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Lignocellulosic Biomass
Wei Yan, Tapas C. Acharjee, Charles J. Coronella, and Victor R. Vasquez
Chemical and Metallurgical Engineering Department, University of Nevada, MS170 Reno, NV 89557; coronella@unr.edu
(for correspondence)
Published online 5 August 2009 in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/ep.10385
Torrefaction is a process to convert diverse lignocellulosic biomass feedstocks into an energy dense homogeneous solid, a pretreatment for subsequent thermochemical conversion. Loblolly pine was treated by
wet torrefaction (hot compressed water, 2002608C)
and dry torrefaction (nitrogen, 2503008C), with
mass yield of solid product ranging between 57 and
89%, and energy densication to 108136% of the
original feedstock. The solid product has been characterized, including proximate analysis, ber analysis,
ultimate analysis, and equilibrium moisture. In both
dry and wet torrefaction, increasing temperature
results in decreased mass yield and increased energy
densication, and results in a solid with increased
carbon content, decreased oxygen content, and
decreased volatiles. The biomass is transformed into a
fuel similar to a low-rank coal. Generally, the wet torrefaction process produces a solid with greater energy
density than dry torrefaction, with the same mass
yield. The ber analysis indicates that hemicellulose
is quickly removed during wet torrefaction, and the
solid product contains substantial quantities of aqueous soluble compounds. The equilibrium moisture
content of solids produced by both processes is somewhat decreased from that of the biomass feedstock,
indicating a hydrophobic solid suitable for storage and
transportation. 2009 American Institute of Chemical
Engineers Environ Prog, 28: 435440, 2009
eliminated for widespread successful commercialization [2, 3]. In both cases, feedstock handling is
complex due to the diverse nature of important feedstocks, including commercial timber, agricultural residues as diverse as rice hulls, corn stover and wheat
chaff, and energy crops such as switch grass. Seasonal availability and low forest density make feedstock logistics complex and expensive. To solve these
problems, there is a need for a process to homogenize the feedstocks, while simultaneously producing
a stable, energy-dense, solid fuel. Two distinct thermal pretreatment technologies are investigated in this
study: wet torrefaction and dry torrefaction.
In the process we call wet torrefaction, also
known as hydrothermal pretreatment, biomass is
treated in hot compressed water, resulting in three
products, including gases, aqueous chemicals, and a
solid fuel [46]. The temperature is in the range of
2002608C, and the pressures are up to 700 psi. The
solid product contains about 5590% of the mass and
8095% of the fuel value of the original feedstock.
The gas product is about 10% by mass of the feedstock, and the aqueous chemicals, primarily sugars,
make up the balance [79]. On the other hand, dry
torrefaction, sometimes called low-temperature pyrolysis, is a process in which the biomass is heated in
an inert gas environment at temperatures ranging
from 200 to 3008C [3, 1012]. The dry torrefaction
reaction has two products, a solid and a gas. The
solid has about 6080% of the mass, and approximately 7090% of the fuel value of the original biomass [1012].
Both torrefaction processes exhibit some common
features. The solid product has a higher energy density relative to the starting biomass feedstock in both
cases. Both solid products are easily friable and have
an aroma similar to wood char. The reaction mechanisms of both torrefaction processes are poorly understood. The objective of this work is to investigate how
Wet Torrefaction
Wet torrefaction of loblolly pine was performed in
a 100-mL Parr bench-top reactor (Moline, IL) at temperatures ranging from 200 to 2608C. The temperature of the reactor was controlled using PID controller. The reactor pressure was not controlled but indicated by a pressure gauge and ranged from 200 to
700 psi, approximately in accord with the water
vapor pressure. For each run, a mixture of loblolly
pine and water (water:biomass 5 5:1, w/w) was
loaded into the reaction vessel. The biomass sample
size was about 2 g. Prior to the reaction, the biomass
was stirred manually to ensure complete wetting.
Nitrogen was passed through the reactor for 10 min
to purge oxygen out of the reactor. The reactor was
heated up in 1530 min and maintained at the
desired temperature for a desired period of time
(5 min). Then, the reactor was cooled to room temperature rapidly by immersion in an ice bath. The gas
sample was released. The liquid sample and solid
sample were separated and collected for further analysis.
Dry Torrefaction
Dry torrefaction of loblolly pine was carried out in
the 100-mL Parr reactor described above, but tted
with a glass sample holder to separate the biomass
from the hot reactor walls. The pretreatment was performed with a nitrogen ow rate of 10 mL (STP)/min.
The glass sample loader with biomass particles
(5 g) were placed in the center of reactor. The torrefaction temperature was between 250 and 3008C
and was controlled using a PID controller. The temperature program consists of a dynamic heating period following by an isothermal period. After a
desired isothermal reaction period (80 min), the
sample was cooled to room temperature with continuous nitrogen ow through the reactor. The solid
sample was collected for further analysis.
436 October 2009
Analytical Methods
Proximate Analysis
Pretreatment
Wet torrefaction
Dry torrefaction
Temperature
(8C)
Mass
yield (%)
HHV
(cal/g)
Energy
densication ratio
Energy
yield (%)
200
230
260
250
275
300
88.7
70.6
57.0
83.8
74.2
60.5
5043.3
5276.8
6342.5
5005.4
5207.2
5627.4
1.08
1.13
1.36
1.07
1.12
1.21
95.8
79.8
77.5
89.7
83.1
73.2
Table 2. Ultimate analysis of biomass feedstock and thermal pretreated solid products.
Pretreatment
Biomass
Wet torrefaction
Dry torrefaction
Temperature (8C)
200
230
260
250
275
300
C (%)
50.25
54.72
56.05
72.07
50.73
52.27
54.81
Wet and dry torrefaction of loblolly pine were performed at various temperatures. All thermal pretreatments and analytical experiments were performed at
least twice, and mean values are reported. Mass yield,
energy densication ratio, and energy yield are three
important measures in this study, which are dened
as:
Mass yield
H (%)
5.97
6.03
5.94
4.90
6.21
6.13
5.94
N (%)
0
0.14
0.09
0.16
0.12
0.15
0.14
S (%)
0
0
0
0
0
0
0
O (%)
43.34
39.11
37.92
22.89
42.94
41.45
39.11
Table 3. Proximate analysis of biomass feedstock and thermal pretreated solid products.
Pretreatment
Biomass
Wet torrefaction
Dry torrefaction
Temperature (8C)
Moisture (%)
Volatiles (%)
Ash (%)
200
230
260
250
275
300
3.6
1.3
1.3
1.3
0
0
0
83.7
87.1
83.8
73.2
87.7
83.0
82.3
12.3
12.4
15.8
26.3
11.8
16.4
17.0
0.4
0.5
0.4
0.5
0.5
0.6
0.7
Table 4. Fiber analysis of biomass feedstock and thermal pretreated solid products; conversion of individual
ber components, relative to initial starting feedstock.
Pretreatment
Temperature
(8C)
Hemicellulose
(%)
Cellulose
(%)
Lignin
(%)
Aqueous
solubles (%)
11.9
54.0
25.0
8.7
Wet torrefaction
200
0.4
47.4
27.8
24.3
230
0
44.1
30.2
25.3
260
0
33.9
33.8
31.8
Dry torrefaction
250
9.2
51.0
34.1
5.2
275
6.5
52.7
36.7
3.5
300
2.3
32.7
62.1
2.2
B. Conversion of individual ber components, relative to initial starting feedstock
Wet torrefaction
200
97.0
22.1
1.4
2147.7
230
100.0
42.3
14.7
2105.3
260
100.0
64.2
22.9
2108.3
Dry torrefaction
250
35.2
20.9
214.3
49.9
275
59.5
27.6
28.9
70.1
300
88.3
63.4
250.3
84.7
Ash
(%)
0.4
0.5
0.4
0.5
0.5
0.6
0.7
A negative conversion indicates a ber compound that was apparently produced by torrefaction.
Table 5. Equilibrium moisture content of biomass feedstock and thermal pretreated solid products.
Pretreatment
Biomass
Wet torrefaction
Dry torrefaction
Temperature
(8C)
EMC (%),
RH 5 11.3%
EMC (%),
RH 5 83.6%
200
230
260
250
275
300
3.5
1.8
0.9
0.4
2.3
2.2
2.3
15.6
12.8
8.2
5.3
10.4
8.7
8.7
biomass has been transformed into a fuel with properties resembling low rank coal. The reduced EMC
indicates that the pretreated solid is more hydrophobic and can be easily stored to accommodate seasonal availability. Although both thermal pretreatments show some common features, the reaction
mechanism is quite different as reected by the ber
analysis. In wet torrefaction, hemicellulose is very reactive even at 2008C, while both cellulose and lignin
can be dissolved partially at higher temperatures.
Both cellulose and hemicellulose are somewhat reactive in dry torrefaction, producing a solid that resists
dissolution, similar to lignin. The solid product produced by dry torrefaction is not at all soluble by ber
analysis measurements.
This study reports analysis on initial scoping
experiments; there is no attempt to optimize the conditions of torrefaction. In particular, the optimal reaction time and temperature have not been identied,
nor have reaction kinetics. Pretreated biomass presumably will be pelletized for feeding to a thermochemical conversion process, and there is no attempt
here to describe the solid characteristics for required
handling (friability, morphology, etc.). To establish
techo-economic feasibility, mass and energy balance
of both torrefaction processes and the subsequent
thermal conversion process (e.g. gasication or fast
pyrolysis) must be investigated as well. We anticipate
further reports from our lab and from other labs on
these issues.
ACKNOWLEDGMENTS
CONCLUSION
LITERATURE CITED