Journal of Analytical and Applied Pyrolysis, 13 (1988) 221-231 221

Elsevier Science Publishers B.V., Amsterdam - Printed in The Netherlands

FIRST CHEMICAL EVENTS IN PYROLYSIS OF WOOD

WILLIAM F. DeGROOT, WEI-PING PAN l, M. DALILUR RAHMAN

and GEOFFREY N. RICHARDS *

Wood Chemistry Laboratory University of Montana, Missoula, MT 59812 (U.S.A.)

(Received July 13th, 1987; accepted September 21st, 1987)

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.

Cellulose; Fourier transform infrared spectroscopy; hemicellulose; lignin; pyrolysis; wood.

INTRODUCTION

The major recent trends in studies of pyrolysis of lignocellulosic materials,

usually with the object of maximizing yields of pyrolytic oils, are towards
more rapid pyrolysis and to some extent towards higher temperatures [l].
We have been concerned with mechanisms of pyrolysis at low temperature
as part of an on-going study of smoldering combustion of lignocellulosics,
which involves conditions under which both pyrolysis and combustion

* Present address: Department of Chemistry, Western Kentucky University, Bowling Green,

KY 42101, U.S.A.

0165-2370/88/$03.50 0 1988 Elsevier Science Publishers B.V.

222

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

The pyrolysis was studied by combined TG and FTIR (TG-FTIR). The

TG system was based on a Cahn R-1000 electrobalance with a resistively
coated temperature-programmed furnace surrounding the sample pan. Tem-
perature was measured by a thermocouple positioned 1 mm below the pan.
The TG system was interfaced to a laboratory microcomputer system for
data acquisition and for control of the temperature programme. This system
consisted of a Tektronix 4051 microcomputer with a ROM-based A/D
converter and a real time clock (Trans-Era) and a Hewlett-Packard Model
6002A programmable power supply for TG furnace control. The gas outlet
of the TG system was coupled to the FTIR system by a 1 m x 1 mm I.D.
PTFE tube which was heated to 100C. The effluent from the connecting
tube entered a 100 mm X 10 mm I.D. heated gas cell in a Nicolet MX-1
FTIR system.
Black cottonwood (Populus trichocarpa) sapwood, air-dried, was Wiley-
milled repeatedly to - 80 mesh and stored at - 20 o C until required. In the
thermal regime giving the results shown in Fig. 4, an 1%mg sample of wood
was heated under nitrogen (30 ml/mm) from 30 to 120 o C at 10 o C/mm,
held at 120C for 10 min, then heated to 250C at 10 C/mm and held at
250 C. The times in Fig. 4 are given from the start of this regime. FTIR
spectra were taken at 3-min intervals.
Calibration of FTIR spectra was carried out using wavelengths and
compounds shown in Table 1. For the four cases where the product was a
liquid at room temperature the calibration was carried out by placing a
sample of the pure liquid in a covered aluminum pan on the thermal balance
in air at 30 ml/mm at several appropriate constant temperatures, and IR
spectroscopy on the evolved vapor normally showed constant reading after
about 10 min. When constancy in rate of weight loss and spectrum were
achieved, the IR absorbance was related to the concentration of the vapor in
the gas stream, and in all cases this relationship was linear over the range of
temperatures used (including zero values). The IR bands and temperatures
used in each case are detailed in Table 1. Where a range of wavenumbers is
 223

TABLE 1
Infrared absorbances used to quantify the first volatile products from pyrolysis of wood and
conditions used for calibration

Compound Wavenumber Temperature Rate of weight loss

(cm-) (C) @S/mm)
Carbon dioxide 2240-2400 -
Acetic acid 1140-1230 23,30 16, 32
Water 1653 23,30 17,61
Formic acid 1105 23,26 12.6, 30.0
Methanol 1032 23,30 42.6, 137

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.

RESULTS AND DISCUSSION

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
--

60 120 180 min

Fig. 1. Weight loss of cottonwood by pyrolysis at 250 C under nitrogen.

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.

The most likely source of carbon dioxide at low temperature is the

decarboxylation of uranic acids in the hemicelluloses and pectins. The
amount of carbon dioxide generated in the first 80 min of heating is ca. 0.37
mmol/g of wood, calculated from Fig. 4. The uranic acid content of the
wood, presumed to be predominantly 4-0-methylglucuronic acid (MGA)
and galacturonic acid, is ca. 0.26 mmol/g of wood, calculated from Table 3.
The form of the carbon dioxide curve in Fig. 4 shows continuing production
of carbon dioxide at a lower level into the steady-state pyrolysis region. It
is evident therefore that the initial wave of rapidly produced carbon dioxide
corresponds quite well to the uranic acid content. It is concluded therefore
that the initial low-temperature peak in carbon dioxide formation in Fig. 4
corresponds to decarboxylation of the uranic acid components, and in
confirmation of this, the uranic acid analysis of the wood heated for 50 rnin
was found to have fallen to 1.7% from the original 4.9% (Table 3).

TABLE 2
Yield of volatile products by infrared detection as percentage of total weight loss; cot-
tonwood at 250 C in nitrogen

Compound Percentage of total weight loss

Methanol 3.5 3.7 3.8 4.4
Formic acid 5.0 6.4 8.2 7.0
Acetic acid 7.5 15.5 19.0 23.0
Carbon dioxide 10.5 9.2 12.0 13.2
Water 21.5 18.3 16.0 13.2

Total 47.5 53.1 59.0 60.8

Time at 250 o C (min) 11 23 40 58

Total weigth loss (X) 5.5 8.0 11.0 12.5
 227

TABLE 3
Analyses of cottonwood after heating at 250 o C under nitrogen

Compound Percentage dry weight

(anbydroglycoses) Original dry wood After heating for 50 min
Rhamnose 0.2 0
Arabinose 0.5 Trace
Xylose 15.8 12.3
Mannose 3.0 2.4
Glucose 51.3 51.3
Uranic acid 4.9 1.7
Total carbohydrate 75.7 67.7
Vanillin 2.7 1.8
Syringaldehyde 5.7 2.2

Weight loss (W) 0 11.9

The amount of methanol produced in the first waves (up to 60 min

heating) was ca. 0.13 mmol/g of wood from Fig. 4 and there are two
possible sources, viz. decomposition of MGA units of the hemicelluloses or
degradation of syringyl and guaiacyl units in lignin. The MGA units are
likely to comprise about half of the total uranic acid content, the balance
being due to pectic substances. Earlier studies in this laboratory [4] of the
total cell wall uranic acid content of cottonwood sapwood, after removal of
pectic substances by acid washing, indicate a MGA content of 0.087
mmol/g of wood. On this basis, the maximum yield of methanol possible
from pyrolysis of hemicellulose MGA units would have been ca. 0.06
mmol/g of wood (Table 3 shows that about two thirds of the uranic acids
are lost at this stage). A very small amount of methanol may also be derived
from methyl ester groups in pectic substances. We conclude therefore that at
least part of the early waves of methanol formation on heating is derived
from lignin. In confirmation of this conclusion, wood heated for 50 min
(Table 3) gave much reduced yields of vanillin (from 2.7 to 1.8%) and
syringaldehyde (from 5.7 to 2.2%) on nitrobenzene oxidation. The fate of the
lignin units which degrade at 250C to yield methanol is not known.
Another recent study of primary pyrolysis products of lignin by direct mass
spectrometry [5] has shown three waves of methanol formation, with the first
wave coinciding with formation of formaldehyde and conifer-y1 alcohol. In
this earlier work, however, the pyrolysis was carried out at 800-900C. We
have also observed a third wave of methanol production from cottonwood at
higher temperatures (350C) and will report on this study at a later date.
We found no evidence of formaldehyde formation at 250C and although
this is an early product of high-temperature pyrolysis, it is not a significant
product at lower temperature. Coniferyl alcohol would not have been
228

detected in our system because it is not sufficiently volatile, but it should be

noted that this product retains its methoxyl group, and therefore its forma-
tion does not represent the source of the methanol from lignin.
The formation of methanol by pyrolysis of lignin is in contrast to some
recent studies of pyrolysis of phenoxymethyl groups in coals and related
model compounds. Thus Chu et al. [6] concluded that the phenoxymethyl
groups in some methylated coals pyrolyse to produce mainly methane and
carbon monoxide. Also, Vuori [7] has studied the pyrolysis of several
hydroxymethoxybenzenes and observed the same two procucts leading him
to the conclusion that the pyrolyses occur by homolytic mechanisms. In
these examples from coal chemistry the phenoxymethyl groups are very
similar to those in lignin, and similar pyrolysis mechanisms might have been
anticipated. A major difference in the two systems, however, is the forma-
tion of much larger amounts of water from the polysaccharides in the
pyrolysis of wood, and in these circumstances it is more likely that a
heterolytic hydrolysis mechanism may account for the formation of methanol
from the phenoxymethyl groups of lignin.
The formation of acetic acid shown in Fig. 4 commenced considerably
after carbon dioxide and methanol and was still continuing at a significant
level at the end of the experiment. The obvious source of this acid is the
hydrolysis of the acetyl ester groups of the 4-0-methylglucuronoxylans,
utilizing water which is abundantly produced in other pyrolytic reactions of
the polysaccharides. In hardwoods the ratio of acetyl groups to xylose units
is typically about one acetyl to seven xyloses [S]. Using this ratio and the
xylose value from Table 3 we derived a maximum possible acetic acid yield
of 0.84 mmol/g of wood. The observed yield of acetic acid after 80 min
heating derived from Fig. 4 is ca. 0.33 mmol/g of wood. We conclude
therefore that the acetyl groups of the hemicelluloses pyrolyze relatively
slowly at 250 o C and that a large proportion survives prolonged heating at
this temperature. It may be noted in passing that the partial acetylation of
cellulose has been utilized to improve thermal stability [9].
The production of formic acid from the heated wood commenced at a low
level simultaneously with carbon dioxide and methanol from the earliest
stages of pyrolysis and continued at a significant level throughout the
experiment. The mechanisms leading to production of this acid are un-
known. We speculate that it is more likely to be derived from pyrolysis of
hemicelluloses than from lignin or (at 250 o C) from cellulose, and there may
be parallels with the formation of high yields of the same product in
anaerobic alkaline degradation of cellulose, also by unknown mechanisms.
Water is the major product of pyrolysis. After 80 min of heating the
amount indicated by Fig. 4 is ca. 1.4 mmol/g of wood. At that stage Fig. 1
indicates that the total weight loss of the wood is 127 mg/g of wood. The
results discussed above suggest that most of the products of the pyrolysis
have originated from decomposition of hemicelluloses and if we assume an
 229

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

Decarboxylation of uranic acid

PECTIC SUBSTANCES _ Loss of arabinose
HEMICELLULOSES Decrease in xylose
Loss of acetyl groups

WOOD Chain scission

CELLULOSE _____+ Transglycosylation
25O"C/N2 Small decrease in glucose

Loss of some methanol

LIGNIN _____,
IOther degradation?

Fig. 5. First chemical events in pyrolysis of wood.

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.

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