C pyrolysis temperature with a heating rate of 50 C/min and
The conversion of raw material to liquid and gaseous products was 0.224 > Dp > 0.150 mm particle size raw material.
calculated by subtraction of amount of solid (bio-char) left behind
in the reactor. The amount of gas evolved was calculated by sub-
3. Results and discussion
traction of amount of solid and liquid products from 20, the amount
of initial raw material. From the first group of experiments, it was
3.1. Effect of temperature and heating rate on product yields
found that 500 C pyrolysis temperature and 50 C/min heating rate
provide the optimum conditions for producing highest amount of
The results of pyrolysis and distribution of products obtained at
liquid products in the non-catalytic experiments. In the second
different temperatures with different heating rates without catalyst
group of experiments, two different catalysts (ZnO and Al2O3) with
are given in Table 2. The effects of temperature and heating rate on
different ratios (5%, 10%, 15%) were added to reactor and pyrolysis
product yields are given in Fig. 4. The data given in the Fig. 4. were
experiments at the same temperatures used in non-catalytic runs
obtained from the experimental runs (Table 2) at different tem-
with constant heating rate of 50 C/min were carried out to
peratures ranging from 350 C to 600 C with heating rates of 15,
investigate the effect of catalyst and catalyst ratio on product yields.
30, 50 C/min. It can be seen from Fig. 4 that temperature has a
After completion of all experiments, the product yields were
positive effect either sharply or slightly on both conversion and
calculated and expressed on dry and ash free basis. Third group of
liquid product yield. According to results, when temperature is
experiments was performed to determine the effect of particle size
increased from 350 to 500 C, liquid product yield increases from
on product yields. Four different particle size (0.850 > Dp > 0.425,
38.61% to 43.07% at a heating rate of 15 C/min, from 40.52% to
0.425 > Dp > 0.300, 0.300 > Dp > 0.224, 0.224 > Dp > 0.150)
43.55% at a heating rate of 30 C/min and from 41.89% to 45.02% at a
samples were used and pyrolysis experiments were carried out at
heating rate of 50 C/min. So, the highest liquid product yield was
the optimum conditions of 500 C pyrolysis temperature with a
obtained at 500 C with a heating rate of 50 C/min in the non-
heating rate of 50 C/min and 100 cm3/min nitrogen gas flow rate.
catalytic runs. Beyond at 500 C, even though the conversion has
Fig. 5. The effect of aluminium oxide catalyst ratio on the products yields.
T. Aysu, M.M. Küçük / Energy 64 (2014) 1002e1025 1007
Fig. 6. The effect of zinc oxide catalyst ratio on the products yields.
increased steadily, the liquid yields have decreased to 41.04%, In one of the studies carried out by Özbay et al. [22], apricot
41.78%, and 42.37% at 600 C at heating of rates of 15, 30, 50 C/min pulps was pyrolyzed in a fixed-bed reactor under different pyrolysis
respectively. According to literature, temperature is the most conditions to determine the role of final temperature, sweeping gas
important parameter on product yields [17e21]. flow rate and steam velocity on the product yields and liquid
Table 3 Table 4
The conversiona and distribution of products obtained by pyrolysis of Ferula ori- The conversiona and distribution of products obtained by pyrolysis of Ferula ori-
entalis L. at different temperatures with ZnO catalyst. entalis L. at different temperatures with Al2O3 catalyst.
Temperature ( C) Conversion (%) Solid (%) Liquid (%) Gas (%) Temperature ( C) Conversion (%) Solid (%) Liquid (%) Gas (%)
Table 5
The results of elemental analyses of some of the bio-chars.
450 C
Carbon 51.46 52.87 54.70
Hydrogen 7.001 6.861 6.746
Nitrogen 0.964 0.382 0.435
Oxygenb 40.575 39.887 38.119
H/C molar ratio 1.632 1.557 1.479
O/C molar ratio 0.591 0.565 0.522
Higher heating 20.19 20.59 21.36
value (MJ/kg)
400 C
Carbon 51.89 52.67 53.50
Hydrogen 7.003 6.971 6.943
Nitrogen 0.994 1.054 1.154
Oxygenb 40.113 39.305 38.403
H/C molar ratio 1.619 1.588 1.557
O/C molar ratio 0.579 0.559 0.538
Higher heating 20.42 20.78 21.19
value (MJ/kg)
a
Weight percentage on dry and ash free basis.
b
Fig. 8. The effect of sweeping gas flow rate on the product yields. By difference.
T. Aysu, M.M. Küçük / Energy 64 (2014) 1002e1025 1009
Fig. 9. (continued).
3.2. Effects of catalysts and ratio of catalysts on product yields aluminium oxide (Fig. 5), even though it has much more positive
effect on conversion than zinc oxide, the liquid product yields
The effects of catalysts and catalyst ratios on conversion are have constantly decreased as the ratio of catalyst increased at all
given in Figs. 5 and 6. The data given in the Figs. 5 and 6 were pyrolysis temperatures. The liquid product yield, which was
obtained from the experimental runs given in Tables 3 and 4. 41.89% without catalyst, reached the maximum value of 40.11%
Pyrolysis experiments with catalysts were carried out at a constant with 15% aluminium oxide catalyst at 350 C. The gaseous product
heating rate of 50 C/min at the same temperatures used in non- yields for both catalysts have increased with increasing catalyst
catalytic runs to determine both effects of catalysts (ZnO and ratios when compared with non-catalytic runs. For example, the
Al2O3) and catalyst ratio (5, 10, 15%) on the product yields. As seen gas product yield of 23.59% at 350 C has increased to 36.06% at
from Figs. 5 and 6, catalysts have shown different effects on 600 C in the catalytic run with 10% zinc oxide. Similar results
product yields. Both catalysts have increased the conversion with were observed in the previous studies [31e33].
increasing temperature and catalyst ratios compared with non- There are many pyrolysis studies regarding the effect of catalysts
catalytic runs. Of them, aluminium oxide is more effective than on product yields of biomass samples in recent years. The usage of
zinc oxide in terms of conversion. The highest conversion (79.24%) catalyst could make significant changes on the properties and
was obtained with 15% aluminum oxide in the catalytic runs at yields of pyrolysis products. Generally, using catalyst has been
600 C temperature. On the other hand, effects of catalysts on increased the liquid yields while in some studies, it had negative
liquid product yields were different from each other. Namely, in effect and decreased the liquid product yields [34e41]. Similar
the experiments performed with zinc oxide (Fig. 6), the liquid results were obtained for bio-char and gaseous product yields
product (bio-oil) yields have increased steadily as the ratio of which were either increased or decreased by using catalysts
catalyst increased at the temperatures of 350, 400, 450 and 500 C [42,43]. The liquid product obtained in pyrolysis contains an
but have decreased at the temperatures of 550 and 600 C. As for aqueous phase and bio-oil or oil phase which is generally named as
T. Aysu, M.M. Küçük / Energy 64 (2014) 1002e1025 1011
pyrolytic liquid. It is a black liquid containing highly oxygenated oxide on the product yields of pyrolysis of rice husk at 550 C
compounds used as boiler fuel in power stations for heat produc- temperature and the sweeping gas (nitrogen) flow rate of 150 cm3/
tion. If it is intended to be used as transportation fuels, they should min. In accordance with our results obtained with zinc oxide
be upgraded first by hydrodeoxygenation to produce aromatics or catalyst at 550 C and 600 C, they found out that the liquid product
hydrocarbons, or catalytic cracking by using zeolite to produce light yields were decreased approximately 6% (wt) with increasing
aromatic hydrocarbons and light alkanes. Aluminium oxide as catalyst ratio while gaseous products were increased. The bio-char
catalyst, having acidic sites on it, can speed up the dehydration, yields were not affected by the ratio of catalyst and kept constant.
decarbonylation and hydrogeration reactions occur during pyroly- They also observed that the viscosity of the bio-oil obtained by
sis. The carbon and hydrogen in the feedstock are converted to using zinc oxide catalyst was significantly lower than that of the
carbon monoxide and hydrogen gases. The removal of oxygen to bio-oil obtained without catalyst.
water, carbon monoxide and carbon dioxide may result in low bio-
oil yields [40,44].
3.3. Effect of particle size on product yields
One of the recent studies in which zinc oxide was used as
catalyst carried out by Zhou et al. [45]. They have used different
The effect of particle size on the product yields obtained by
ratios of biomassecatalyst mixtures to investigate the effect of zinc
pyrolysis experiments at constant temperature of 500 C and at a
constant heating rate of 50 C/min is given in Fig. 7. As it is seen volatile yields. Uniform heating could be established with suffi-
from Fig. 7, change in particle size did not effect significantly py- ciently small particle size samples. It has been reported that par-
rolysis yields. The highest conversion and liquid yield were 73.85% ticle size less than 5 mm does not have significant effect on the
and 45.02% obtained with a particle size of 0.224 > Dp > 0.150 mm process rate. The results of our study show that
respectively. When particle size is increased 0.224 > Dp > 0.150 to 0.224 > Dp > 0.150 mm and 0.300 > Dp > 0.224 mm particle size
0.850 > Dp > 0.425, the liquid yield decreased from 45.02% to samples are the most suitable for obtaining high liquid yields from
43.29% and gas yield from 28.83% to 27.54% while bio-char yield pyrolysis of F. orientalis L. [3,49].
increased from 26.15% to 29.17%. These results are consistent with In a recent work, biomass cellular structure is reported as
the previous studies reported in literature, that is, increase in another element that needs to be taken into account to explain the
particle size leads to greater temperature gradients inside the decreases in liquid yield with increasing biomass particle size. It is
particles and the core temperature of the particles is lower than proposed that the cell structure may affect the pyrolysis behaviour
the surface which causes higher bio-char yield and lower bio-oil of biomass, such as the release of alkaline or alkaline earth
and gas yields [46e48]. metallic species. In the preparation of small biomass particles
The effect of particle size is explained in terms of heating rate ranging between 0.18 and 0.6 mm by using a cutting mill, much of
in which bigger particles will heat up more slowly causing lower the cellular structure of biomass is destroyed. The diffusion of
temperature of average particles which result in less amounts of pyrolysis products which were formed inside wood cells is
affected seriously by cell walls. The increase of intensity of sec- rate, reaching the maximum values at 200 cm3/min, and then
ondary reactions in the closed cells may cause to decrease in the decreased. The gas and bio-char yields, on the other hand, first
yield of liquid yield. That is to say, during pyrolysis process, cell decreased with increasing sweeping gas flow rate, reaching the
contents in the small particles are released much more easily than minimum values at 200 cm3/min, and then start to increase. The
in the big particles [50,51]. liquid product yield was increased from 45.02% to 46.87%, when
nitrogen flow rate was increased from 100 cm3/min to 200 cm3/min
3.4. Effect of sweeping gas flow rate on product yields and then decreased to 42.56% at 300 cm3/min flow rate. The gas
yield was decreased from 28.83% to 27.26%, when nitrogen flow
The effect of sweeping gas flow rate on product yields was rate was increased from 100 cm3/min to 200 cm3/min and then
determined by performing the pyrolysis experiments with different increased to its maximum value of 29.68% at 300 cm3/min flow rate.
nitrogen gas flow rates using the optimum conditions (particle size: As for bio-char yield, it decreased to its minimum value of 25.87% as
0.224 > Dp > 0.150, temperature: 500 C, heating rate:50 C/min) nitrogen flow rate was increased from 100 cm3/min to 200 cm3/min
obtained in the first group of experiments. Fig. 8 shows the effect of and then decreased to its maximum value of 27.76% at 300 cm3/min
sweeping gas flow rate on product yields. As seen from Fig. 8, the flow rate. Ignoring the small differences in the values obtained in
maximum liquid product yield of 46.87% was obtained at a our study from previous studies, similar results have been reported
sweeping gas flow rate of 200 cm3/min. The conversion and liquid in the literature [17,21,24,52,53] regarding the effect of sweeping
product yields were increased with increasing sweeping gas flow gas on pyrolysis products yields.
According to the reports in literature, the role of sweeping gas is elemental, FT-IR and GCeMS. All analyses were carried out at sci-
to minimize the secondary reactions including thermal cracking, entific and technological research center in Malatya Inonu Uni-
repolymerisation and recondensation by removing the form the versity. Elemental analyses were performed with LECO CHNS 932
formed products from the hot zone and hence to maximize the Elemental Analyser and infrared analysis with a Perkin Elmer
liquid product yield. The reason for decrease in liquid product Spectrophotometer. The GCeMS analyses were performed on Agi-
yields and increase in gaseous product yields at higher flow rates is lent GCeMS 7890A/5975C series. The column (HP-INNOWAX,
because of either poor cooling or fast leaving of pyrolysis vapours length: 60 m, I.D.: 0.250 mm, film: 0.25 mm and temperature limits:
before condensation [17,21,24,54,55]. from 40 C to 260 C) and injector temperatures were the same as
those for GC. Chemical constituents were identified by comparison
3.5. Characterization of bio-chars and bio-oils by elemental, FT-IR of their retention indices with literature values [56,57] and their
and GCeMS analysis mass spectral data with those from the Wiley7n.1, ADAMS.1 and
NIST05a.L mass spectral databases.
Out of sixty one products, some of the selected bio-chars and The results of elemental analyses of five bio-chars and nine bio-
bio-oils obtained at various conditions were analyzed and charac- oils are given in Tables 5 and 6 respectively. Tables 5 and 6 show
terized by chromatographic and spectroscopic techniques such as that both bio-chars and bio-oils have higher carbon contents and
Table 7
Main chemical compounds present in the bio-oils obtained at 500 C.
Monoaromatics
1 Furfural C5H4O2 96.08 1.00 3.36 4.03
2 2-Furancarboxaldehyde, 5-methyl- C6H6O2 110.11 e 1.23 e
3 2-Acetylfuran C6H6O2 110.11 0.49 1.08 1.01
4 Furan, 2,3,5-trimethyl- C7H10O 110.15 e e 1.27
5 2 (3H)-Furanone, dihydro- C4H6O2 86.08 e 1.44 1.92
6 2-Furanmethanol C5H6O2 98.10 2.09 4.87 3.97
7 2 (5H)-Furanone, 3-methyl- C5H6O2 98.10 e 0.36 0.47
8 2 (5H)-Furanone C4H4O2 84.07 e 1.13 e
9 2 (3H)-Furanone C4H4O2 84.07 e e 0.87
10 Guaiacol <ortho> C7H8O2 124.14 e 8.14 9.27
11 Mequinol C7H8O2 124.13 5.31 e e
12 Phenol, 2-methoxy-3-methyl- C8H10O2 138.16 0.44 e e
13 Phenol, 2-methoxy-4-methyl- C8H10O2 138.16 1.35 1.54 0.64
14 Cresol <ortho> C7H8O 108.14 1.60 2.73 3.02
15 Phenol C6H6O 94.11 3.25 3.73 6.75
16 p-Ethyl guaiacol C9H12O2 152.19 e e 0.68
17 Benzeneethanol, 2-methoxy- C9H12O2 152.19 e 0.58 e
18 Phenol, 4-ethyl-2-methoxy- C9H12O2 152.19 2.08 e e
19 Phenol, 2-ethyl- C8H10O 122.16 0.91 0.42 0.56
20 Phenol, 2,5-dimethyl- C8H10O 122.16 0.71 e 0.64
21 Phenol, 2,6-dimethyl- C8H10O 122.16 1.80 1.41 0.58
22 Phenol, 2,4-dimethyl- C8H10O 122.16 0.63 0.79 0.72
23 Phenol, 2,3-dimethyl- C8H10O 122.16 e e 0.80
24 Phenol, 3,4-dimethyl- C8H10O 122.16 e 2.32 e
25 Phenol, 3,5-dimethyl- C8H10O 122.16 e e 2.06
26 Cresol <para> C7H8O 108.14 1.16 1.58 1.95
27 Cresol <meta> C7H8O 108.14 2.11 e 3.17
28 Phenol, 3-ethyl- C8H10O 122.16 e 1.42 1.09
29 p-Propylguaicol C10H14O2 166.21 0.57 e e
30 2-Methoxy-4-vinylphenol C9H10O2 150.17 3.87 2.32 1.95
31 2,6-Xylenol C8H10O 122.16 0.90 e e
32 Phenol, 2,6-dimethoxy- C8H10O3 154.16 15.64 11.68 7.89
33 3-Allyl-6-methoxyphenol C10H12O2 164.20 e 2.25 e
34 Phenol, 2-methoxy-4-(1-propenyl)- C10H12O2 164.20 5.86 e e
35 2, 3, 5-Trimethoxy toluene C10H14O3 182.22 5.61 e e
36 Phenol, 2,6-dimethoxy-4-(2-propenyl)- C11H14O3 194.22 1.24 e e
37 2,6-Dimethyl-3-(methoxymethyl)-p-benzoquinone C10H12O3 180.20 6.52 0.93 e
38 Cinnamic acid, 3-Hydroxy-4-methoxy- C10H10O4 194.18 1.35 1.44 e
39 Cinnamic acid, 4-Hydroxy-3-methoxy- C10H10O4 194.18 e e 1.27
40 Phenol, 2-methoxy-5-(1-propenyl)-(E)- C10H12O2 164.20 e e 1.54
41 Trans-5,8-Dioxatricyclo [5.1.0.0 (4,5)] oct-2-ene C6H6O2 110.11 e e 1.69
42 2-Propanone, 1-hydroxy-3-(4-hydoxy-3-methoxyphenyl)- C10H12O3 180.20 1.32 e e
43 1, 2-Benzenediol C6H6O2 110.10 3.35 e e
44 2, 5-Dimethoxyterephthalic acid C10H10O6 226.18 6.27 e e
45 Desaspidinol C11H14O4 210.22 2.70 e e
Aliphatics
46 Pentane, 3-methyl- C6H14 86.18 e e 1.56
47 1-Ethyl-4-methylcyclohexane C9H18 126.24 e 0.49 e
e 0.49 1.56
Oxygenated compounds
48 2-Cyclopenten-1-one, 2-methyl- C6H8O 96.13 0.55 0.70 1.56
49 2-Cyclopenten-1-one C5H6O 82.04 e 1.61 1.83
50 2-Decanone C10H20O 156.27 e 0.68 e
51 Butanal, 3-methyl- C5H10O 86.13 e 1.57 e
52 1-Hydroxy-2-butanone C4H8O2 88.11 0.91 e e
53 Acetic acid C2H4O2 60.05 3.27 12.11 20.33
54 1-Penten-3-ol, 2-methyl- C6H12O 100.16 e 1.40 1.44
55 1-Acetoxyacetone C5H8O3 116.11 0.30 e e
56 Propanoic acid C3H6O2 74.07 1.12 2.67 2.53
57 2-Cyclopenten-1-one, 3-methyl- C6H8O 96.13 0.87 1.89 1.52
58 2-Cyclopenten-1-one, 2,3-dimethyl- C7H10O 110.15 0.71 1.31 1.36
59 Pentanoic acid C5H10O2 102.13 e 0.52 e
60 1-methoxy-1,3-cyclohexadiene C7H10O 110.15 0.50 e e
61 Butanoic acid C4H8O2 88.11 0.50 e 0.52
62 4-formyl-4-methyl-tetrahydropyran C7H12O2 128.17 e e 0.45
63 2-Cyclopenten-1-one, 2-hydroxy-3-methyl- C6H8O2 112.13 e e 1.44
(continued on next page)
1020 T. Aysu, M.M. Küçük / Energy 64 (2014) 1002e1025
Table 7 (continued )
Nitrogenated compounds
76 1H-Imidazole, 1-methyl- C4H6N2 82.11 0.95 e 2.32
77 N-Nitrosodimethylamine C2H6N2O 74.08 e 2.15 e
78 Butyric acid hydrazide C4H10N2O 102.14 0.77 e e
79 2-Butanone, 4-(1-piperidinyl)- C9H17NO 155.24 e e 0.39
Polyaromatic compounds
80 Naphthalene, 2-methyl- C11H10 142.20 e e 0.37
81 1H-Inden-1-one, 2,3-dihydro- C9H8O 132.16 e 1.06 0.93
e 1.06 1.30
lower oxygen content than the original raw material and accord- Bio-oils identified by GCeMS consist of complex mixtures of
ingly have higher heating values when compared with higher organic compounds These compounds can be grouped into four
heating value of the raw material. As shown in Tables 5 and 6, the different classes of monoaromatics, aliphatics, oxygenated com-
higher heating values of bio-chars and bio-oils were higher than pounds, nitrogenated compounds, aromatic compounds and de-
20 MJ/kg, in comparison with the low higher heating value rivatives. Monoaromatics include benzene and derivatives, toluene,
(16.16 MJ/kg) of the raw material. furans, phenols and derivatives. Aliphatics are mainly composed of
FT-IR spectrums of bio-chars obtained at 450 and 500 C. are alkanes, alkenes and their derivatives while oxygenated com-
given in Fig. 9. When they are compared with raw material, there pounds contain aldehydes, ketones, esters and carboxylic acids.
have been significant changes in the FT-IR spectrum as a result of Amines and amides such as pyridine and pyrazole are classified as
pyrolysis. The OeH stretching vibration band at 3335 cm1 has nitrogenated compounds.
been almost disappeared for all bio-chars which shows that the In accordance with the previous studies reported in literature
oxygen was removed from raw material during pyrolysis which [34,45,58e61] most of the identified compounds of bio-oils are
causes the phenolic and aromatic structures to crack producing phenolics and its derivatives are formed by degradation of lignin in
carbonaceous solid products. The FT-IR spectrums of bio-chars are the raw material. They consist of phenols, methoxy phenols, alkyl
very similar to each other. The observed weak bands between phenols and eugenol. As bio-oils obtained by pyrolysis can be used
2500 cm1 and 2600 cm1 are assigned to aliphatic CeH stretching. not only as a fuel in engines or boilers, but also as a valuable organic
The CeC stretching vibrations between 1350 and 1650 cm1 indi- chemicals, phenols could be considered as one of them for its
cate the presence of aromatics and alkanes. The CeO stretching commercial value.
absorbance peaks observed between 1050 and 1350 cm1 indicate Bio-oils are composed of mainly aldehydes, ketones and phenolic
the presence of primary, secondary and tertiary alcohols, phenols, compounds. Most of these compounds are formed from the degra-
ethers and esters. FT-IR analyses prove that the bio-chars obtained dation of lignin and the others are from cellulose. The most abundant
by pyrolysis are mainly composed of aromatic and aliphatic compounds in the bio-oils are acetic acid, 2,6-dimethoxy phenol,
compounds. guaiacol, furfural and furan derivatives. During pyrolysis of woody
FT-IR and GCeMS spectrums of twelve bio-oils (without and biomass, hemicelluloses decompose first (200e280 C) forming the
with catalyst) obtained at 500 C, 450 C, 400 C, 350 C which acidic compounds such as acetic acid. On the other hand, decom-
mostly represent the whole are given in Figs. 10e17. The list of the position of cellulose (240e350 C) produces levoglucosan as the
compounds identified by GCeMS in Figs. 14e17 is given in primary breakdown product during thermal treatment, but other
Tables 7e10 respectively. As expected, bio-oils produced by anhydroglucoses, furan and furan derivatives are also produced.
degradation of hemicellulose, cellulose and lignin of biomass Phenols and derivatives such as 2,6-dimethoxy phenol and guaiacol,
contain many types of compounds having different molecular the majority of the compounds in bio-oils, are obviously the primary
structures and molecular weights. Number and types of com- products of degradation of lignin (280e500 C) during pyrolysis [62].
pounds obtained at higher temperatures are greater than at lower The FT-IR spectrums confirm and are consistent with the list of
temperatures. That means that the degradation of lignin is not compounds in Tables 7e10. Absorbance peaks of the OeH or NeH
complete and continue as the temperature is further increased. vibrations between 3100 and 3700 cm1 indicate the presence of
T. Aysu, M.M. Küçük / Energy 64 (2014) 1002e1025 1021
Table 8
Main chemical compounds present in the bio-oils obtained at 450 C.
Monoaromatics
1 Furfural C5H4O2 96.08 1.42 1.79 3.56
2 2-Acetylfuran C6H6O2 110.11 1.03 1.16 1.19
3 2-Furancarboxaldehyde, 5-methyl- C6H6O2 110.11 0.97 e 1.43
4 Furan, 2,5-dimethyl- C6H8O 96.13 1.54 e e
5 2-Furanmethanol C5H6O2 98.10 4.21 2.94 4.28
6 2 (5H)-Furanone C4H4O2 84.07 0.71 e 1.29
7 2 (3H)-Furanone C4H4O2 84.07 e 1.20 e
8 2 (3H)-Furanone, dihydro- C4H6O2 86.08 e 1.50 1.83
9 Furan, 2-methoxy- C5H6O2 98.10 e e 1.00
10 Benzene, 1-fluoro-2-methoxy- C7H7FO 126.13 0.66 e e
11 Guaiacol <ortho> C7H8O2 124.14 9.29 7.95 7.31
12 1-ethoxy-2-methoxy-4-methylbenzene C10H14O2 166.21 0.66 e e
13 Phenol, 2-methoxy-4-methyl- C8H10O2 138.16 1.90 1.03 1.04
14 Cresol <ortho> C7H8O 108.14 1.12 3.47 3.41
15 Phenol C6H6O 94.11 3.81 7.23 5.54
16 Benzeneethanol, 2-methoxy- C9H12O2 152.19 e e 0.55
17 Phenol, 4-methyl-2-methoxy- C8H10O2 138.16 e 1.07 e
18 Phenol, 2-ethyl- C8H10O 122.16 e 1.05 e
19 Phenol, 2,6-dimethyl- C8H10O 122.16 e 1.11 0.93
20 Phenol, 2,4-dimethyl- C8H10O 122.16 e 1.14 1.04
21 Phenol, 4-ethyl-2-methoxy- C9H12O2 152.19 3.09 e e
22 Cresol <para> C7H8O 108.14 1.22 2.36 1.90
23 Cresol <meta> C7H8O 108.14 e 3.75 3.73
24 Phenol, 3,5-dimethyl- C8H10O 122.16 e e 3.43
25 Phenol, 2,3-dimethyl- C8H10O 122.16 e 1.00 e
26 Phenol, 3,4-dimethyl- C8H10O 122.16 e 3.21 e
27 Phenol, 3-ethyl- C8H10O 122.16 e 1.66 2.69
28 Eugenol C10H12O2 164.20 1.16 3.05 2.05
29 2-Methoxy-4-vinylphenol C9H10O2 150.17 4.05 2.25 1.92
30 Phenol, 2,5-dimethyl- C8H10O 122.16 e 1.29 e
31 Phenol, 2,6-dimethoxy- C8H10O3 154.16 13.67 16.59 10.35
32 2,3,5,6-Tetrafluoroanisole C7H4OF4 180.10 e 1.27 e
33 Trans-5,8-Dioxatricyclo [5.1.0.0 (4,5)] oct-2-ene C6H6O2 110.11 e 3.68 e
34 Phenol, 2-methoxy-4-(1-propenyl)-(E)- C10H12O2 164.20 4.58 e e
35 3-Furancarboxylic acid, 2,5-dimethyl-, methyl ester C8H10O3 154.16 4.04 e e
36 2,6-Dimethyl-3-(methoxymethyl)-p-benzoquinone C10H12O3 180.20 4.34 e e
37 Phenol, 2,6-dimethoxy-4-(2-propenyl)- C11H14O3 194.22 4.52 e e
Aliphatics
38 3-Hexyne C6H10 82.14 e 1.18 1.88
39 3-Heptyne C7H12 96.17 e e 0.74
40 3-Methyl pentane C6H14 86.18 e 1.14 1.54
41 Bicyclo [2.2.2] octane C8H14 110.19 e 0.96 e
e 3.28 4.16
Oxygenated compounds
42 2-Cyclopenten-1-one, 2-methyl- C6H8O 96.13 1.00 e e
43 2-Cyclopenten-1-one, 3-methyl- C6H8O 96.13 e 1.07 2.26
44 1-Hydroxy-2-butanone C4H8O2 88.11 2.22 e e
45 Acetic acid C2H4O2 60.05 7.95 10.95 12.67
46 1-Acetoxyacetone C5H8O3 116.11 0.65 e e
47 1-Penten-3-ol, 2-methyl- C6H12O 100.16 1.90 1.15 1.61
48 Propanoic acid C3H6O2 74.07 2.61 1.68 2.47
49 2-Cyclopenten-1-one, 2,3-dimethyl- C7H10O 110.15 e e 1.60
50 Butanoic acid C4H8O2 88.11 0.88 e e
51 Ethylcyclopentenolone C7H10O2 126.15 0.97 e e
52 2-Butenoic acid, 2-methyl-, (E)- C5H8O2 100.12 0.95 e e
53 2-Butenoic acid, 3-methyl- C5H8O2 100.12 1.23 e e
54 1,2-Cyclopentanedione, 3-methyl- C6H8O2 112.13 e 1.61 2.36
55 2-Cyclopenten-1-one, 2-hydroxy-3-methyl- C6H8O2 112.13 3.26 e e
56 2-Cyclopenten-1-one, 3-ethyl-2-hydroxy- C7H10O2 126.15 1.45 e e
57 4H-Pyran-4-one, 3-hydroxy-2-methyl- C6H6O3 126.03 0.92 e e
58 3-Pentanone, 2,2-dimethyl- C7H14O 114.19 e e 5.12
59 2-Propenoic acid, 3-(4-hydroxy-3-methoxyphenyl)- C10H10O4 194.18 e 1.72 2.81
60 Cinnamic acid, 4-hydroxy-3-methoxy- C10H10O4 194.18 e e 1.19
61 n-Hexadecanoic acid C16H32O2 256.42 2.90 e e
Table 8 (continued )
Nitrogenated compounds
62 1H-Pyrazole, 3-methyl- C4H6N2 82.10 1.97 e e
63 N-Nitrosodimethylamine C2H6N2O 74.08 e 1.27 e
64 2-Ethyl-5-(2-fluorobenzylideneamino)-1,3,4-thiadiazole C11H10FN3S 235.28 e e 2.05
65 1H-Imidazole-2-carboxaldehyde, 1-methyl- C5H6N2O 110.11 1.15 e e
Polyaromatic compounds
66 1H-Inden-1-one, 2,3-dihydro- C9H8O 132.16 e 1.29 1.23
e 1.29 1.23
Other compounds
67 Triethylaluminum C6H15Al 114.16 e 3.23 e
e 3.23 e
Table 9
Main chemical compounds present in the bio-oils obtained at 400 C.
Monoaromatics
1 Benactyzine C20H25NO3 327.41 0.97 e e
2 Furfural C5H4O2 96.08 2.26 2.68 e
3 Ethanone, 1-(2-furanyl)- C6H6O2 110.11 1.16 e e
4 2-Furancarboxaldehyde, 5-methyl- C6H6O2 110.11 e 1.21 e
5 Furan, 2,3,5-trimethyl- C7H10O 110.15 1.05 e e
6 p-Benzoquinone C6H4O2 108.09 5.25 e e
7 2-Furanmethanol C5H6O2 98.10 2.56 3.51 2.55
8 2 (5H)-Furanone C4H4O2 84.07 e 1.98 e
9 2 (3H)-Furanone C4H4O2 84.07 1.28 e 0.90
10 2 (3H)-Furanone, dihydro- C4H6O2 86.08 2.10 1.36 e
11 4-Fluorophenol C6H5FO 112.10 1.21 e e
12 Mequinol C7H8O2 124.13 6.76 e e
13 Guaiacol <ortho> C7H8O2 124.14 e 7.19 7.75
14 Cresol <2-methoxy-para> C8H10O2 138.16 e 1.02 e
15 Cresol <ortho> C7H8O 108.14 1.55 2.91 1.90
16 Phenol C6H6O 94.11 5.91 5.70 6.25
17 Benzeneethanol, 2-methoxy- C9H12O2 152.19 e 1.76 0.70
18 Phenol, 2,6-dimethyl- C8H10O 122.16 e 1.70 e
19 Phenol, 2,4-dimethyl- C8H10O 122.16 e 1.76 0.70
20 Cresol <para> C7H8O 108.14 1.09 1.65 1.80
21 Cresol <meta> C7H8O 108.14 1.16 2.83 2.35
22 Phenol, 2-ethyl- C8H10O 122.16 e 2.56 2.05
23 Phenol, 3-ethyl- C8H10O 122.16 e 1.69 3.55
24 2-Methoxy-4-vinylphenol C9H10O2 150.17 e 2.16 1.80
25 2-Pentanone, 4,4-dimethyl- C7H14O 114.19 1.86 e 7.00
26 Phenol, 3,4-dimethyl- C8H10O 122.16 1.94 e e
27 Eugenol C10H12O2 164.20 e e 4.50
28 Phenol, 2,6-dimethoxy-4-(2-propenyl)- C11H14O3 194.22 1.86 e 2.90
29 Phenol, 2,6-dimethoxy- C8H10O3 154.16 7.43 13.52 21.00
30 Phenol, 2-methoxy-4-(1-propenyl)-(E)- C10H12O2 164.20 e 2.66 e
31 Trans-5,8-Dioxatricyclo [5.1.0.0 (4,5)] oct-2-ene C6H6O2 110.11 e 4.76 e
32 5-formyl-2-furancarboxylic acid C6H4O4 140.09 e e 2.55
33 1,2-diethoxybenzene C10H14O2 166.22 e e 7.65
34 1,3-Isobenzofurandione C8H4O3 148.11 0.19 e e
Aliphatics
35 Pentane, 3-methyl C6H14 86.18 1.67 1.65 e
36 2-Octene, (E)- C8H16 112.21 1.75 e e
37 2-Octene, (Z)- C8H16 112.21 0.22 e e
3.64 1.65 e
T. Aysu, M.M. Küçük / Energy 64 (2014) 1002e1025 1023
Table 9 (continued )
Oxygenated compounds
38 2-Cyclopenten-1-one C5H6O 82.04 2.37 1.98 e
39 2-Cyclopenten-1-one, 2-methyl- C6H8O 96.13 0.85 e e
40 1-Hydroxy-2-pentanone C5H10O2 102.13 e e 1.65
41 1-Penten-3-one, 2-methyl- C6H10O 98.14 2.41 1.04 e
42 2-Cyclopenten-1-one, 3-methyl- C6H8O 96.13 1.90 1.02 1.05
43 Propanoic acid C3H6O2 74.07 3.77 1.98 1.90
44 Acetic acid C2H4O2 60.05 22.36 14.09 5.95
45 2,3-Dimethyl-2-cyclopenten-1-one C7H10O 110.15 1.40 e e
46 Hexanal, 2-ethyl- C8H16O 128.21 e 5.59 e
47 Bicyclo [3.3.0] oct-1 (2)-en-3-one- C8H10O 122.16 1.13 e e
48 1,4:3,6-Dianhydro-.alpha.-d-glucopyranose C6H8O4 144.13 e e 2.55
49 2,5-Cyclohexadiene-1,4-dione C6H4O2 108.09 6.10 e e
50 2-Cyclopenten-1-one, 2-hydroxy-3-methyl- C6H8O2 112.13 e 1.74 1.65
51 2-Propenoic acid, 3-(4-hydroxy-3-methoxyphenyl)- C10H10O4 194.18 e 2.62 e
52 4H-1-Benzopyran-4-one, 3,5,8-trimethoxy-2-methyl- C13H14O5 250.02 1.86 e e
53 2-Pentadecanone C15H30O 226.40 e e 1.60
Nitrogenated compounds
54 N-Nitrosodimethylamine C2H6N2O 74.08 3.22 1.89 e
55 Isopropyl,methoxy pyrazine C8H12N2O 152.19 1.40 e e
4.62 1.89 e
Polyaromatic compounds
56 1H-Inden-1-one, 2,3-dihydro- C9H8O 132.16 e 1.79 1.50
57 Phenanthrene, 1,2-epoxy-1,2-dihydro- C14H10O 194.22 e e 1.25
e 1.79 2.75
Table 10
Main chemical compounds present in the bio-oils obtained at 350 C.
Monoaromatics
1 Furfural C5H4O2 96.08 2.61 e e
2 2 (3H)-Furanone, dihydro- C4H6O2 86.08 1.48 e 2.82
3 2-Furanmethanol C5H6O2 98.10 3.46 3.31 7.05
4 2 (5H)-Furanone C4H4O2 84.07 1.29 1.78 e
5 2 (3H)-Furanone- C4H4O2 84.07 e e 3.29
6 Guaiacol <ortho> C7H8O2 124.14 5.46 e 12.22
7 Cresol <ortho> C7H8O 108.14 4.29 2.97 1.88
8 Phenol C6H6O 94.11 7.97 12.64 11.75
9 Phenol, 3,5-dimethyl- C8H10O 122.16 1.49 e e
10 Phenol, 2,4-dimethyl- C8H10O 122.16 1.29 e e
11 Cresol <para> C7H8O 108.14 3.29 e e
12 Cresol <meta> C7H8O 108.14 6.12 3.55 e
13 Phenol, 3,4-dimethyl- C8H10O 122.16 4.29 3.36 e
14 Phenol, 3-ethyl- C8H10O 122.16 2.42 e e
15 Phenol, 4-ethyl- C8H10O 122.16 e 2.58 e
16 2-Methoxy-4-vinylphenol C9H10O2 150.17 1.49 3.25 3.29
17 Guaiacol <ortho> C7H8O2 124.14 e 11.65 e
18 Phenol, 2,6-dimethoxy- C8H10O3 154.16 12.93 12.98 17.26
19 Benzene, 1,4-dimethoxy- C8H10O2 138.16 e 1.73 e
20 Trans-5,8-Dioxatricyclo [5.1.0.0 (4,5)] oct-2-ene C6H6O2 110.11 4.17 e 4.23
21 1,2-Benzenedicarboxylic acid, dihexyl ester C24H38O4 390.55 e e 1.86
22 1,3-Isobenzofurandione C8H4O3 148.11 e e 0.47
Aliphatics
23 2,4-Dimethyl-1-heptene C9H18 126.24 e e 1.88
(continued on next page)
1024 T. Aysu, M.M. Küçük / Energy 64 (2014) 1002e1025
Table 10 (continued )
1.50 e 10.34
Oxygenated compounds
27 Lyxitol, 1-O-nonyl- C14H30O5 278.38 2.56 e e
28 2H-Pyran, tetrahydro- C5H10O 86.13 e 1.65 e
29 Heptane, 1,1-dimethoxy- C9H20O2 160.25 e e 3.76
30 Acetic acid C2H4O2 60.05 19.64 e e
31 Propanoic acid C3H6O2 74.07 3.22 2.23 e
32 3-Pentanone, 2,2-dimethyl- C7H14O 114.19 4.92 e e
33 2-Pentanone, 4,4-dimethyl- C7H14O 114.19 e e 8.30
34 3-Hexanone, 5-methyl- C7H14O 114.19 e 14.98 e
35 2,5-Cyclohexadiene-1,4-dione C6H4O2 108.09 e e 0.94
36 2-Decanone C10H20O 156.27 e 2.48
37 1,4:3,6-Dianhydro-.alpha.-d-glucopyranose C6H8O4 144.13 e 2.06 e
Nitrogenated compounds
38 Hydrazine, 1,1-dimethyl- C4H8N2 60.10 e 1.32 3.29
39 1H-Pyrazole-4-carboxylic acid, 3-methyl- C5H6N2O2 126.11 e e 2.35
40 Maleic hydrazide C4H4N2O2 112.09 1.65 e e
41 Benzothiazole, 2-amino-6-methyl- C8H8N2S 164.23 2.46 e e
42 2-Propenamide, N-(4-aminobutyl)-3-(3,4-dihydroxyphenyl)-, (E)- C13H18N2O3 250.29 e 5.45 e
Polyaromatic compounds
43 1H-Inden-1-one, 2,3-dihydro- C9H8O 132.16 e 2.23 e
44 4 (3H)-Quinazolinone, 2-methyl-3-(2-methylphenyl)- C16H14N2O 250.29 e e 4.23
45 1H-Indole, 2-methyl-3-phenyl- C15H13N 207.27 e 2.64 e
46 3-Benzyl-idene-6-methoxy-chroman-4-one C17H14O3 266.28 e e 0.67
e 4.87 4.90
Other compounds
47 Selenium dioxide dimer O2S 110.95 e 1.78 e
48 Stannane, butyltriethyl- C10H24Sn 263.00 e 3.38 e
e 5.16 e
the abundant compounds of phenols and alcohols and the absor- optimum condition for bio-oil formation is at 500 C with a heating
bance peaks of CeH and ]CeH vibrations between 2900 and rate of 50 C/min in the non-catalytic runs. The effects of different
3000 cm1 show the presence of alkanes and alkenes. The typical catalysts on degradation of F. orientalis L. were also investigated and
carbonyl group (C]O) stretching vibrations at about 1710 cm1 in types of catalysts have changed both product distribution and
bio-oils show that aldehydes, ketones or carboxylic acids were selectivity. Zinc oxide was found to be more effective than
produced by degradation of raw material. The C]C stretching vi- aluminium oxide in terms of bio-oil formation. Besides, the effects of
brations at about 1608 cm1 in bio-oils prove the presence of al- particle size and sweeping gas flow rate on product yields were also
kenes. Presence of alcohols and esters could be confirmed by CeH determined under the optimum temperature and heating rate con-
bending vibrations between 880 and 1300 cm1 and CeO ditions. The composition of the bio-oils was characterized by chro-
stretching vibrations between 1200 and 1300 cm1 in bio-oils. matographic and spectroscopic techniques as well as the calorific
Aromatic compounds are confirmed by the aromatic C]C values of bio-chars and bio-oils. It was found that pyrolysis oil is a
stretching vibrations between 1450 and 1550 cm1. Benzene de- complex mixture of aromatic, oxygenated, and nitrogenated organic
rivatives and phenol compounds are thought to be formed from compounds. The obtained bio-oils have higher heating values than
decomposition of lignin. On the other hand, the decomposition of the raw material. The GCeMS results of bio-oils indicate that the
hemicellulose and cellulose produces mainly alkanes, aldehydes, pyrolysis of F. orientalis L. is a promising process for both renewable
alcohols, carboxylic acids, furan and its derivatives. fuel production and chemical feedstock. However, more trials with
different catalysts should be performed in a pilot scale plant.
4. Conclusion
Acknowledgements
In this study, pyrolysis of a specific biomass (F. orientalis L.) was
performed to obtain solid (bio-char) and liquid (bio-oil) products This study was supported by Yuzuncu Yil University Research
under different heating rate conditions at temperatures ranging from Fund, and we gratefully acknowledge the financial support of this
350 to 600 C with and without catalyst. It was found that the study (no: 2013-FBE-D004).
T. Aysu, M.M. Küçük / Energy 64 (2014) 1002e1025 1025
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