TEMPLATE DESIGN 2008

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Physicochemical Properties and Thermal Decomposition of Various Biomass
Annie Gallagher and Sushil Adhikari
Biosystems Engineering Department, Auburn University, Auburn, Alabama 36849.


Introduction
Objectives
Methods
References
1) Thermal Analysis
Thermogravimetric Analysis- Run with Shimadzu
Model TGA-50H, Columbia, MD, and data was
analyzed with TA-60 and Excel. 0.5mg of sample
were heated from 30-850C at 5,10,15, and
20C/min with air and nitrogen atmospheres at a
flow rate of 30mL/min.
Differential Scanning Calorimeter- DSC (model
Q200, TA instruments, New Castle DE) was
performed with Nitrogen at a flow rate of
20 mL/min at a heating rate of 10C/min.








2) Physicochemical Properties
Proximate Analysis- completed according to the
National Renewable Energy Laboratorys (NREL)
laboratory analytical procedure.
Energy Content- 0.5 grams of biomass was
analyzed with IKA C200 calorimeter.
Determine optimal biomass and operating parameters for
thermochemical conversion based on:
1)Thermal Analysis
Degradation profiles
Reaction Kinetics
2)Physicochemical Properties
Proximate Analysis
Energy Content


Methods
Results/ Discussions Thermal Analysis
Acknowledgements

Results/ Discussion Physicochemical
Properties 1) Thermal Analysis

Thermogravimetric Analysis
Observed Thermal Behavior- Shows thermal decomposition as a function of temperature.













Derivative Thermogram (DTG curves)- Shows the rate of decomposition over time at various temperatures. Kinetics of
thermal decomposition is modeled by Equation 1:












Activation Energy From the isoconversional method of Friedman, Equation 2:
Conclusions
National Science Foundation Competitive Grant no. 1149940.
2) Physicochemical Properties
1) Loblolly Logging Residue is the worst option for
thermochemical conversion to biofuels.

2) Hybrid Poplar, Aspen, and Loblolly Pine Chips are the
three best biomass samples for thermochemical
conversion.

3) Mass loss rate, and the temperature at which cellulose
and hemicellulose degrade increase with heating rate, in
both air and nitrogen atmospheres.

4) Rates of decomposition of Hemicellulose, Cellulose,
and Lignin varies greatly with in the 6 samples.

5) Weight loss in the temperature range 30-175C is
mainly due to water loss. The majority of thermal
decomposition occurs between 175-550C.

6) In a nitrogen atmosphere Hemicellulose degrades
within a heating range of 255-273C, Cellulose degrades
between the temperatures of 240-400C.

7) In an air atmosphere Hemicellulose degrades within a
heating range of 282-326C, Cellulose degrades between
the temperatures of 334-365C, and Lignin degrades at
temperatures of 412-500C.
Carter, Chad Lee. "Physicochemcial Properties and Thermal
Decomposition of Torrified Woody Biomass and Energy Crop."
(2012): n. pag. Print.
Fasina, Oladiran, and Brad Littlefield. "TG-FTIR Analysis of Pecan
Shells Thermal Decomposition." Fuel Processing Technology
(2012): 61-66. Print.
Jankovic, B., S. Mentus, and M. Jankovic. A Kinetic Study of the
Thermal Decomposition Process of Potassium Metabisulfite. Rep.
Journal of Physics and Chemistry of Solids, 19 Sept. 2007. Web.
Biomass has the potential to decrease dependence of
foreign oil, increase the amount of available fuel, and
reduce carbon emissions down to zero. Biomass is
generally defined as organic material composed mainly of
cellulose, hemicellulose, and lignin with trace amounts of
extractives and inorganic material. Each biomass
possesses a unique composition and hence specific
different physicochemical properties. Kinetic constants
must be determined for each individual biomass due to the
fact that no universal constants exists that can be applied
to obtain accurate modeling of kinetic pathways for
various types of biomass. Better understanding of the
specific physicochemical and thermal decomposition of
biomass can lead to more efficient and sustainable
biomass conversion through thermochemical processes.
Figure 1: Mass loss from thermal decomposition of
biomass samples under nitrogen atmosphere at
10C/min.
Figure 2: DTG pyrolysis profile for samples at 10C/min
Table 2: Proximate analysis and HHV for samples.
Sample
HHV
(kJ/g)
Ash
Content (%)
Volatile
Matter (%)
Moisture
Content (%)
Fixed
Carbon(%)
Loblolly Pine
Chips
18.79 0.97 83.44 7.14 85
Loblolly Logging
Residue
17.99 7.16 74.43 7.05 11.36
Hybrid Poplar 18.34 1.00 84.14 7.67 7.19
Switchgrass 03 18.06 1.35 85.29 7.99 5.37
Switchgrass 43 18.05 3.73 79.44 8.44 8.39
Aspen 18.52 1.32 83.98 6.54 8.16
Differential Scanning Calorimeter (DSC) Energy to thermally decompose biomass samples during pyrolysis.
Biomass
Energy Required
(MJ/kg)
Energy Required
(MJ/kg) % of Energy in Biomass
30-175C 175-550C
Loblolly Pine
Chips
1.45 0.21 8.83
Loblolly Logging
Residue
2.07 0.15 12.34
Hybrid Poplar 1.36 0.20 8.52
Switchgrass 03 2.19 0.16 13.01
Switchgrass 43 2.30 0.23 13.98
Aspen 1.67 0.17 9.92
Table 1: Energy required to thermally decompose biomass
1
0
1
2
3
H
eatF
low
(W
/g)
0 100 200 300 400 500 600
Temperature(C)
Aspen 3A.001
RebelFP11B.001
UT_SWG_03B.001
UT_SWG_43B.001
DirtyChipsPile#2A.001
D94510.001
ExoUp UniversalV4.5ATAInstruments
Figure 4: Heat flow during thermal decomposition of biomass at
10C/min in nitrogen.
Figure 3: DTG combustion profile for samples at 10C/min
Figure 1: Shimadzu TGA-50H Thermogravimetric Analyzer
0
0.02
0.04
0.06
0.08
0.1
0.12
100 200 300 400 500 600 700 800 900
M
a
s
s
L
o
s
s
R
a
t
e
(
m
i n
-1
)

Temperature (C)
Loblolly Logging Residue
Loblolly Pine Chips
Switchgrass 03
Switchgrass 43
Hybrid Poplar
Aspen
_____ Aspen
_ _ _ Loblolly Logging Residue
____ . Switch grass 03
___ _ _ Switch grass 43
___ ___ Loblolly Pine Chips
____ _ Hybrid Poplar
0
10
20
30
40
50
60
70
80
90
100
0 100 200 300 400 500 600 700 800 900
M
a
s
s
C
h
a
n
g
e
(
%
)

Temperature (C)
Switchgrass 03
Loblolly Logging Residue
Loblolly Pine Chips
Switchgrass 43
Hybrid Poplar
Aspen 3
Figure 2: Mass loss from thermal decomposition of biomass
samples under air atmosphere at 10C/min.
0
0.02
0.04
0.06
0.08
0.1
0.12
0.14
0.16
0.18
0.2
100 200 300 400 500 600 700 800 900
M
a
s
s
L
o
s
s
R
a
t
e
(
m
i n
-1
)

Temperature (C)
Hybrid Poplar
Aspen
Switchgrass 03
Loblolly Pine Chips
Switchgrass 43
Loblolly Logging Residue
0
10
20
30
40
50
60
70
80
90
100
0 100 200 300 400 500 600 700 800 900
M
a
s
s
C
h
a
n
g
e
(
%
)

Temperature (C)
Loblolly Pine Chips
Switchgrass 03
Aspen
Loblolly Logging Residue
Switchgrass 43
Hybrid Poplar
Table 1: Activation energies (kJ/mol) for constant conversion percent ()
under nitrogen atmospheres.
Sample 10% 20% 30% 40% 50% 60% 70%
Loblolly Pine Chips 64.8 147.1 180.8 147.0 155.0 162.9 166.4
Loblolly Logging
Residue 62.2 180.1 190.1 232.3 211.8 247.5 611.3
Hybrid Poplar 134.3 137.5 138.0 159.2 150.4 154.0
Switchgrass 03 38.4 129.9 111.0 91.1 83.4 105.9 111.3
Switchgrass 43 155.4 174.3 166.8 161.4 159.7 187.4
Aspen 71.9 123.7 143.7 155.3 157.0 154.2 159.4
Kinetics of thermal decomposition:
Equation 2 is derived by taking the natural log of the
kinetics of thermal decomposition, Equation 1:

Where is the fractional mass loss, defined as:

Where m
o
m
f
and m are the original, final and mass at
time t respectively.