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Direct Conversion of Sunower Shells to Alkanes and Aromatic

Compounds
Shipeng Guo, Libin Wu, Chao Wang, Jinhua Li, and Zhengyu Yang*
Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Graduate UniVersity of
Chinese Academy of Sciences, Beijing 100101, China
ReceiVed April 24, 2008. ReVised Manuscript ReceiVed July 10, 2008
Deoxy-liquefaction runs were performed at nal temperatures of 350, 400, 450, and 500 C, with only 10
wt % distilled water as medium. The inuence of the nal temperature on the properties of biopetroleum
obtained from sunower shell samples (with kernels 5 wt %) via deoxy-liquefaction was examined in relation
to the yield and distribution of products (i.e., gas, solid, liquid), especially the compositions of oil products.
Furthermore, the liquid oil with a maximum yield and H/C molar ratio of 1.99 and higher heating value (HHV)
of 46.9 MJ/kg was obtained at 450 C. The biopetroleum analyzed by gas chromatography-mass spectrometry
(GC-MS) with the National Institute of Standards and Technology (NIST) 98 MS library was mainly composed
of benzene derivatives, phenolic derivatives, and alkanes (C
7
-C
19
). What is special is that the content of
(Z,Z)-9,12-octadecadienoic acid (RT ) 21.26 min), which came from the few sunower kernels decreased
from 21.32% at 350 C to zero at 500 C. This suggested that deoxy-liquefaction in a closed system could
realize not only the deoxygenation of biomass but the deoxygenation of linoleic acid by controlling the nal
temperature. Moreover, the biopetroleum obtained can be upgraded to transport fuel or separated for chemical
products.
1. Introduction
With the increasing demand for energy and the rising
atmospheric greenhouse gas levels, renewable energy should
be widely explored to renovate the energy source structure and
keep sustainable development safe.
1
Biomass as a clean and
renewable energy resource has become more and more attractive
to industry in the past 20 years. It is estimated to contribute
10-14% of the total energy supply in the world.
2-4
In addition,
biomass has zero net emission of CO
2
and has very low contents
of sulfur, nitrogen, and ash, which gives lower emissions of
SO
2
, NO
x
, and soot than conventional fossil fuels.
1
Therefore,
it has great potential for alleviating energy problems, such as
the greenhouse effect and the depletion of fossil energy
sources.
5,6
Recently, biomass has been widely used as an alternate energy
source in developing countries because the economies of these
countries are based largely on agriculture and forestry. One of
the major drawbacks is the low efciency of using biomass. In
China, biomass is widely used for cooking and heating via
biomass combustion with a thermal efciency only between 10
and 30%.
7
In addition, storage and transport also limit the use
of biomass. On the basis of the above standpoints, the
liquefaction of biomass has attracted more attention in the world.
In the thermo-chemical conversion processes, biomass can
be converted into liquid fuels and chemicals indirectly through
gasication to syngas followed by catalytic F-T conversion
and direct liquefaction. Typical direct liquefaction processes
* To whom correspondence should be addressed. Telephone: +86-(0)10-
64888781. Fax: +86-(0)10-64879375. E-mail: zhengyuyang@vip.sina.com.
(1) Zhang, Q.; Chang, J.; Wang, T.; Xu, Y. Review of biomass pyrolysis
oil properties and upgrading research. Energy ConVers. Manage. 2007, 48,
8792.
(2) Xu, C.; Etcheverry, T. Hydro-liquefaction of woody biomass in sub-
and super-critical ethanol with iron-based catalysts. Fuel. 2008, 87, 335
345.
(3) Mckendry, P. Energy production from biomass (part 1): Overview
of biomass. Bioresour. Technol. 2002, 83, 3746.
(4) Putun, A. E.; Uzun, B. B.; Apaydin, E.; Putun, E. Bio-oil from olive
oil industry wastes: Pyrolysis of olive residue under different conditions.
Fuel Process. Technol. 2005, 87, 2532.
(5) O

zbay, N.; Putun, A. E.; Putun, E. Structural analysis of bio-oils


from pyrolysis and steam pyrolysis of cottonseed cake. J. Anal. Appl.
Pyrolysis 2001, 60, 89101.
(6) Ates, F.; Putun, A. E.; Putun, E. Catalytic pyrolysis of perennial
shrub, Euphorbia rigida in the water vapour atmosphere. J. Anal. Appl.
Pyrolysis 2005, 73, 299304.
(7) Meng, N.; Leung, D. Y. C.; Leung, M. K. H.; Sumathy, K. An
overview of hydrogeng production from biomass. Fuel Process. Technol.
2006, 87, 461472.
Figure 1. Schematic diagram of the closed reactor system.
Energy & Fuels 2008, 22, 35173522 3517
10.1021/ef800283k CCC: $40.75 2008 American Chemical Society
Published on Web 08/08/2008
include fast pyrolysis and high-pressure direct liquefaction.
8
Fast
pyrolysis is an effective biomass conversion with high liquid
yield, in the absence of air at atmospheric pressure, with a
heating rate of about 300 C/min.
9
Many researchers have
obtained liquid oil by fast pyrolysis.
10,11
However, the oil
obtained from fast pyrolysis consists mainly of oxygenous
compounds, such as aldehydes, ketones, esters, and ethers, and
has a low heating value (20-25 MJ/kg); therefore, it can not
be used as transport fuels before upgrading. Furthermore, its
acidity and corrosion made it hard to store. Whereas, high-
pressure direct liquefaction technology has the potential for
producing liquid oils with much higher heating values. However,
(8) Xu, C.; Lad, N. Production of heavy oils with high caloric values
by direct liquefaction of woody biomass in sub/near-critical water. Energy
Fuels 2008, 22, 635642.
(9) Goyal, H.; Seal, D.; Saxena, R. C. Bio-fuels from thermochemical
conversion of renewable resources: A review. Renewable Sustainable Energy
ReV. 2008, 12, 504517.
(10) Luo, Z. Y.; Wang, S. R.; Liao, Y. F.; Zhou, J. S.; Gu, Y. L.; Cen,
K. F. Research on biomass fast pyrolysis for liquid fuel. Biomass Bioenergy
2004, 26, 455462.
(11) Zhang, S. P.; Yan, Y. J.; Ren, Z. W. Analysis of liquid product
obtained by the fast pyrolysis of biomass. J. Chin. Sci. Technol. 2001, 27,
666668.
Table 1. Elemental Composition of Sunower Shells
ultimate analysis (%) sunower shells
C 41.52
H 6.08
O
a
38.90
N 1.48
S 0.30
ash 11.72
empirical formula (excluded ash) CH
1.76
O
0.71
N
0.03
H/C molar ratio 1.76
O/C molar ratio 0.71
HHV (MJ/kg) 13.89
a
By difference.
Figure 2. Yields of products at the heating rate of 80 C/min.
Figure 3. Compositions of gas at different nal temperatures.
Table 2. Comparison of Biopetroleum at 450 C with Diesel
properties methods biopetroleum diesel
density at 30 C (kg/m
3
) ASTM D 1298 875 838
viscosity at 50 C (cSt) ASTM D 88 30 2.1
ash point (C) ASTM D93 65 54
elemental analysis (wt %)
C 82.18 86.58
H 13.61 13.29
O
a
2.92 0.01
N 1.29 65 ppm
S 0.11
empirical formula CH
1.99
O
0.03
N
0.01
H/C molar ratio 1.99 1.84
O/C molar ratio 0.03
HHV (MJ/kg) Dulongs formula 46.9 48.5
a
By difference.
Figure 4. GC-MS spectra of the liquid oil obtained at (a) 350 C, (b)
400 C, (c) 450 C, and (d) 500 C.
3518 Energy & Fuels, Vol. 22, No. 5, 2008 Guo et al.
the abundant solvents, such as alcohols
2,12
and hot compressed
water,
13
consume a lot of heat in the reaction, which renders it
an expensive process. In addition, the product can be a tarry
lump, which is difcult to handle.
9
In this paper, dry sunower shells were chosen for preparing
liquid oil with only 10 wt % distilled water as a medium at the
heating rate of 80 C/min. Experiments were conducted in an
airtight reactor in different nal temperatures of 350, 400, 450,
and 500 C, and the inuence of the nal temperature on the
yield and distribution of products was examined. The liquid oil
with a maximum yield and H/C molar ratio of 1.99 and higher
heating value (HHV) of 46.9 MJ/kg was obtained at 450 C.
The liquid oil analyzed by gas chromatography-mass spec-
trometry (GC-MS) with the National Institute of Standards and
Technology (NIST) 98 MS library was mainly composed of
alkanes (C
7
-C
19
) and benzene and phenolic derivatives, and
the elemental analysis was similar to that of petroleum; therefore,
the term biopetroleum is applied to the oil. Moreover, in this
liquefaction process, only 10 wt % distilled water was added
as medium and the most oxygen in biomass was released in
the forms of CO and CO
2
. There is only 2.9 wt % oxygen
contained in the oil; therefore, this liquefaction process can be
called deoxy-liquefaction (may also be classied as a hydro-
thermal process).
2. Experimental Section
2.1. Pretreatment of Sunower Shells. Sunower shells that
have been taken from the Tong county of Beijing were milled and
then screened to give fractions with particle diameters in the range
of 0.1-0.2 mm. Then, the samples were dried in a vacuum drying
oven at the temperature of 60 C for 24 h.
2.2. Experimental Procedure. Similar to the methods described
in the literature,
14,15
the deoxy-liquefaction experiments were carried
out with a tubular stainless-steel reactor (length of 100 mm and
internal diameter of 10 mm), and the schematic diagram is shown
in Figure 1. The sample (5.0 g) with 10 wt % distilled water as
medium was placed in the reactor and then heated from room
temperature to the nal temperature at a xed heating rate of 80
C/min and maintained for 20 min. The initial atmosphere of the
airtight reactor was vacuum, while the nal pressure of the system
can reach 12-20 MPa after heating. The nal pressure which,
increased with nal temperature, has nearly no effect on the results.
The reactor was airtight during the whole reaction. Two to three
duplicate runs have been conducted, and the error under the same
conditions was ensured within 8%.
After heated, the reactor was cooled to room temperature. Gas
products were collected by an injector for the volume measurement,
and the compositions were analyzed by GC to calculate the mass
of gas products. Then, the residue was further distilled from room
temperature to 400 C at normal pressure to obtain water and
biopetroleum, which oated on the water. The water can be
extracted by an injector, and then biopetroleum was analyzed by
GC-MS, while the functional groups analysis was carried out by
Fourier transform infrared spectroscopy (FTIR). The water product
was gathered and weighed to calculate the generated water (GW)
from biomass by reducing the water added as medium. Finally,
the solid char was removed, and the elemental analysis was
performed.
2.3. Characterization. The elemental compositions (C, H, and
N) of the biomass and products (liquid and char) were analyzed
using Elementar Vario EL (Germany). The oxygen content was
calculated by difference, assuming that the content of sulfur (S) in
the biomass and products was negligible, because of the trace
(12) Miller, J. E.; Evans, L.; Littlewolf, A.; Trudell, D. E. Bath
microreactor studies of lignin and lignin model compound depolymerization
by bases in alcohol solvents. Fuel 1999, 78, 13631366.
(13) Qu, Y.; Wei, X.; Zhong, C. Experimental study on the direct
liquefaction of Cunninghamia lanceolata in water. Energy 2003, 28, 597
606.
(14) Wang, C.; Du, Z.; Pan, J.; Li, J.; Yang, Z. Direct conversion of
biomass to bio-petroleum at low temperature. J. Anal. Appl. Pyrolysis 2007,
78, 438444.
(15) Li, J.; Wu, L.; Yang, Z. Analysis and upgrading of bio-petroleum
from biomass by direct deoxy-liquefaciton. J. Anal. Appl. Pyrolysis 2008,
81, 199204.
Table 3. GC-MS Characterization of 26 Typical Compounds Obtained at 450 C
peak RT compound relative content % formula M
w
1 2.95 heptane 2.78 C
7
H
16
100
2 3.8 toluene 7.28 C
7
H
8
92
3 5.08 ethylbenzene 3.31 C
8
H
10
106
4 5.5 nonane 3.39 C
9
H
20
128
5 6.05 6,6-dimethylcycloocta-2,4-dienone 0.42 C
10
H
14
O 150
6 7.05 decane 4.2 C
10
H
22
142
7 8.11 tricyclo[4.2.2.0(1,5)]decan-7-ol 2.06 C
10
H
16
O 152
8 8.66 1-(1-oxopentyl)- 1H-imidazole 4.86 C
8
H
12
N
2
O 152
9 9.66 4-(2,5-dihydro-3-methoxyphenyl)butylamine 4.63 C
11
H
19
NO 181
10 10.18 (1,2,3,3a,4,6a-hexahydropentalen-2-yl)-dimethyl-amine 3.78 C
10
H
17
N 151
11 10.94 3-ethyl-5-methyl-phenol 1.86 C
9
H
12
O 136
12 11.61 2-butyl-1-octanol 4.68 C
12
H
26
O 186
13 13.01 tetradecane 4.46 C
14
H
30
198
14 14.28 pentadecane 7.03 C
15
H
32
212
15 15.5 hexadecane 6.59 C
16
H
34
226
16 16.68 heptadecane 16.08 C
17
H
36
240
17 17.78 octadecane 4.46 C
18
H
38
254
18 18.93 2-heptadecanone 3.78 C
17
H
34
O 254
19 19.85 estra-1,3,5(10)-trien-17a-ol 1.55 C
18
H
24
O 256
20 20.88 2-nonadecanone 7.40 C
19
H
38
O 282
21 21.26 (Z,Z)-9,12-octadecadienoic acid 4.32 C
18
H
32
O
2
280
22 22.92 nonadecane 0.44 C
19
H
40
268
23 24.28 3-ethyl-5-(2-ethylbutyl)-octadecane 0.22 C
26
H
54
366
24 24.98 3-octyl-,cis-oxiraneoctanoic acid 0.05 C
18
H
34
O
3
298
25 26.02 3-ethyl-5-(2-ethylbutyl)-octadecane 0.28 C
26
H
54
366
26 26.47 olean-12-ene-3,15,16,21,22,28-hexol, (3a,15a`,16a`,21a,22a`)- 0.05 C
30
H
50
O
6
506
27 28.33 3-ethyl-5-(2-ethylbutyl)-octadecane 0.05 C
26
H
54
366
total value of the relative content (%) 100.01
Sunower Shells to Alkanes and Aromatic Compounds Energy & Fuels, Vol. 22, No. 5, 2008 3519
content of sulfur in biomass, char, and biopetroleum. The higher
heating value was calculated by Dulongs formula.
13,16
HHV (MJ/kg) )[338.2C wt %+1442.8(H wt %-
O wt %/8)] 0.001
The compositions of gas product were analyzed by a gas
chromatogram (GC122, Shanghai, China) with a thermal conductiv-
ity detector (TCD). GC-MS analysis was performed using a trace
GC ULTRA Thermo gas chromatograph coupled with the mass
selective detector (DSQ, Italia). The temperature increased from
50 C (held for 1 min) to 250 C (held for 10 min) at the heating
rate of 10 C/min. Compounds in the biopetroleum were identied
by means of the NIST 98 MS library with the 2002 update. The
FTIR spectra of the biopetroleum were recorded using a Bruker
Tensor 27 infrared spectrophotometer.
3. Results and Discussion
3.1. Biomass Characterization. The elemental analysis of
the sunower shells was shown in Table 1. The empirical
formula calculated is CH
1.76
O
0.71
N
0.03
, with a H/C molar ratio
of 1.76, just in the range of petroleum of 1.6-1.8,
17
but the
HHV of 13.89 MJ/kg is very low. According to the theory
concluded in former research, the H/C molar ratio should be
increased and the oxygen should be released in the forms of
CO and CO
2
to obtain liquid oil with a HHV from biomass.
18
3.2. Effects of Temperature on the Yields of Products.
The experiments were performed at different nal temperatures
(16) Scholze, B.; Meier, D. Characterization of the water-insoluble
fraction from pyrolysis oil pyrolytic lignin. Part I. PY-GC/MS, FTIR, and
functional groups. J. Anal. Appl. Pyrolysis 2001, 60, 4154.
(17) Dinesh, M.; Charles, U. P. J.; Philip, H. S. Pyrolysis of wood/
biomass for bio-oil: A critical review. Energy Fuels 2006, 20, 848889.
Table 4. GC-MS Characterization of 51 Typical Compounds Obtained at 500 C
peak RT compound relative content % formula M
w
1 2.68 benzene 1.35 C
6
H
6
78
2 2.91 heptane 0.59 C
7
H
16
100
3 3.23 7-oxo-octanoic acid 0.14 C
8
H
14
O
3
158
4 3.51 11-hexadecyn-1-ol 0.23 C
16
H
30
O 238
5 3.72 toluene 5.75 C
7
H
8
92
6 3.98 octane 1.79 C
8
H
18
114
7 4.72 4-hydroxy-4-methyl-2-pentanone 2.11 C
6
H
12
O
2
116
8 5.01 ethylbenzene 6.33 C
8
H
10
106
9 5.49 p-xylene 3.95 C
8
H
10
106
10 5.97 tricyclo[4.2.2.0(1,5)]decan-7-ol 1.49 C
10
H
16
O 152
11 6.58 1-ethyl-4-methyl-benzene 4.13 C
9
H
12
120
12 6.84 phenol 4.53 C
6
H
6
O 94
13 7.12 1,3,5-trimethyl-benzene 3.66 C
9
H
12
120
14 7.58 1,2,4-trimethyl-benzene 1.16 C
9
H
12
120
15 8.04 2-methyl-phenol 5.41 C
7
H
8
O 108
16 8.39 3-methyl-phenol 6.29 C
7
H
8
O 108
17 8.61 undecane 3.92 C
11
H
24
156
18 8.98 2,5-dimethyl-phenol 1.1 C
8
H
10
O 122
19 9.55 2,4-dimethyl-phenol 6.46 C
8
H
10
O 122
20 9.84 3-ethyl-phenol 3.42 C
8
H
10
O 122
21 10.13 geranyl isovalerate 4.82 C
15
H
26
O
2
238
22 10.88 3-ethyl-5-methyl-phenol 2.87 C
9
H
12
O 136
23 11.18 2-ethyl-4-methyl-phenol 1.54 C
9
H
12
O 136
24 11.56 geranyl isovalerate 2.69 C
15
H
26
O
2
238
25 11.96 2-methyl- Naphthalene 1.78 C
11
H
10
142
26 12.19 1-ethylidene-1H-indene 1.14 C
11
H
10
142
27 12.45 7-hydroxy-1,3,4,5,6,7-hexahydro-2H-naphthalen-4a-ylmethyl ester acetc
acid
0.35 C
13
H
20
O
3
224
28 12.63 1-ethylideneoctahydro-7a-methyl-,cis-1H-indene 0.35 C
12
H
20
164
29 12.94 tetradecane 1.2 C
14
H
30
198
30 13.28 o-[(1,2,3,4-tetrahydro-2-naphthyl)methyl]-hydrocinnamic acid 0.9 C
20
H
22
O
2
294
31 13.65 1,4-dimethyl-naphthalene 1.73 C
12
H
12
156
32 13.94 1,4-dimethyl-naphthalene 0.4 C
12
H
12
156
33 14.23 pentadecane 2.43 C
15
H
32
212
34 14.51 3,5-dimethyl-indolizine 0.98 C
10
H
11
N 145
35 14.99 1,6,7-trimethyl-naphthalene 0.46 C
13
H
14
170
36 15.45 hexadecane 1.8 C
16
H
34
226
37 15.78 5,8,11,14-eicosatetraynoic acid 0.12 C
20
H
24
O
2
296
38 16.02 5,8,11,14-eicosatetraynoic acid 0.45 C
20
H
24
O
2
296
39 16.61 heptadecane 2.86 C
17
H
36
240
40 17.24 2-nonadecanone 2,4-dinitrophenylhydrazine 0.32 C
25
H
42
N
4
O
4
462
41 17.72 octadecane 0.93 C
18
H
38
254
42 18.18 5,8,11,14-eicosatetraynoic acid 0.05 C
20
H
24
O
2
296
43 18.77 nonadecane 1.32 C
19
H
40
268
44 19.41 1-heptatriacotanol 0.18 C
37
H
76
O 536
45 19.75 9-hexyl-heptadecane 0.66 C
23
H
48
324
46 20.72 9-hexyl-heptadecane 0.92 C
23
H
48
324
47 21.99 octacosane 1.06 C
28
H
58
394
48 22.79 3-(octadecyloxy)propyl ester stearic acid 0.09 C
39
H
78
O3 594
49 26.66 1-(2-acetoxyethyl)-3,6-diazahomoadamantan-9-one oxime 0.11 C
13
H
21
N
3
O
3
267
50 26.97 9-hexyl- heptadecane 0.78 C
23
H
48
324
51 28.31 2-pentadecanone 0.84 C
15
H
30
O 226
total value of the relative content (%) 99.94
3520 Energy & Fuels, Vol. 22, No. 5, 2008 Guo et al.
with a heating rate of 80 C/min, and the relationship between
nal temperature and yields of products is shown in Figure 2.
The liquid oil yield increased from 18% (350 C) to the
maximum yield of 19.2% (450 C) and then decreased to 5.25%
(500 C). Although the oil yield is a little lower than that referred
in other literature,
19-21
the oil contains more alkanes with a
HHV. Therefore, it has more potential to be a substitute for
petroleum fuels.
As shown in Figure 2, the gas yield increased with a nal
temperature rising from 350 to 500 C, which was mentioned in
Sensozs literature.
22
Additionally, the curve of the char yield was
similar to that of gas, which is completely reversed to previous
studies of cellulose and lignocelluloses.
23
Maybe the difference
could be attributed to this unique reactor system(airtight, lowwater
medium, and 80 C/min heating rate). It can be seen that the molar
content of CO
2
(76-92%) was much greater than that of CO
(5-8%), CH
4
(1-13%), C
2
H
6
(0-4%), and H
2
(1-2.5%). This
is advantageous for preserving hydrogen atoms in biomass and
removing oxygen atoms in the forms of CO
2
and CO, leading to
the higher H/Cmolar ratio and lower O/Cratio in the biopetroleum.
In addition, it is helpful to increase the H/C molar ratio on the
condition that hydrogen release can be controlled to as little as
possible. As is well-known, hydrogen was removed in the forms
of CH
4
, C
2
H
6
, and H
2
in the deoxy-liquefaction process. Therefore,
more attention should be paid to the yields of CH
4
, C
2
H
6
, and H
2
obtained at different nal temperatures. As shown in Figure 3, the
content of CH
4
increased rapidly from 3.5 to 12.5%, with the nal
temperature rising from 450 to 500 C, while there were few
changes in C
2
H
6
and H
2
. This suggests that higher temperature
could accelerate the dehydrogenation process, in which carbon re-
assembled to formchar. Besides, the production of generated water,
as a liquid product formed in the dehydration process,
24
also
consumed hydrogen atoms. Therefore, a higher nal temperature
is disadvantageous for increasing the H/C molar ratio and heating
value of the biopetroleum.
In summary, to obtain the maximum yield of biopetroleum
at this heating rate, the nal temperature should be controlled
below 500 C.
3.3. Properties of Biopetroleum. For the investigation of the
potential use of the biopetroleum as a source of transport fuel, the
physical properties of the biopetroleum obtained at the nal
temperature of 450 C were determined according to American
Society for Testing and Materials (ASTM) standards and compared
to that of diesel fuel
25
in Table 2. By comparison, the viscosity of
biopetroleum is extremely higher than that of diesel fuel; therefore,
the viscosity must be decreased by blending with diesel or
upgrading before being used as transport fuels. The density was
875 kg/m
3
at 30 C, which is lower than water and other bio-oil.
16
Elemental analysis was conducted, and the empirical formula was
assessed to be CH
1.99
O
0.03
N
0.01
with a heating value of 46.9 MJ/
kg. The oxygen content of biopetroleum has a great decrease
compared to the feedstock, but it is still a little higher than that of
diesel fuel. Thus, biopetroleum is quite reactive and not as stable
as diesel fuel. On the basis of the above description, the biopetro-
leum must be upgraded, for example, by distilling or blending with
diesel oil to be used as transport fuel directly.
3.4. GC-MS Analysis of the Biopetroleum. The GC-MS
spectra of the liquid oil obtained at different nal temperatures are
shown in Figure 4, and the peaks were identied by means of the
NIST 98 MS library. The compositions of the liquid oil obtained
at 500 C were more complex than those at 350, 400, and 450 C,
and the leading compounds were benzene derivatives (31.84%)
and phenolic derivatives (31.62%), which were present in the
section (RT )2.68-12.63 min). In contrast, the main compounds
(C
7
-C
19
alkanes) obtained at 350, 400, and 450 C were present
in the section (RT ) 13-29 min). Additionally, the biopetroleum
with the maximum yield was obtained at 450 C. Therefore, as a
representative, the compounds obtained at 450 and 500 C were
listed in Tables 3 and 4, respectively.
(18) Wang, C.; Pan, J.; Li, J.; Yang, Z. Comparative studies of products
produced from four different biomass samples via deoxy-liquefaction.
Bioresour. Technol. 2008, 99, 27782786.
(19) Putun, A. E.; Apaydin, E.; Putun, E. Bio-oil production from
pyrolysis and steam pyrolysis of soybean-cake: Product yields and composi-
tion. Energy 2002, 27, 703713.
(20) O

zbay, N.; Putun, A. E.; Uzun, B. B.; Putun, E. Biocrude from


biomass: Pyrolysis of cottonseed cake. Renewable Energy 2001, 24, 615
625.
(21) Piyali, D.; Anuradda, G. Bio-oil from pyrolysis of cashew nut
shellsA near fuel. Biomass Bioenergy 2003, 25, 113117.
(22) S ensoz, S.; I

lknur, D.; Gercel, H. F. Olive bagasse (Olea europea


L.) pyrolysis. Bioresour. Technol. 2006, 97, 429436.
(23) Valenzuela-Calahorro, C.; Bernalte-Garcia, A.; Gomez-Serrano, V.;
Bernalte-Garc a, M. J. Inuence of particle size and pyrolysis conditions
on yield, density and some textural parameters of chars prepared from holm-
oak wood. J. Anal. Appl. Pyrolysis 1987, 12, 6170.
(24) Czernik, S.; Bridgwater, A. V. Overview of applications of biomass
fast pyrolysis oil. Energy Fuels 2004, 18, 590598.
(25) Onay, O.; Kockar, O. M. Pyrolysis of rapeseed in a free fall reactor
for production of bio-oil. Fuel 2006, 85, 19211928.
Figure 5. Effect of the nal temperature on the components of liquid
oil.
Figure 6. FTIR analysis of the biopetroleum (450 C).
Table 5. Properties of Char in Different Temperatures
ultimate analysis (W/W %) 350 C 400 C 450 C 500 C
C 45.61 43.73 43.62 52.48
H 2.05 1.70 1.79 1.99
N 2.77 2.54 2.69 2.91
O
a
12 15.85 15.72 11.36
ash 37.56 36.17 36.17 31.25
a
By difference.
Sunower Shells to Alkanes and Aromatic Compounds Energy & Fuels, Vol. 22, No. 5, 2008 3521
The contents of the organic compounds mainly composed of
benzene derivatives (6.72-20.61%), alkanes (20.61-49.98%),
and phenolic derivatives (0-31.62%) at different nal temper-
atures are shown in Figure 5. The maximum content of alkanes
was achieved at 450 C, and the maximum benzene and phenolic
derivatives content was obtained at 500 C. Besides, the decrease
of alkanes at the higher nal temperature was accompanied by
an increase of benzene and phenolic derivatives. As is well-
known, phenolic derivatives mainly originate from the three
main structural monomers of lignin: guaiacylpropane, syringyl-
propane, and p-hydroxyphenylpropane. In a monomeric guaiacyl
unit, the bond energies of the methyl C-O and the aromatic
C-O of the methoxyl group are 245 and 356 kJ/mol, respec-
tively, and that of the aromatic C-O of the hydroxyl group is
414 kJ/mol.
26
Theoretically, the cleavage of aromatic C-O bond
of the methoxyl group is more difcult than that of the methyl
C-O bond, but in this deoxy-liquefaction system, lots of
dimethyl-phenol, methyl-phenol, and phenol were detected in
the liquid oil and no alkyl pyrocatechol was found. This indicates
that the oxygen in methoxyl was easy to remove, while the
removal of oxygen in the phenolic hydroxyl group was difcult.
As shown in Table 4, many new kinds of methyl- and
ethyl- phenolic and benzene derivatives were detected at 500
C, and the maximum content of benzene and phenolic
derivatives of liquid oil was obtained at this nal temperature
(Figure 5). The normal C-C bond energy is about 380 kJ/mol,
which is easy to break by thermal excitation. Thus, it is possible
that under higher temperature, more CH
3
and CH
3
CH
2
radicals
formed because of the cleavage of alkanes and alkyl C-C bond
and methyl C-O bond and then combined with phenolic and
benzene products that formed in the decomposition and rear-
rangement of biomass. The phenolic and benzene derivatives
were more stable; therefore, more phenolic and benzene
derivatives were generated at higher nal temperature. Ad-
ditionally, distilled water has also been found to be very effective
for promoting free-radical reactions.
27
The content of other oxygenous compounds in liquid oil
decreases as the temperature rises. For example, (Z,Z)-9,12-
octadecadienoic acid (RT )21.26 min), a linoleic acid produced
from the few sunower kernels (5 wt % of the samples) mixed
in sunower shells was detected in liquid products of 350, 400,
and 450 C, which was not mentioned in other literature. The
concentration of (Z,Z)-9,12-octadecadienoic acid decreased from
21.32% at 350 C to zero at 500 C. This is consistent with the
change trends of other oxygenous compounds, indicating that
deoxy-liquefaction in this closed system could realize not only
the deoxygenation of biomass but also the deoxygenation of
linoleic acid by controlling the nal temperature. In addition, a
higher nal temperature benets the process of removing oxygen
in the form of CO
2
and CO, resulting in low oxygen content in
the oil. However, in Figure 2, both generated water (GW) and
char increased with a nal temperature rising and the oil yield
decreased to the lowest value at 500 C, which indicates that
the carbonization and dehydration processes both become more
active at a higher nal temperature. Thus, to obtain the oil
products with the maximum yield and high quality, the nal
temperature should be controlled at 450 C.
3.5. FTIR Analysis of Biopetroleum. The FTIR spectra of
biopetroleum obtained at 450 C is shown in Figure 6. The C-H
stretching vibrations between 2800 and 3000 cm
-1
and C-H
deformation vibrations between 1350 and 1475 cm
-1
indicate
the presence of alkane groups. The peaks between 3300 and
3500 cm
-1
are characteristics of -OH groups, and the relative
intensity is much lower than that shown in other literature.
22,28-30
The absorption of CdO stretching vibrations between 1680 and
1800 cm
-1
is compatible with the presence of ketone and
aldehyde groups. In addition, the CdC stretching vibrations
between 1500-1675 cm
-1
indicate the existence of alkenes and
aromatics, and the absorption peaks of substituted aromatic
groups are also observed at 650-800 cm
-1
. In summary, these
results are consistent with the GC-MS analysis of the
biopetroleum.
3.6. Composition Analysis of Char. The char products were
removed and stored in a vacuum drying oven at the temperature
of 60 C for 24 h. The elemental analysis was conducted, and
the results were shown in Table 5.
As can be seen from Table 5, produced chars have a high xed
carbon content, high ash, and little hydrogen content. The char
with the highest xed carbon content was obtained at 500 C, which
is in accordance with the conclusion that dehydrogenation and
carbonization both become more active at a higher nal temper-
ature. Hydrocarbons were difcult to regenerate in the char as a
result of the low H/C molar ratio (about 0.25). The heating value
of the char is calculated at about 15 MJ/kg, nearly the same with
that of biomass; therefore, it could be briquetted with the addition
of some biomass powder for combustion.
4. Conclusion
In this study, the biopetroleum was obtained from sunower
shells by deoxy-liquefaction in a closed reactor with the heating
rate of 80 C/min at different nal temperatures of 350, 400,
450, and 500 C. Only 10 wt % distilled water was added as a
medium in the reactor, which is lower than that in other high-
pressure liquefactions. The oil with the maximum yield (19.2%)
was produced at 450 C, and the empirical formula was
calculated as CH
1.99
O
0.03
N
0.01
with a H/C ratio of 1.99 and HHV
of 46.9 MJ/kg, which were both in the range of petroleum. The
biopetroleum analyzed by GC-MS with the NIST 98 MS
library was mainly composed of alkanes (C
7
-C
19
) and deriva-
tives of benzene and phenol. It has more potential to be a
substitute for petroleum fuels than the oil that consisted mainly
of aldehydes, ketones, esters, and ethers.
The effect of the nal temperature on the yield and distribu-
tion of products was studied in this paper. The decrease of
aliphatic hydrocarbons at the higher nal temperature was
accompanied by an increase of aromatic compounds. In addition,
(Z,Z)-9,12-octadecadienoic acid (RT )21.26 min) as a different
product in these experiments decreased with the nal temper-
ature rising. The deoxygenation process was companied with
the processes of dehydrogenation and carbonization, and the
three processes could be accelerated by increasing temperature.
A higher temperature was helpful to remove oxygen from
oxygenous compounds, but the oxygen in the phenolic hydroxyl
group was difcult to remove. Therefore, it can be concluded
that the temperature should be controlled at 450 C to obtain
the biopetroleum with a high yield and high quality.
The biopetroleum obtained from sunower shells by direct
deoxy-liquefaction had better properties to be a potential
candidate as a kind of vehicle fuel or as a source of chemicals.
The upgrading work on this subject is still in progress, although
it remains a promising and challenging task.
EF800283K
(26) Demirbas, A. Mechanisms of liquefaction and pyrolysis reactions
ofbiomass. Energy ConVers. Manage. 2000, 41, 633646.
(27) Akiya, N.; Savage, P. E. Roles of water for chemical reactions in
high-temperature water. Chem. ReV. 2002, 102, 27252750.
(28) Zhang, S.; Yan, Y.; Li, T.; Ren, Z. Upgrading of liquid fuel from
the pyrolysis of biomass. Bioresour. Technol. 2005, 96, 545550.
(29) Uzun, B. B.; Putun, A. E.; Putun, E. Fast pyrolysis of soybean
cake: Product yields and compositions. Bioresour. Technol. 2006, 97, 569
576.
(30) Williams, P. T.; Nugranad, N. Comparision of products from the
pyrolysis and catalytic pyrolysis of rice husks. Energy 2000, 25, 493513.
3522 Energy & Fuels, Vol. 22, No. 5, 2008 Guo et al.

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