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"Biomass Pyrolysis of Extractive Compounds "
Mark Jarvis
Introduction to Research
MCEN 5208
11/15/04
Modeling of wild fires is complicated by the heterogeneity of the chemical and
morphological properties of the fuel. To date, the most advanced models are from
Morvan and coworkers. They expanded on early models simplistic assumption that
radiation is the primary mode of fire spread (Rothermal). They state that while this is
important, it is not the only factor in fire propagation. In effort to develop a more
complete model that accounts for more complex fire behavior than a single flame front
moving through a fuel bed, they began to incorporate reaction mechanisms for single step
pyrolysis and combustion of a fuel bed comprised of pine needle litter. Their detailed
physical approach covered radiation heat transfer, and convective heat transfer due to the
turbulent fluidic conditions generated by combustion, but the makeup of the fuel bed was
based on average kinetic data empirically obtained from thermogravimetric analysis
(TGA) of forest fuel (Morvan et al 2001&2004). While this does provide fairly good
input to model for water release, char formation and primary pyrolysis, more detailed
chemistry is needed to understand extreme fire behaviors such as flames jumping from
tree to tree, tree to ground, etc. Since it is computationally expensive to include every
possible chemical compound present in forest fuel, a careful analysis of what parts of the
fuel contribute most to fire spread are in order.
In this region of the United States the fuel is primarily from softwood (i.e.
coniferous) plants, so the chemical makeup of these of particular interest. Wood is a
heterogeneous material generally divided into two groups: high molecular weight
structural components (cellulose, hemicellulose, and lignin) and low molecular weight,
nonstructural components (extractives and inorganics). Extractives are defined as those
compounds that can be extracted from wood with neutral solvents. Generally, these
comprise only about 15% of the weight of dry wood but are of great industrial and
scientific interest due to the wide range of chemical species, and hence properties, present
in this fraction. Of special interest to wild fire behavior is the class of volatile
extractives, commonly called essential oils. These components include cyclic
hydrocarbons (terpenes and terpenoids), aliphatic hydrocarbons, phenols, alcohols,
ethers, aldehydes and lactones (Hon and Shiraishi, 2000). Turpentine, the essential oil of
pines, consists mainly of monoterpenes. Much of the research on extractives has been
motivated by a need in the biofuel industry to eliminate such compounds from potential
feedstocks, but the characterization techniques and quantification data are useful for
wildland fire modeling. However, little attention was paid to the detailed pyrolysis
chemistry of the extractive components. The process of pyrolysis (heating a compound
till it breaks apart), which is an important step in biomass fuel extraction, is at the heart of
wild fire spread because the fuel particles must break apart before a combustion reaction
with oxygen can occur. It has been shown that extractive compounds are among the first
to be released during heating of biomass (Oasmaa et al 2002). Not surprisingly, the
fraction of extractive compounds in bark is four to five times that of bark free wood, and
needles have seven to eight times that of bark free wood (Pappa et al 2000). The
predominant volatile extractive in softwoods has been shown to be monoterpenes
(C10H16), and other terpenoids (Back et al 2000). Other researches have reported similar
findings from indepth chemical analysis of leaves, needles, and barks. Specifically,
Brown et al 2003 separated samples collected from western United States forests into
whole wood, bark, leaves (&needles), and branches that were then heated to produce
pyrolysis gases which were then analyzed by molecular beam mass spectroscopy
(MBMS). The chemical composition determined from these methods was then combined
with their results from wet chemical analysis to observe how the chemical composition
differed before and after pyrolysis. The pyrolytic data showed significant correlations
between extractive content and the leaves, needles, and bark (LNB). Combined with the
wet chemistry data showed a strong linear relationship between extractive content and the
LNB fraction. The mass spectroscopy peaks of the LNB point to terpenic compounds
and is in agreement with other research. In thermal degradation experiments with needles
from Pinus halepensis, Statheropoulos et al 1997 found that at 200300C low volatility
extractive constituents were released from the sample. They further characterized the
volatile species with differential ion mass spectroscopy (DIMS) and found that at under
400C pine needle pyrolysis produces various volatile organic molecules, many of which
are terpenoids. Challinor J.M. 1996 also employed GC/MS techniques to characterize the
origin of wood extractives by pyrolysisgas chromatography. In particular, the author
examines several extractive species found in nine different pine tree species, a major
component of western forest biomass. Ba et al, 2004 characterized the biooils found
after the vacuum pyrolysis of softwood bark. The authors identified via
thermogravimetric (TG) and gas chromatography (GC) analysis, the chemical
composition of the water soluble and waterinsoluble fractions of bark. Gronli et al have
measured the thermogravimetric curves for both hard and soft woods. They propose
devolatilization mechanisms consisting of three parallel reactions and two further
reactions and their respective activation energies for biomass extractives.
In conclusion, there is much evidence in the literature implicating extractive
compounds as an important factor in fire propagation. It has also been illustrated here
that a particular class of volatile extractives, the terpenoids, represents compounds that
require more study to elucidate their reaction chemistry in a forest fire situation. Since the
terpenes are so volatile, they play a large part in atmospheric chemistry, and hence much
of the knowledge concerning their gasphase reactions has been done in this field
(Aschmann et al 2002, and Paulson et al 1998).
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