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ABSTRACT
Wood has been heated at 250 o C on a thermal balance and the evolved gases have been
analyzed by Fourier transform infrared spectroscopy (FTIR). The heated wood has been
analyzed for glycoses, uranic acids and by nitrobenzene oxidation to vanillin and syringalde-
hyde. About 60% of the weight loss is accounted for by five compounds, which are the only
products detected in the gases by FTIR. These products are water, carbon dioxide, methanol,
acetic acid and formic acid. By relating the rates of formation of these compounds to weight
loss, the following major conclusions are reached regarding the first chemical events in
pyrolysis of wood. Uranic acids in the hemicelluloses and pectic substances decompose very
readily to yield carbon dioxide, water, char (or char precursors) and perhaps some methanol.
This decomposition may lead to further pyrolysis of the xylose units to which the uranic acids
are attached in the hemicelluloses. Acetyl ester groups in the hemicelluloses are much more
resistant to pyrolysis, but are released slowly as acetic acid. A small proportion of the
potential methanol product is released very readily and at least part of this product is derived
from lignin. Formic acid is released at a slow and continuing rate at 250 o C by unknown
mechanisms and is probably derived from degradation of hemicelluloses.
INTRODUCTION
reactions occur [2]. This paper describes the investigation of the first volatile
products of pyrolysis of a wood under conditions which we believe are of
relevance in smoldering combustion, and it is anticipated that the pyrolysis
pathways which may be deduced from such products will in some instances
also be relevant to the first stages of rapid and high-temperature pyrolysis.
The major experimental technique has been to couple thermogravimetry
(TG) to vapor phase Fourier transform infrared spectrometry (FTIR) in
order to relate the qualitative and quantitative yields of volatile products to
weight loss in the pyrolyzing wood.
EXPERIMENTAL
TABLE 1
Infrared absorbances used to quantify the first volatile products from pyrolysis of wood and
conditions used for calibration
specified, the concentration was related to the integrated peak area between
these values; where a single wavenumber is specified, this represents a
Q-band and the peak height was used for calibration. In the case of water,
the height of a major peak at 1653 cm-i in the spectrum fine structure was
used. For calibration of carbon dioxide the natural atmospheric concentra-
tion of 0.033% (v/v) was used, and for carbon monoxide a commercial
reference mixture of 0.930% carbon dioxide and 0.953% carbon monoxide in
nitrogen was then used to derive a relative IR response with respect to
carbon dioxide.
Cottonwood was selected for this study because it has been the subject of
previous chemical and thermal studies in this laboratory [3]. In selecting the
pyrolysis temperature it was necessary to compromise between the need to
keep the temperature as low as possible, so as to limit reactions to the first
steps in pyrolysis, and the need to produce measurable concentrations of
pyrolysis products in the gas stream. The latter parameter is related to the
flow-rate of the inert gas (nitrogen) over the sample, but it was evident that
too great a reduction in this flow could have two deleterious effects. Firstly
there would be a danger of secondary pyrolysis due to slow removal of
primary pyrolysis products from the heated zone and secondly the greater
the time lag between pyrolysis and FTIR measurement, the greater the
possibility of secondary reaction of primary products in the gas phase. A gas
flow-rate of 30 ml/min was set as reasonable compromise of the above
events after preliminary experiments had shown that the TG curves were
insensitive to flow-rates down to this value.
Fig. 1 shows the rate of weight loss at 250 C. Pyrolysis occurs at
significant rates at much lower temperatures, but the rate of production of
volatiles was too low for adequate accuracy in the FTIR. The general form
of the curve suggests the occurrence of initial rapid weight loss followed by a
224
OC/min 25OC
--
continuing steady state rate of weight loss. In order to reveal the first
chemical events in the pyrolysis our investigation was concentrated on the
first rapid weight loss phase, i.e. up to about 1 h at 250 C. The FTIR
spectra given by the effluent gas after 20 min at 250 OC are shown in Figs. 2
and 3, together with spectra of methanol, acetic acid and formic acid. The
latter three compounds, together with water and carbon dioxide, were the
only compounds identified in the spectra from wood under these conditions
and it was concluded that no other JR-absorbing materials were present in
100.0
WOOD 2~~/150mln
925
I I
METHANOL
I
30 4400 3250 2000 1400 000
WAVENUMBER
Fig. 2. Spectra of gases evolved from cottonw~ at 250 * C.
225
97.5-
-0 m
-- 0
w e- _
I
ii
2 FORMIC ACID
F
5
2950.
2
I-
<
a METHANOL
92.5-
90.0 I I
1300 1200 1100 1000 900 800 700
WAVENUMBER
Fig. 3. Spectra of gases evolved from cottonwood at 250 o C against authentic formic acid and
methanol.
significant amount in the pyrolysis gases reaching the IR cell. The system
was calibrated for the five volatile pyrolysis products, as indicated in the
experimental section and shown in Table 1 using the height of the Q-bands
for methanol and formic acid, the height of a selected single frequency for
water and integrated areas under major peaks for carbon dioxide and acetic
acid.
Using the above calibrations and pyrolysis conditions the yields of the
five volatile products were followed by spectra taken at 3-n-A intervals from
wood heated at 250 C in nitrogen, and results are shown in Fig. 4
(mol/min). In this figure the wood reaches 250 o C at 32 min (see Experi-
mental section) and evidently much pyrolysis is already occurring by that
time. Evidently the dominant product on both a weight and molar basis is
water, peaking soon after the sample reaches 250 C. It is significant,
however, that both carbon dioxide and methanol peak at about the time the
sample reaches 250 C and both of these products appear to be formed in
the first pyrolysis reactions of the wood. In Table 2 the yields of the five
volatile products detected by FTIR are compared with the weight loss in the
wood and it is evident that 40-50s of the total volatile material from the
wood was condensed before reaching the FTIR cell.
Fig. 4. Volatile products from cottonwood at 250 C under nitrogen.
TABLE 2
Yield of volatile products by infrared detection as percentage of total weight loss; cot-
tonwood at 250 C in nitrogen
TABLE 3
Analyses of cottonwood after heating at 250 o C under nitrogen
average monomer weight of ca. 150 for these polysaccharides, then 127
mg/g of weight loss corresponds to ca. 0.85 mm01 of hemicellulose mono-
mer degraded per g of wood. On this admittedly very approximate basis, the
pyrolysis of an average monomer unit of hemicellulose yields ca. 1.6 mol of
water, and there is no doubt that the major part of the balance of products
from the pyrolyzed units is converted ultimately to char.
The fate of the glycose units in general is shown in Table 3. The glycose
analyses were carried out by hydrolysis, initially with 72% sulfuric acid,
followed by reduction to alditols, acetylation and gas chromatography as
described earlier, using myo inositol added to the wood as internal standard
before hydrolysis and correcting for acid degradation of glycoses [8]. Uranic
acids were determined on the same hydrolysates using the 3-hydroxydi-
phenyl reagent [lo]. The heated wood samples were resistant to complete
hydrolysis by the normal procedure, presumably because of hornification
as a result of the heating [ll]. These samples were reactivated by keeping
under a small amount of water (vacuum-degassed) at room temperature for
one day, then freeze-dried before hydrolysis. The accuracy of the glycose
analytical procedure is not high, but several generalizations can be drawn.
The trace components rhamnose (from pectic substances) and arabinose
(from hemicelluloses and pectic substances) are completely decomposed
after 50 mm heating. The arabinose is present predominantly as L-
arabinofuranoside units; these are the most acid-sensitive glycosidic linkages
present in the wood and it is not surprising that they are also the most
sensitive to pyrolysis. The mannose is present in the wood as glucomannan
and is apparently relatively resistant to pyrolysis. The greatest change in the
major glycose components occurs with xylose (15.8-12.3%). Although the
observed glucose content is the same in the heated wood as in the original
wood, the 11.9% concurrent weight loss translates to an actual loss of 12% of
the total glucose units originally present, compared with an actual loss of
32% of the total xylose units originally present. This difference is rather
surprising since the xylan and glucan chains are chemically so similar. The
relative rate constants for acid hydrolysis (which may be relevant to relative
ease of pyrolysis) of B-D-xylopyranosides and P-D-glucopyranosides are
4.8 : 1 [12] and although this difference does suggest a higher rate of
pyrolysis of the former, the observed difference between loss of xylose and
loss of glucose is greater than expected. A possible explanation of this effect,
however, is associated with the facile pyrolysis of the uranic acid units,
many of which are glycosidically attached to the 2-position of xylose units in
the hemicelluloses. We have concluded above that the decarboxylation of
these uranic acids is one of the first chemical events in pyrolysis and it is
likely that after decarboxylation the subsequent decomposition of the uranic
acid residue will influence the reactivity of the xylose unit to which it is
attached. Similar predictions can be made with respect to the effects of the
facile pyrolysis of L-arabinofuranoside units on the reactivity of the xylose
230
units to which they are attached. This type of speculation leads to the
suggestion that the xylose units which are lost in the mild pyrolysis are those
at the branch points of the xylan chain.
The relatively small loss of glucose units in the heated wood does not
mean that most of the cellulose remains unchanged under the above heating
regime. Earlier research in this laboratory [13] has indicated that the
molecular weight of the cellulose is likely to fall to less than half after 50
min heating due to pyrolysis scission reactions in the amorphous regions,
and it is probable that some subsequent reformation of glucosidic linkages
results in transglycosylation. The glucose in the heated wood therefore is
probably not entirely present as 1,4-/3-o-glucopyranosyl units, but conver-
sion of glucose to volatile products under our conditions is certainly very
small.
The general conclusions regarding the predominant first chemical events
in pyrolysis of wood are summarized in Fig. 5.
ACKNOWLEDGEMENT
The work was partly funded by a grant from the Center for Fire
Research, National Bureau of Standards.
REFERENCES
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