1421
To increase the overall ethanol yield from softwood, the steam pretreatment stage
can be carried out in two steps. The two-step pretreatment process was evaluated
from a techno-economic standpoint and compared with the one-step pretreatment
process. The production plants considered were designed to utilize spruce as raw
material and have a capacity of 200 000 tons/year. The two-step process resulted in a
higher ethanol yield and a lower requirement for enzymes. However, the two-step
process is more capital-intensive and has a higher energy requirement. The estimated
ethanol production cost was the same, 4.13 SEK/L (55.1 /L) for both alternatives.
For the two-step process different energy-saving options were considered, such as a
higher concentration of water-insoluble solids in the filter cake before the second step,
and the possibility of excluding the pressure reduction between the steps. The most
optimistic configuration, with 50% water-insoluble solids in the filter cake in the feed
to the second pretreatment step, no pressure reduction between the pretreatment steps,
and 77% overall ethanol yield (0.25 kg EtOH/kg dry wood), resulted in a production
cost of 3.90 SEK/L (52.0 /L). This shows the potential for the two-step pretreatment
process, which, however, remains to be verified in pilot trials.
Introduction
The enzymatic process for the production of fuel
ethanol from lignocellulosic materials has been recognized as the most promising option in terms of ethanol
yield and low production cost (1-3). In this process, the
pretreatment step is of vital importance because cellulose
in its native form cannot be hydrolyzed to any great
extent by enzymes. In softwood the cellulose is the
primary sugar source for ethanol production, and mannan, the main constituent of the hemicelluloses, is the
second. It has been shown that cellulose and mannan
have different optima in terms of sugar recovery in the
pretreatment step (4, 5). Cellulose requires a higher
temperature than hemicellulose for optimal sugar recovery. During steam pretreatment, the sugars formed may
be degraded. Glucose, which is liberated from the cellulose, is further degraded to 5-hydroxymethylfurfural
(HMF), levulinic acid, and formic acid. The hydrolysis of
hemicellulose generates pentoses, which are converted
to furfural and formic acid. These degradation products,
together with lignin degradation products and released
organic acids, act as inhibitors in the fermentation step
(6-9) and in the enzymatic hydrolysis step (10). More
severe pretreatment conditions will cause greater degradation of hemicellulosic sugars with loss of yield and
possible inhibition as a consequence (7, 9, 11). However,
a rather high severity is required to enhance the enzymatic digestibility of the cellulose (8, 12). Steam pretreatment is improved by using an acid catalyst such as
H2SO4 or SO2. The acid increases the recovery of hemicellulosic sugars and improves the enzymatic hydrolysis
of the solid residue (13-17).
* To whom correspondence should be addressed. Tel: +46 (0)46 82 97. Fax: +46 (0)46 45 26. E-mail: guido.zacchi@
chemeng.lth.se.
10.1021/bp049931v CCC: $27.50
1422
pretreatment step utilizing recycled evaporation condensates available at 60 C as washing water. The content
of water-insoluble solids (WIS) in the filter cake is
assumed to be 30% in the base case process, but this
parameter was varied to study the impact on the ethanol
production cost. In the simulations it was assumed that
filtration is carried out in a counter-current fashion in
two stages, and the relation between the addition of
washing water and washing efficiency was based on
studies of the removal of lignin from pulp (26). The
amount of washing water was adjusted to remove 95%
of the sugars, and sugars fed to the second step were
assumed to be unaffected, i.e., not degraded to byproducts. The whole filtrate from the washing step together
with the slurry leaving the second step is transferred to
the SSF step.
An alternative to the two-step process described above
is to exclude the flashing after the first pretreatment step
and to dewater and wash the material under pressure.
The filtrate in this process configuration is flashed to
atmospheric pressure, and the latent heat in the vapor
is recovered at 95 C (HX8 in Figure 2). Because the
pressure, and thus the temperature, of the slurry is
maintained, the amount of steam needed in the second
step is decreased. The addition of washing water also
results in a decrease in the temperature of the slurry
being fed to the second step. It has been shown, however,
that sugars not washed out, e.g., those fed to the second
step, are degraded to a lower extent than might be
expected. In a study by Soderstrom et al. (27) two-step
1423
Figure 3. Composition of raw material and yields after pretreatment, expressed as g/100 g dry raw material. For the two-step case
yields are given as overall yields from both the first and the second step.
1424
Methods
The methodology used in this work is similar to that
described previously (28); however, a brief description,
including the updates to the model, is provided here.
Aspen Plus from Aspen Technology (25) was used to
simulate the process. Rigorous material and energy
balance calculations using detailed equipment models
were carried out to determine flow rates, composition,
and energy flow for all streams in the process. Sizing of
the equipment was carried out utilizing the Icarus
Process Evaluator (IPE) (29) and by using rules of thumb
(30). Equipment cost was estimated using the IPE,
various reports, and vendor quotations. The cost of the
pretreatment reactors was based on a quotation from
Stake Technology (31). To evaluate the consistency of the
equipment cost provided by the IPE, vendor quotations
were obtained from a Swedish engineering company. The
process equipment compared was columns, pumps, heat
exchangers, and vessels including fermentors. The cost
cost
raw material
wood
chemicals
sulfur dioxide
lime
defoamer
sodium hydroxide
(NH4)2HPO4
MgSO4
enzymes
byproduct income
solid fuel
carbon dioxide
utilities
electricity
cooling water
process water
other costs
labor (per employee)
insurance
unit
0.42
1.5
0.70
20.0
2.00
1.50
4.41
19.0
0.79
0.03
250
0.14
1.40
500 000
1
maintenance
SEK/kg DM
SEK/kg
SEK/kg
SEK/kg
SEK/kg
SEK/kg
SEK/kg
SEK/106 FPU
SEK/kg DM
SEK/kg
SEK/MWh
SEK/m3
SEK/m3
SEK/year
% of fixed capital
investment
% of fixed capital
investment
()
C2 ) C1
A2
A1
0.6
1425
Table 2. Composition of Streams in the Base Cases of One- and Two-Step Pretreatmenta
one-step
stream
liquid phase
water
hexoses
pentoses
others
25.0
18.2
0.9
solid phase
hexosans
pentosans
lignin
acetyl groups
15.0
1.8
7.0
0.2
total flow
50.0
temp (C)
pressure (bar)
25
1
7.6
3.6
0.0
1.4
0.0
0.4
two-step
5
31.1
4.8
1.4
1.4
14.9
4.9
3.6
0.0
0.8
0.0
0.3
8.6
0.1
6.6
18.2
217
22
8.9
144
4
4.0
100
1
53.9
14.9
100
1
217
22
5.6
144
4
3.9
100
1
30.2
4.6
1.7
1.0
38.7
0.2
0.1
0.1
47.8
4.4
1.6
1.0
19.5
10.0
0.2
6.6
10.0
0.2
6.6
54.3
55.9
54.7
70
1
82
1
100
1
10
9.8
4.7
0.0
0.3
0.0
0.1
11
90.5
6.1
1.8
1.7
7.8
6.2
19.5
217
22
10.1
144
4
4.7
100
1
114.0
91
1
one-step
two-step
pressure (bar)
14.1
11.6
15.2
-2.8
-2.5
0.0
-5.9
-3.5
12.0
22
22
4
1
-4.3
-2.6
7.2
0.73
4
1
1.37
1426
Table 4. Costs in the Base Case Processes
one-step
yearly cost
MSEK
M$
two-step
cost/L EtOH
SEK
yearly cost
cents MSEK
raw matl
83.0 11.1
1.41 18.8
chemicals
50.4
6.7
0.86 11.4
byproducts -31.3 -4.2 -0.53 -7.1
utilities
11.5
1.5
0.20
2.6
other costs
37.9
5.1
0.64
8.6
capital
91.5 12.2
1.55 20.7
total
243
32.4 4.13 55.1
M$
cost/L EtOH
SEK
cents
83.0 11.1
1.36 18.1
51.5
6.9
0.84 11.2
-29.5 -3.9 -0.48 -6.4
12.1
1.6
0.20
2.6
39.3
5.2
0.64
8.6
96.4 12.9
1.58 21.0
253
33.7 4.13 55.1
1427
1428
Conclusions
Figure 9. Summary of costs. One-step BC: one-step base case, 71.8% ethanol yield. Two-step BC: two-step base case, washing
water at 60 C, 74.6% ethanol yield. Two-step worst case: slurry from the first step cooled to 20 C, 30% WIS in filter cake, and
74.6% ethanol yield. C95%: no flashing after first step, washing water at 180 C, 50% WIS in filter cake, and 74.6% ethanol yield.
optimistic case: no flashing after first step, no washing, 50% WIS in filter cake, 77.0% ethanol yield.
Acknowledgment
The Swedish Energy Agency is gratefully acknowledged for its financial support.
1429
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