Torrefaction Reaction Kinetics of Southern Pine Wood

Gerald Lindo, Sudhagar Mani & Jim Kastner

Department of Biological and Agricultural Engineering The University of Georgia, Athens, GA 30602. web: www.biorefinery.uga.edu

Introduction
Torrefaction, a relatively mild pyrolysis reaction under anoxic condition, is of interest in the thermo-chemical conversion of biomass to energy and fuels because of its favorable effects on biomass energy density, feedstock reactivity, and possible elimination of tar precursors. It is a solid state hydrolysis of hemicellulose in the biomass using thermal treatment ay low temperature. This process produces a solid product (torrefied biomass) that has superior fuel quality for any thermo-chemical conversion processes into fuels and power. power The main objective of this study was to determine the torrefaction reaction kinetics of southern pine wood using Thermal Gravimetric with Mass Spectrometry (TG-MS) analyzer. In this study, a kinetic model of biomass torrefaction was developed in the temperature range of 200-300C and kinetic mass-loss parameters for the torrefaction of southern pine wood were presented. presented A simple hemi-cellulose hemi cellulose decay model was proposed to predict the torrefaction reaction kinetics. The torrefaction kinetic data will be critical to understand the torrefaction process, to design, develop and simulate the torrefaction reactors commercial scale applications and to investigate the downstream thermo-chemical conversion processes.

Torrefaction Model Development, Implementation and Analysis

Material & Methods Clean white pine chips ground to 0.25 mm mesh Powder samples were used at the TG-MS to target temperature at 10o C/min under nitrogen environment. Samples were held at target temperature for 3 h to obtain mass loss data. Mass loss data was used to study the torrefaction reaction kinetics.
Torrefaction Reaction

k1
Hemicellulose(a)

Activated Intermediate(b)

k2

Solid products(c)

kv2 kv1
Volatileproducts
-t(k 1-kv 1) a(t) = mho*e

k1 b(t)= mho* e-t(k2-kv2 ) e-t(k1-kv1) k2 k1+ kv 1+ kv2 k1k2 k1 k2 kv 1 kv2 (k1 kv 1)e-t(k2-kv2 ) + ( k2 kv2)e-t(k1-kv1) c(t)= mho* (k2 + kv2)(k1 kv1`)(k2 k1+ kv1+ kv2))

))
0.0 2.2E03 1.8E03 2.0

30 3.0 2.0

Arrheniusplotfork1

4.6 46 1.8E03 4.8

Arrheniusplotfork2
2.0E03 2.2E03

00 0.0 1.8E03 1.0

Arrheniusp plotforkv1
2.0E03

Arrheniusplotforkv2
2.0E03 2.2E03

ln(kv1)

ln(k2)

1.0 0.0 1.8E03 1.0 2.0 2.0E03 2.2E03

ln(kv2) 1/T(K1)

ln(k1)

4.0 6.0 8.0 10.0

2.0 3.0 4.0

5.0

1/T(K1)

5.2

1/T(K1)

1/T(K1)

Objectives
To postulate a model for mass loss during the torrefaction of pine wood and obtain relevant kinetic parameters. To study the effect of torrefaction at various holding temperatures on mass loss kinetics and off-gas composition in downstream thermal conversion processes.

Di i Distinct non-Arrhenius A h i behavior b h i of f k values l were observed. b d This Thi differs diff f from previous i reports in i literature. li

Downstream Effects of Torrefaction

Integrating torrefaction with combustion, gasification & pyrolysis Preliminary study
remainingfra action 1.2 1 0.8 0.6 0.4 0.2 0

Comparisonofcombustionoftorrefied biomass,untreatedbiomassandcoal
t225 t235 t250 t260 t275 t285 t300 rawpine coal 0 500 1000 1500

Pine powder samples were initially torrefied at various temperatures and the samples were directly combusted (with air), gasified (with limited oxygen) and pyrolyzed (with nitrogen) The off nitrogen). off-gas gas emission from each conversion processes were monitored using MS with a selective ion monitoring approach. The analyzed results indicated that no effect on mass loss kinetics data during combustion, gasification, pyrolysis processes were observed. Combustion behavior of torrefied biomass was compared with low sulfur coal. Torrefied and raw pine powder samples were highly reactive compared to coal samples. MS analysis data indicated that significant reduction off-gas concentrations of acetol in gasification and both acetol and acetic acid in pyrolysis was observed.

Acknowledgement
The authors gratefully acknowledge the financial support for this project from Traditional Industries Program (TIP3) of State of Georgia, USA & Office of Vice Precedence Research at UGA.

Time

For more Information, contact:

Dr. Sudhagar Mani, UGA Ph: (706) 542-2358; email: smani@engr.uga.edu

A kinetic model for mass loss during the torrefaction of southern pine was developed. It was found that the mass loss cannot be adequately described as a single step process, and that the kinetic parameters do not follow a typical Arrhenius relationship. More detailed study of the chemical reaction and mass transfer events that occur during torrefaction is required to further understand this process. This will allow for model validation and justification via investigation of the intermediate stages of torrefaction; and will further our understanding of the effects of torrefaction on the downstream conversion processes. Detailed HPLC and NMR studies on torrefied material are forthcoming. This research poster is presented in the 2009 Bioenergy Engineering Conference held in Bellevue, Washington, October 11-14, 2009.

Conclusions and Future Research