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Abstract
To meet the increasing need for bioenergy several raw materials have to be considered for the production of e.g. bioethanol and biogas.
In this study, three lignocellulosic raw materials were studied, i.e. (1) winter rye straw (Secale cereale L), (2) oilseed rape straw (Brassica
napus L.) and (3) faba bean straw (Viciafaba L.). Their composition with regard to cellulose, hemicellulose, lignin, extractives and ash
was evaluated, as well as their potential as raw materials for ethanol and biogas production. The materials were pretreated by wet
oxidation using parameters previously found to be optimal for pretreatment of corn stover (195 1C, 15 min, 2 g l1 Na2CO3 and 12 bar
oxygen). It was shown that pretreatment was necessary for ethanol production from all raw materials and gave increased biogas yield
from winter rye straw. Neither biogas productivity nor yield from oilseed rape straw or faba bean straw was signicantly affected by
pretreatment. Ethanol was produced by the yeast Saccharomyces cerevisiae during simultaneous enzymatic hydrolysis of the solid
material after wet oxidation with yields of 66%, 70% and 52% of theoretical for winter rye, oilseed rape and faba bean straw,
respectively. Methane was produced with yields of 0.36, 0.42 and 0.44 l g1 volatile solids for winter rye, oilseed rape and faba bean straw,
respectively, without pretreatment of the materials. However, biogas productivity was low and it took over 50 days to reach the nal
yield. It could be concluded that all three materials are possible raw materials for either biogas or ethanol production; however,
improvement of biogas productivity or ethanol yield is necessary before an economical process can be achieved.
r 2007 Elsevier Ltd. All rights reserved.
Keywords: Ethanol; Biogas; Lignocellulosic biomass; Winter rye (Secale cereale L.); Oilseed rape straw (Brassica napus L.); Faba bean straw (Viciafaba L.)
1. Introduction
Increased concern for the security of oil supply and the
negative impact of fossil fuels on the environment,
particularly greenhouse gas emissions, has put pressure
on society to nd renewable alternatives [1]. Bioenergy
from renewable resources is already today a viable
alternative to fossil fuels; however, to meet the increasing
need for bioenergy several raw materials have to be
considered. Lignocellulose is the most abundant organic
material on earth and is therefore a promising raw material
for bioenergy production [2].
Bioethanol can be produced from e.g. sugars, starch and
various lignocellulosic materials such as straw, wood and
waste [3]. While the production of ethanol from sugars and
Corresponding author. Tel.: +45 4677 4195; fax: +45 4677 4122.
0961-9534/$ - see front matter r 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biombioe.2007.06.001
Please cite this article as: Petersson A, Thomsen MH, Hauggaard-Nielsen H, Thomsen AB. Potential bioethanol and biogas production using
lignocellulosic biomass from winter rye, oilseed rape and faba bean. Biomass and Bioenergy (2007), doi:10.1016/j.biombioe.2007.06.001
ARTICLE IN PRESS
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Please cite this article as: Petersson A, Thomsen MH, Hauggaard-Nielsen H, Thomsen AB. Potential bioethanol and biogas production using
lignocellulosic biomass from winter rye, oilseed rape and faba bean. Biomass and Bioenergy (2007), doi:10.1016/j.biombioe.2007.06.001
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2.5. Biogas
3. Analysis methods
3.1. Dry matter and ash content
Duplicates of 0.5 g solid material or 10 ml of liquid
sample were dried at 105 1C overnight to determine the dry
weight. The samples were thereafter heated to 550 1C for
3 h to determine the ash content.
3.2. Analysis of carbohydrates in solid fraction
The amounts of extractives were determined in the raw
materials by extraction in boiling ethanol for 24 h prior to
hydrolysis. To quantify the sugar polymers in the raw
material and the solid fraction after wet oxidation, a twostep acid hydrolysis was performed. The rst hydrolysis
step was performed at 30 1C for 60 min with 1.5 ml of
H2SO4 (72%) for 0.16 g DM. Then 42 ml water was added
and the second step was performed at 121 1C for 60 min.
The hydrolysate was ltered and the dried lter cake
subtracted for ash content is reported as Klason lignin.
4. Calculations
In order to evaluate the pretreatment, the recovery of
sugars in the ltrate or the solid was calculated according
to Eq. (1). The yields after enzymatic hydrolysis were
calculated according to Eq. (2) for cellulose and Eq. (3) for
hemicellulose. Product yields for ethanol and biogas are
reported as g product per 100 g raw material or as liter
per g volatile solids (VS) for biogas yield. The amount of
biogas resulting from the inoculum (measured in bottles
only containing inoculum) was subtracted from the total
biogas formed before the yield was calculated.
Recoveryfiltrate=solid
Hydrolysis yieldcellulose
massglucose after enzymatic hydrolysis 0:9
100%
Please cite this article as: Petersson A, Thomsen MH, Hauggaard-Nielsen H, Thomsen AB. Potential bioethanol and biogas production using
lignocellulosic biomass from winter rye, oilseed rape and faba bean. Biomass and Bioenergy (2007), doi:10.1016/j.biombioe.2007.06.001
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hydrolysis 0:88
100%.
Faba beana
92.9
90.7
92.1
40.8
22.3
1.2
ND
2.6
16.1
5.1
7.1
4.9
27.3
15.0
2.7
2.0
2.2
14.2
9.6
10.1
17.0
28.4
12.4
4.0
2.2
1.8
14.4
7.9
8.8
20.2
Winter rye
Dry weight
% of DW
Glucan
Xylan
Galactan
Mannan
Arabinan
Klason
Ash
Extractives
Residual
Raw material
Hydrolysis yieldhemicellulose
!
massxylosearabionose after enzymatic
and
Cellulose
Hemicellulose
Cellulose
Hemicellulose
Cellulose
Hemicellulose
0
10
15
gram 100
Raw material
20
25
gram-1
Solid phase
30
35
40
dry weight
Liquid phase
Fig. 1. Cellulose and hemicellulose in 100 g dry raw material (both black
bars) shown together with recovery after wet oxidation of 100 g dry
material. The recovered cellulose and hemicellulose are divided into
amounts found in the solid phase (gray bars) and amounts found in the
liquid phase (white bars). Average values and standard deviation reported
for triplicate measurements.
Please cite this article as: Petersson A, Thomsen MH, Hauggaard-Nielsen H, Thomsen AB. Potential bioethanol and biogas production using
lignocellulosic biomass from winter rye, oilseed rape and faba bean. Biomass and Bioenergy (2007), doi:10.1016/j.biombioe.2007.06.001
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Cellulose
Hemicellulose
Sugar polymer
Winter rye
with the other ltrates (Fig. 4). The ethanol yields (Table 2)
without ltrate were 66%, 70% and 52% of the theoretical
for winter rye, oilseed rape and faba bean straw,
respectively. This is higher than what could enzymatically
be converted (which were 49%, 58% and 43%, respectively). S. cerevisiae does not consume pentoses such as
xylose and therefore xylose, which is released during the
enzymatic hydrolysis, accumulated (Fig. 5).
Oilseed
Faba bean
Winter rye
Oilseed
Faba bean
0
10
20
30
40
50
Yield (%) of monomeric sugar
No pretreatment
60
Wet oxidation
Ethanol (gram)
Winter rye
Oilseed rape
Faba bean
2.0
1.5
1.0
0.5
0.0
0
Methane (ml)
200
150
100
50
0
0
20
40
60
0
20
40
60
Incubation time (days)
20
40
60
Fig. 3. Ethanol formation (closed symbols) in simultaneous saccharication and fermentation (SSF) of 8 g lter cake in 60 ml ltrate or with 60 ml water
for winter rye, oilseed rape and faba bean straw (upper row). Using the same raw materials, methane formation was measured (open symbols) from 0.3 g
raw material in 5 ml water, or 5 ml wet oxidized material (lower row). The biogas asks, and the asks containing only manure, were all inoculated with
20 ml manure.
Please cite this article as: Petersson A, Thomsen MH, Hauggaard-Nielsen H, Thomsen AB. Potential bioethanol and biogas production using
lignocellulosic biomass from winter rye, oilseed rape and faba bean. Biomass and Bioenergy (2007), doi:10.1016/j.biombioe.2007.06.001
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6. Discussion
Both biogas and ethanol can clearly be produced from
the lignocellulosic raw materials evaluated in this study
(Fig. 3). For ethanol production, it was necessary to
include a pretreatment step in order to increase enzymatic
hydrolysis (Fig. 2). However, pretreatment only had a
signicant effect on the production of biogas from winter
rye straw, while biogas productivity and yield were similar
for untreated and wet oxidized materials of both oilseed
rape straw and faba bean straw. In this study, xed
parameters for wet oxidation previously found in optimization of corn stover pretreatment were used [14]. This was
done by a screening of the three raw materials, but since
winter rye straw, oilseed rape straw and faba bean straw
have quite different chemical compositions (Table 1), the
pretreatment effect is expected to be improved when
optimized separately for each specic raw material and
thereby yields and productivities can potentially be
increased. Furthermore, inhibitors are partly formed by
10
2.5
2.0
1.5
1.0
0.5
Malic acid
Winter rye
Succinic acid
Formic acid
Faba bean
Raw material
Glycolic acid
Filtrate
Acetic acid
Oilseed rape
After
Faba bean
Before
Oilseed rape
Raw material
After
Winter rye
After
0.0
Before
Before
3.0
Filtercake
Fig. 5. Xylose concentrations before and after simultaenous saccharication and fermentation (SSF). Xylose concentration in the ltrate (black
bars), xylose released as monomers during SSF originating from ltrate
(gray bars) and from lter cake (white bars). Average values and standard
deviation are reported for duplicate measurements.
Table 2
Bioethanol and methane production determined as yield (g (100 g dry raw material)1) and percentage of theoretical yield for winter rye, oilseed rape and
faba bean straw comparing conversion without any pretreatment (untreated) and with a wet oxidation pretreatment step (WO)
Treatment
Ethanol
Methane
Ethanol yield
(g (100 g DM)1)
% of theoretical
yield
Methane yield
(g (100 g DM)1)
% of theoretical
yield
Winter rye
Untreated
WO
WO lter cake
0.59
13.5
15.4
2.5
56
66
18.2
24.4
72
96
Oilseed rape
Untreated
WO
WO lter cake
0.97
9.93
10.9
6.3
61
70
18.8
20.4
78
85
Faba bean
Untreated
WO
WO lter cake
1.04
8.3
8.4
6.5
50
52
18.9
18.4
77
75
For ethanol, the yields are also reported for the WO lter cake where the solid and liquid fractions were separated by ltration. The theoretical ethanol
yield was based on glucan content in the raw material and the theoretical methane yield was based on the assumption that the formula for volatile solids
was CH2O and that the volatile solids was stoichiometrically converted into carbon dioxide and methane.
Please cite this article as: Petersson A, Thomsen MH, Hauggaard-Nielsen H, Thomsen AB. Potential bioethanol and biogas production using
lignocellulosic biomass from winter rye, oilseed rape and faba bean. Biomass and Bioenergy (2007), doi:10.1016/j.biombioe.2007.06.001
ARTICLE IN PRESS
A. Petersson et al. / Biomass and Bioenergy ] (]]]]) ]]]]]]
sugar degradation and thus optimal pretreatment conditions can both increase sugar recovery as well as lower the
formation of inhibitors.
Judging by the selection of present raw materials and the
selected pretreatment conditions, biogas seems to be the
most favorable product, compared with ethanol, primarily
because of higher yields compared with the theoretically
expected (Table 2). Pretreatment did not have a signicant
effect on biogas production from oilseed rape straw or faba
bean straw, which simplies the production and lowers the
production cost and energy use. Biogas productivity was,
however, rather low, but this was probably a result of
acclimatization of the microorganisms and thus the
productivity would be increased in a continuous process.
Ethanol has advantages over biogas e.g. since it is a
liquid fuel that can readily be integrated into existing fuel
supply systems and directly substitute fossil fuels in the
transportation sector. In order to make an economically
feasible process out of ethanol production, ethanol yields
need to be as high as possible while production costs are
kept as low as possible. The yield of ethanol could be
increased, compared with what was found in this study,
with optimized pretreatment conditions and if the microorganism used could convert the pentoses originating from
the hemicellulose fraction into ethanol. From the raw
material analysis, it can be concluded that the maximum
theoretical ethanol yield based on all available sugars in
e.g. winter rye is 38.20 g (100 g)1 DW. Another fact that
will contribute to the ethanol production economy is that
lignin is not affected in the process, but can be burned and
the energy used in the process.
When evaluating faba bean and oilseed rape as potential
bioenergy raw materials, additional agroecosystem services
need to be included like break crop effects in cereal-rich
rotations reducing the survival of nematode populations,
suppressing leaf and root diseases such as take-all fungus,
and reducing weeds [20,23,24] and consequently reducing
the potential need for pesticides diminishing pollution as
well as indirect energy use.
It can be concluded that biogas can easily be produced
from winter rye straw, oilseed rape straw and faba bean
straw. However, biogas productivity has to be optimized to
increase the gas production level. For production of
ethanol, the pretreatment needs to be optimized and a
strain or combination of strains or microorganisms should
be used so that all sugars are effectively converted into
ethanol. The selected present raw materials offer different
services to the agroecosystems, and with the right local
selection of crops and adaptation to the current crop
production it seems promising for farmers to provide the
society with biomass resource for energy production.
Acknowledgments
The authors are thankful to Mr. Tomas Fernqvist, Mrs.
Ingelis Larsen and Dr. Anders Thygesen for technical
assistance. This work was nancially supported by Det
strategiske Forskningsrad by the project 2104-06-0004Bio.REF: Biorenery for sustainable reliable economical
fuel production from energy crops.
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lignocellulosic biomass from winter rye, oilseed rape and faba bean. Biomass and Bioenergy (2007), doi:10.1016/j.biombioe.2007.06.001
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Please cite this article as: Petersson A, Thomsen MH, Hauggaard-Nielsen H, Thomsen AB. Potential bioethanol and biogas production using
lignocellulosic biomass from winter rye, oilseed rape and faba bean. Biomass and Bioenergy (2007), doi:10.1016/j.biombioe.2007.06.001