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Biomass Combustion Study: Model Compounds of Lignin Pyrolysis

Literature Review
Sandor Rosta
November 15, 2004
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The goal of my research is to identify the chemistry of lignin is necessary to
the model compounds associated with be able to use this resource to its fullest
the pyrolysis of the biomass constituent potential.
lignin. This is being done as part of a
larger study aimed at further Biomass pyrolysis involves heating of
understanding the combustion raw biomass or organic waste material
chemistry of biomass gasification and in the absence of an oxidizer in order to
how it relates to wild land fires. extract reaction products for later
Biomass materials like wood and plants application [6]. Though lignin has been
are essentially composite materials of studied extensively, literature related to
organic polymers comprised of the pyrolysis of lignin is scarce [2].
cellulose, hemicellulose, lignin, and This is unfortunate since a major
extractive compounds like oils, and component of my work depends on
waxes. There is evidence that biomass compiling pyrolysis products from the
combustion behaves as the existing literature. Since that body of
superposition of the combustion work isn’t that extensive, I don’t have a
chemistry of these constituent parts big frame of reference to compare
[6,7,9]. results with.

Lignin is the second most abundant The studies I found that do focus
organic substance on earth [16]. Its primarily on lignin pyrolysis were done
primary biological function is to provide for a variety of reasons. Investigations
plants with strength and durability. into using lignins for alternative fuels [2]
Lignified tissures are comparable to was considered, also identifying
fiber-reinforced plastics in which the specific biomass source materials from
lignin represents the plastic binder and sampling fire emissions [11].
the cellulose the reinforcing fibers [15]. Experiments were done to determine
Lignin is a high–molecular-mass various kinetic parameters like primary
randomly cross-linked polymer and secondary reactions of lignin
consisting of an irregular array of pyrolysis products [14], and primary
differently bounded hydroxy- and pyrolysis of Kraft lignin at high heating
methoxy- substituted phenyl-propane rates [8]. And one experiment was
units [7]. The removal of lignin from conducted to validate the use of
wood is a major concern in the pyrolysis-gas chromatography-mass
chemical pulping of wood for paper spectrometry (Py-GC-MS) [5].
production, which is one of the ten
largest industrial activities in North The most significant aspect of these
America [15]. About 50 million tons of studies to me, are the tables of
chemically separated lignins are pyrolysis products formed. It is known
produced annually throughout the that the pyrolysis reaction of lignin is
world, of which about 1% is currently strongly influenced by temperature,
sold [15]. So a further understanding of heating rate, and the nature of the
carrier gas. Also, the nature of lignin, unclear.
its composition, and various functional
groups have significant effects on the The string of continuity that runs
lignin, conversion, and product yields through most of the experiments in the
[2]. So, since the conditions under literature is the method of species
which these experiments have been detection. Pyrolysis thermally
done are different, comparing the degrades polymers into small
results from each one and drawing fragments which are separated by gas
conclusions about the most significant chromatography and identified with
products is a non-trivial task. mass spectrometry [5]. [2,5,8,12,15,17].
Thermogravimetric analysis is also
Another important factor in these performed [2]. Since the literature
pyrolysis experiments is the type of results were somewhat limited to the
reactor used, and under what topic directly related to my area, I
conditions. A fixed-bed reactor was broadened my search a little to include
used in [2] under and Kraft Lignin was related topics. The methods used in [3]
heated from 298-1073 K. In [5] all and [10] are very similar to methods
analyses were performed using a CDS used to study lignin pyrolysis, but they
Pyroprobe 1000 heated filament are focused on the cellulose
pyrolyzer at 200 C and 290 C. Another compound. The represented data
Pyroprobe 1000 was used in [8] and doesn’t explicitly apply to my study, but
heated up to 1000 C. In [11], the insight can be gained from their
combustion experiments were carried experimental methods. Also included
out in a traditional brick fireplace in an are general biomass pyrolysis studies
older single-family home. No [4,6,7,9,12]. These studies consider all
temperature was given about the fire, components of biomass including
but the instrument analysis reports a lignin. The problem with their reports is
temperature programming of injecting that they don’t account for all the
sample at 65 C and then heating at 10 species that each component breaks
C/min for 21 min and then holding at into, the just lump all the effects into
275 C for 21 minutes. In [13] pyrolysis lignin, or hemicellulose. They are
was performed with ferromagnetic useful though as precedence for what
wires having a Curie temperature of results should be obtained when the
510 C, held at 50C for 3 min, and time comes to run simulations on the
programmed to 250 C at a rate of 3 model compounds that I need to
C/min. In [14], stainless steel microtube determine.
bomb under heating conditions that are
1. Brown, AL; Hames, BR; Daily, JW; et al. “Chemical analysis of solids and
pyrolytic vapors from wildland trees” ENERGY & FUELS, 17, 1022-1027 (2003)

2. Ferdous, D; Dalai, AK; Bej, SK; et al. Pyrolysis of lignins: Experimental and
kinetics studies,” ENERGY & FUELS, 16 (6): 1405-1412 (2002)

3. Brown, AL; Dayton, DC; Daily, JW, “A study of cellulose pyrolysis chemistry
and global kinetics at high heating rates,” ENERGY & FUELS, 15 1286-1294
(2001)

4. Zhou, XY; Mahalingam, S, “Evaluation of reduced mechanism for modeling


combustion of pyrolysis gas in wildland fire” COMBUSTION SCIENCE AND
TECHNOLOGY, 171, 39-70 (2001)

5. Bocchini, P; Galletti, GC; Camarero, S; et al. “Absolute quantitation of lignin


pyrolysis products using an internal standard,” JOURNAL OF
CHROMATOGRAPHY A, 773 (1-2): 227-232 (1997)

6. Miller, RS; Bellan, J, “A generalized biomass pyrolysis model based on


superimposed cellulose, hemicellulose and lignin kinetics,” COMBUSTION
SCIENCE AND TECHNOLOGY, 126 97-137 (1997)

7. Alen, R; Kuoppala, E; Oesch, P, “Formation of the main degradation


compound groups from wood and its components during pyrolysis,” JOURNAL
OF ANALYTICAL AND APPLIED PYROLYSIS, 36, 137-148 (1996)

8. Caballero, JA; Font, R; Marcilla, A, “Study of primary pyrolysis of Kraft lignin at


high heating rates: yields and kinetics,” JOURNAL OF ANALYTICAL AND
APPLIED PYROLYSIS, 36, 159-178 (1996)

9. Raveendran, K; Ganesh, A; Khilar, KC, “Pyrolysis characteristics of biomass


and biomass components,” FUEL, 75, 987-998 (1996)

10. Antal, MJ; Varhegyi, G, “Cellulose Pyrolysis Kinetics - The Current State
Knowledge, “INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH, 34 703-
717 (1995)

11. Simoneit, BRT; Rogge, WF; Mazurek, MA; et al. “Lignin Pyrolysis Products,
Lignans, and Resin Acids as Specific Tracers of Plant Classes in Emissions from
Biomass Combustion,” ENVIRONMENTAL SCIENCE & TECHNOLOGY, 27
2533-2541 (1993)

12. Evans, RJ; Milne, TA, “Molecular Characterization of the Pyrolysis of


Biomass .1. Fundamentals,” ENERGY & FUELS, 1 123-137 (1987)

13. Saizjimenez, C; Deleeuw, JW, “Lignin Pyrolysis Products - Their Structures


and Their Significance as Biomarkers,” ORGANIC GEOCHEMISTRY, 10 869-876
(1986)

14. Jegers, HE; Klein, MT, “Primary and Secondary Lignin Pyrolysis Reaction
Pathways,” INDUSTRIAL & ENGINEERING CHEMISTRY PROCESS DESIGN
AND DEVELOPMENT, 24 173-183 (1985).

15. B. L. Browning, “The Chemistry of Wood”, Interscience Publishers, London,


(1963).

16. Glasser W. G., Northey, R. A, Schultz, T. P., “Lignin: Historical, Biological, and
Materials Perspectives”, ACS Symposium Series 742, American Chemical
Society, Washington D. C. (2000)