Pergamon

PI I : 80008-6223( 98)00082-7
Carbon Vol. 36, No. 7-8, pp. 1085-1097, 1998
0 1998 Elsevier Science Ltd
Printed in Great Britain. All rights reserved
0008-6223/98 $19.00 + 0.00
ACTIVATED CARBONS FROM YELLOW POPLAR AND
WHITE OAK BY H,PO, ACTIVATION
MARIT J AGTOYEN,* and FRANK DERBYSHIRE
Center for Applied Energy Research, 2540 Research Park Drive, Lexington, KY 4051 I-8410, U.S.A.
(Received 28 October 1997; accepted in revised form 4 December 1997)
Abstract-Results are presented from continuing investigations of the phosphoric acid activation of
hardwoods. Earlier work with white oak has been extended to include yellow poplar. It is found that
the same general chemical and physical changes occur with both precursors. A discussion is presented
on the possible mechanisms of phosphoric acid activation, drawing upon extensive research on the use
of phosphorous compounds as fire retardants for wood and cellulose. Phosphoric acid appears to
function both as an acid catalyst to promote bond cleavage reactions and the formation of crosslinks
via processes such as cyclization, and condensation, and to combine with organic species to form
phosphate and polyphosphate bridges that connect and crosslink biopolymer fragments. The addition
or insertion of phosphate groups drives a process of dilation that, after removal of the acid, leaves the
matrix in an expanded state with an accessible pore structure. It is considered that activation of the
amorphous polymers produces mostly micropores, while activation of crystalline cellulose produces a
mixture of pore sizes. The different response of crystalline cellulose is attributed to a much greater
potential for structural expansion than is possible with the amorphous polymers due, among other
factors, to its higher density and its chemical structure that allows for a more extensive degree of
combination with phosphoric acid, and hence bulking of the cell walls. The pore size distribution
obtained from crystalline cellulose can be altered by increasing the HTT and/or the ratio of acid to
precursor such that, eventually, the structure is dominantly mesoporous. At temperatures above 45OC,
a secondary contraction of the structure occurs when the phosphate linkages become thermally unstable.
The reduction in crosslink density allows the growth and alignment of polyaromatic clusters, producing
a more densely packed and less porous structure. 0 1998 Elsevier Science Ltd. All rights reserved.
Key Words-A. Activated carbon, D. reaction mechanisms.
1. INTRODUCTION
In earlier publications, we have described the results
of investigations to elucidate the chemical, physical
and morphological changes that occur during the
synthesis of activated carbons by the phosphoric acid
activation of white oak (Quercus al&) [ 1,2]. To
examine the general applicability of the findings to
the activation of other hardwoods, the research has
been considerably extended to obtain comparative
information using yellow poplar (Liriodendron tulipif-
era) as an activated carbon precursor. Both white
oak and yellow poplar are hardwoods that grow in
abundance in Kentucky and the southeastern U.S.
[3]. However, they differ in several respects, such as
in their wood cellular structure, biopolymer composi-
tion, density and hardness. This paper describes the
points of correspondence and difference in the beha-
vior of the two hardwoods, and adds new information
about the mechanisms of phosphoric acid activation.
2. EXPERIMENTAL
2.1 Materials
Samples of white oak and yellow poplar were used
as activated carbon precursors, and were in the form
of wood blocks (2.2 cm x 5 cm x 10 cm) and powder
*Corresponding author.
( 100 mesh (< 150 pm)). In order to follow the dimen-
sional changes during reaction, samples of the precur-
sors were prepared as thin sections that were cut
from the blocks. By using parallel sections, separate
specimens of each hardwood contain the same dis-
tinctive morphological features, allowing dimensional
changes during activated carbon synthesis to be
accurately followed and measured: features such as
growth rings survive the process of chemical activa-
tion and can be readily discerned in the carbon
products. Sections were cut in a plane perpendicular
to the axial direction of the tree growth to provide
specimens measuring 2.2 cm x 5.0 cm x 0.15 cm for
the white oak. The yellow poplar was treated in a
similar manner to provide specimens of
2.3 cm x 7.1 cm x 0.16 cm. The white oak sections
contained 6.5% moisture while the yellow poplar
contained 5.7%. For other experiments, the wood
samples were used in powder form. The samples were
all stored in sealed containers. Representative analy-
ses of the two precursors are shown in Table 1 [4].
Notable differences are the higher H/C and O/C
ratios for yellow poplar, the higher content of lignin
and lower content of hemicellulose, and the much
lower density compared to white oak.
2.2 Chemical activation
Samples of wood in the form of sections (about
1 .l g) or powder (24 g) were used without drying
1085
1086 M. JAGI oyrh and I:. DKRRYSHIN
Table I. Typical composition of hardwood precursors [4]
White oak Yellow poplar
Elemental analysis (wt%)
t1 6.1 7.0
0 42.0 47.3
c 51.2 51.3
Biopolymer content (~1%)
Cellulose i 3 -3 52
Hemicellulose 24.1 I4
Lignin 24.6 34.2
Atomic ratios
O/C 0.61 0.7
H/C I .42 I .6i
Density (g cm-) 0.68 0.42
and were soaked in phosphoric acid solution for 1
hour at room temperature to allow penetration of
acid into the wood structure: the proportion of
H,PO, to wood normally used (as-received basis)
was 1.45 g H,PO, or 1.5 x lo- mol of H,PO, per
gram of wood. At this ratio of reagent to precursor,
the amount of reagent is considered to be in excess
[5]. The phosphoric acid was obtained as an 85%
solution and was diluted to a concentration of 28%
before adding to the wood samples. in order to
facilitate wetting and impregnation through increas-
ing the solution volume. In one series of studies, the
ratio of acid to precursor was varied.
Usually, the mixture was then subjected to lou-
temperature heat treatment by heating slowly to
170C in a stainless steel reactor, under flowing
nitrogen at atmospheric pressure It was held at this
temperature for 30 minutes, and then taken to a final
heat treatment temperature (HTT) up to 650C and
held for 1 hour. In some cases, the final HTT was
below 17OC, in which case the mixture was subjected
only to low-temperature heat treatment with a 3 hour
hold time at temperature. Carbons were obtained
at HTT between 75565OC for white oak, and
150&65OC for yellow poplar. The solid products
were leached with distilled water to pH 6 and vacuum
dried at 110C before further characterization. For
comparison, thermally treated samples were prepared
by following the same heat-treatment procedure. but
without phosphoric acid addition. A limited set of
experiments was also made with white oak in which
the ratio of phosphoric acid to precursor was varied
from 0.17 1.45 g acid per gram of wood with a
constant HTT of 500C.
2.3 Analysis and characterization
In selected experiments, an on-line quadrupole
mass spectrometer (VG/Fisons Quadrupole Mass
Spectrometer, Sensorlab 300D-850 with Thermosoft
software) was used to measure the composition of
the gases evolved while heating a sample of wood or
a phosphoric acid-wood mixture (heating rate
2C min- to 600C in an atmosphere of argon). The
gases were analyzed for four constituents that were
present in high concentration: CO (mass 28) CO2
(mass 44), CH, (mass 16. but followed as mass 15.
the CH, radical, to avoid interference from 0) and
llL (mass 2). Water (mass 18) was present in the gas
phase in an approximately constant and relatively
high concentration over the whole temperature range
under study. It was not possible to distinguish
between the water added to the reaction mixture and
that liberated by reaction.
The solid carbon products were characterized by
several techniques: chemical analysis for elemental
composition; optical and scanning electron micro-
scopy; and N, (77 K) adsorption. The morphological
changes during synthesis were examined by micro-
scopic methods and were also quantified by the
measurement of dimensional changes using a
micrometer to determine the distance between growth
rings in the radial direction.
Information on the carbon pore structure was
derived from nitrogen adsorption isotherms obtained
at 77 K on a Coulter Omnisorb 610 automated
surface area analysis system. Surface areas were
calculated from the adsorption isotherms using the
method of Brunauer, Emmet and Teller (BET
method) [6]. The micropore volume W,, (pores less
than 2 nm diameter) was determined using the
Dubinin Raduskevich equation [7]. Mesopore sur-
face areas and volumes were calculated using the
BJH method [8].
3. RESULTS
3.1 Porosity development
In order to select an appropriate ratio of acid to
precursor, a survey was made of the effect of varying
this ratio on porosity development for the white oak
precursor (powder) at a constant heat treatment
temperature (HTT) of 500C Fig. 1. As the ratio of
chemical reagent to wood is increased the micropore
volume increases to a maximum at a ratio of about
0.80 g H,PO,/g wood. At higher ratios, the micropore
0.7 -
*y---*
J--.---_..____
1
0.6 -.
,I
~
,
G 0.5 *.
,
/
;3
,
I
> I
g 0.4 --
.o /
,
I
,
1
,
,
/
F
,
./
0. .
g 0.2 --___:
n
.
.
.
.
.( n
0.1 --
.H
. ..
.-,f
0,
_*.- ,
0 0.5 1
Ratio HBPO, : wood (g/g)
1. 5
Fig. 1. Effect of acid:wood ratio on porosity development
m white oak (HTT =SOOC, H,PO, strength 28%, precur-
sor: sections of wood).
Activated carbons from yellow poplar and white oak 1087
volume is approximately constant or may even
slightly decrease. On the other hand, the mesopore
volume is small at low ratios and then increases more
appreciably as the ratio is raised above about 0.8:
there is no indication that the mesopore volume has
attained a maximum at the highest ratio used here.
Consequently, it can be seen that the ratio of reagent
to precursor is an important variable, and it can be
used to change the pore size distribution in the
activated carbon. The nature of this dependence also
changes with HTT [ 11. In all subsequent experiments,
phosphoric acid was used at a ratio of 1.45 g
H3P0,/g of dry precursor. This ratio was selected as
it gives high micropore and mesopore volumes, and
it is also a value that is typical of the ratios used in
commercial processes [ 5,9].
A comparison of porosity development in activated
carbons produced from white oak and yellow poplar
at a ratio of 1.45 g H,PO,/g is shown as a function
of HTT in Fig. 2. Within the scatter of data it can
be seen that there is a very similar correspondence
of the results for the two precursors. The bands
drawn on the figure enclose the two sets of data.
Micropore development begins at about 150C and
rises to a maximum at about 350C. Mesopores begin
b
0 100 200 300 400 500 600 700
HTT FC)
Fig. 2. Pore volume of activated carbons from white oak
and yellow poplar (H,POjwood = 1.45 g g-l, acid strength
288, precursor: sections of wood).
0 200 400 600 f
Heat treatment temperature (C)
to develop at the higher temperature of about 250C
and the mesopore volume attains a maximum at
500-550C. The different temperature dependencies
of the two ranges of pore volume indicate that
different processes may be involved in the formation
of micropores and mesopores. At the same time, it
should be recalled that the division into pore size
ranges is a convenient convention, and as the pore
structure actually consists of a continuous distribu-
tion of pore sizes, there will clearly be some interde-
pendence of the size ranges. It is apparent from Fig. 2
that most of the increase in the mesopore volume
(above about 350C) corresponds to a decrease in
microporosity, suggesting that pore widening contrib-
utes to the increase in mesopore volume. In conjunc-
tion with the data shown in Fig. 1, it is also apparent
that the pore size distribution can be modified by
selection of the HTT as well as the reagent to
precursor ratio.
3.2 Chemical change
Elemental analyses of the white oak and yellow
poplar carbons produced by phosphoric acid treat-
ment and thermal treatment confirm other reported
results [ 1,2] showing that acid treatment accelerates
the removal of oxygen and hydrogen, at temperatures
as low as 75C, Fig. 3(a)Fig. 3(b). There is little
effect upon thermal reaction until the HTT is at least
150C and a sharp change then occurs between
250-350C. By plotting the atomic ratios H/C versus
O/C (after van Krevelen [lo]), it is found that the
thermal and acid data fall on a straight line with a
gradient of 2.0, showing that the net change in the
transformation of the precursors to carbon products
is the elimination of water, irrespective of whether
phosphoric acid is present or not, Fig. 4. (As will be
discussed below, dehydration is not the only reaction
that can occur.) The effect of phosphoric acid is to
promote dehydration at 150 to 200C lower than
upon thermal reaction.
Some differences are apparent between the two
precursors. While the H and 0 contents of the
carbons follow a similar curve with HTT for the two
8
266 406 600 I
Heat treatment temperature (C)
Fig. 3. Change in oxygen content (a) and hydrogen content (b) of carbons from yellow poplar (YP) and white oak (WO) as
a function of HTT (H,POI activation; H,PO,:wood = 1.45 g g-l, acid strength 28%, precursor: sections of wood).
1088
M. JAG~OYI:N and F. DI:RBYSHIRE
I
0 0.2 0.4 0.6 0.8
O/C Atomic Ratio
Fig. 4. Van Krevelcn diagram for carbons produced
from yellow poplar (YP) and white oak ( WO) (H,PO,
activation; H,PO,:wood = I .45 g g-, acid strength 28%.
precursor: sections of wood).
hardwoods for thermal treatment, they do not corre-
spond for the acid treated products, Fig. 3(a and b).
Specifically, the dehydration of white oak appears to
have a greater temperature dependence than that of
yellow poplar. One possible cause may be the higher
H and 0 content of the parent yellow poplar.
The composition of the gases evolved during ther-
mal and acid treatment is indicated by plots of the
mass spectrometer response for CO/CO, and
CH,/H, versus HTT in Figs 5 and 6, respectively. In
the presence of H,PO,, CO2 and CO begin to be
liberated just below about 100C and their production
increases sharply to a maximum at about 200C.
Thereafter, the generation of both gases declines
continuously with HTT. In the thermal case, CO,
and CO evolution starts at higher temperatures (in
the region of 150~200C) and the amounts of these
lE-09
^h
.%
%
Y
lE-10
El
c
?
L;I
lE-11
Fig. 5. CO and CO, evolution on thermal treatment and
H,P04 activation of white oak (H,PO,:white oak=
1.45 g g-i, acid strength 28%, precursor: white oak powder).
lE-11
0.0 200.0 400.0 600.0
HIT(C)
Fig. 6. CH, and H, evolution profiles during thermal treat-
ment and H,PO, activation of white oak (H,PO,:white
oak=1.45ggm, acid strength 28%, precursor: white oak
powder).
gases increase to maxima between 250&35OC. At all
times the concentrations of CO and COZ in the gas
phase during thermal pyrolysis appear to be lower
than in the presence of phosphoric acid. The origin
of the CO,, and water, is believed to be from both
the lignin and cellulose part of the wood. However,
previous work by Shafizadeh showed that the pres-
ence of 5% H,PO, during the pyrolysis of cellulose
increased water yield from 11 to 21% while the
amount of CO, was unchanged compared to pyrolysis
in the absence of H,PO, [ 111. It is therefore believed
that the increased amount of CO, released on
H,PO, treatment originates from lignin.
Upon acid treatment, there is a very significant
release of methane beginning at around 100C and
rising to a sharp maximum around 250C. The
generation of CH, falls to a minimum between
35OG4OOC and then rises to a second, lower maxi-
mum between 45OG55OC. The release of CH, in the
thermal case is quite different. Here, methane is
produced in much lower amounts and only begins to
become evident at temperatures above about 250C.
The production of H, starts at around 400C in the
presence of H,PO, and also rises to a sharp maximum
at about 550C. Upon thermal pyrolysis the gas
phase hydrogen content is always low and only
slightly increases at HTT above 450C.
Thus it is apparent that dehydration is not the
only means of oxygen and hydrogen removal. In the
presence of phosphoric acid, the former is also
released as oxides of carbon, with maximum pro-
duction at about 200C and the latter as light
hydrocarbon gases, principally methane, rising to a
maximum at about 250C; hydrogen is also liberated
Activated carbons from yellow poplar and white oak 1089
at higher HTT as molecular hydrogen and by second-
ary methane formation.
3.3 Morphology
The changes in the morphology of carbons pro-
duced from white oak relative to the parent wood
have been described earlier [ 11. Similar behavior was
observed with yellow poplar. Observations of fibrous
cells with distinct primary (lignin-rich) and secondary
(high content of crystalline cellulose) cell walls in the
parent wood showed that, after phosphoric acid
treatment to 125C there is evidence of the flow and
redistribution of cellular material. Upon heat treat-
ment to 200C this redistribution causes the formerly
empty cell lumens to be filled. However, the bound-
aries between the primary and secondary cell walls
are still clearly distinguished and the original cell
structure is still recognizable even after heat treatment
to 350C and above. Thus, it appears that there is
relatively little interaction between the crystalline and
amorphous regions. In contrast, thermal treatment
effects a massive disruption to the structural integrity
of the wood. By about 350C the secondary cell walls
have almost disappeared and are no longer distin-
guishable from the primary walls.
From the results of this and the earlier study, it
seems probable that when acid is present the amor-
phous biopolymers (lignin and hemicellulose) are the
primary sources of the redistributed material. Studies
by i3C NMR have shown that, at temperatures as
low as 50C there are detectable changes to the
composition of these biopolymers, and by 150C
there is a measurable increase in the ratio of crystal-
line to amorphous cellulose [2]. The partial depolym-
erization of amorphous biopolymers due to the action
of the acid could account for a limited degree of
mobility and migration. Related studies have shown
that the reflectance of the material that fills the cell
lumens is similar to that of the primary cell wall,
which consists mainly of lignin, whereas the reflec-
tance of the secondary cell wall (cellulosic) is appreci-
ably lower [12]. In other work, it seems that the
reaction of lignin with phosphoric acid can lead to
the formation of a plastic phase during low temper-
ature reaction [ 131, also suggesting that this biopoly-
mer is readily degraded into lower molecular weight
units.
3.4 Dimensional change
The transformation of hardwood to an activated
carbon is accompanied by significant dimensional as
well as morphological change. As has already been
described for white oak, it was found that, upon acid
treatment, there is a contraction at low HTT, fol-
lowed by structural dilation at intermediate HTT
and secondary contraction at high HTT [ 11. The
dilation and secondary contraction have been directly
related to the development and subsequent decline
of porosity. In particular, the onset of dilation mea-
sured on a relatively coarse (millimeter) scale, and
therefore representing a range of structural composi-
tion, and the appearance of microporosity occur at
the same HTT (15OC), and a similar correspondence
is found at a HTT of 250C between the expansion
of the secondary cell walls (in microns), which com-
prise mostly crystalline cellulose, and the develop-
ment of mesoporosity.
The dimensional changes in the radial direction
are compared in Figs 7 and 8 for the thermal and
acid treatment of white oak and yellow poplar as a
function of HTT. Upon thermal treatment, measur-
able contraction commences above about 150 to
200C for both hardwoods, and then progresses
monotonically with increasing temperature. At a
HTT of 450C the overall contraction in the radial
direction is about 20% for white oak and 30% for
yellow poplar.
When phosphoric acid is present, there is measur-
able contraction at temperatures as low as 50C
consistent with the action of the acid in lowering the
temperature threshold for dehydration and weight
loss. The contraction sharply increases to about 18%
for white oak, and 28% for yellow poplar at
0 100 200 300 400 500 600 700
HTT (C)
Fig. 7. Changes in radial dimension of carbons produced
from white oak by H,PO, activation and thermal treatment
(H,PO,:wood= 1.45 g g-r, acid strength 28%, precursor:
sections of wood).-
65~ :
0 100 200 300 400 500 600 7
H7T (C)
Fig. 8. Changes in radial dimension of carbons produced
from yellow poplar by H,PO, activation and thermal
treatment (H,PO,:wood= 1.45 g g-, acid strength 28%.
precursor: sections of wood).
1090
M. J AG IOYEN and F. DI~RRYSHIRI:
100-I 50C. At higher temperatures, the structure
begins to dilate. This process continues with increas-
ing HTT to a maximum between 3OOG45OC. when
the net contraction relative to the original wood
structure is reduced to about 3% for white oak and
13% for yellow poplar. With further increase in HTT.
a second process of contraction then begins. At a
HTT of 650C the overall contraction is 14% for
white oak and 20% for yellow poplar. which means
that the structures are still dilated relative to the
maximum contraction experienced at 100~~ 150 C. It
is to be noted that with both thermal and acid
treatment, the relative dimensional contraction for
the yellow poplar carbons is always about 10% more
than for the white oak series. A possible reason for
this difference may relate to the much higher lignin
content of yellow poplar, Table 1. If, as proposed.
the lignin is readily depolymerized. and can migrate
into empty structural features, then the contraction
of yellow poplar should be appreciably more than
for white oak.
FIN. 9. A combination of two models describing the associa-
tion ot cellulose, polyoses (hemicellulose) and lignin in the
wood cell wall (adapted from Fengel and Wegner [ 141).
With reference to Fig. 2, it can be clearly seen that
the onset of dilation corresponds directly to the
development of microporosity for both hardwoods.
Moreover, despite the differences in the extent of the
initial contraction of white oak and yellow polar, the
overall dilation in both cases is about 15%. and the
micropore and mesopore volumes in the activated
carbons follow the same pathway with HTT. Above
-350C the micropore volume begins to decrease
while the mesopore volume continues to increase to
a maximum between 500~- 550C before it also starts
to decline.
Cellulose
3.5 Mechanisms ofphosphork acid uctivation
The addition of the present data to the information
already published on phosphoric acid activation
allows a reasonably comprehensive account of this
process to be assembled, although there still remain
many facets of this complex system that are poorly
understood. For convenient reference. the salient
changes and phenomena that have been observed in
our own research are summarized in Table 2. 10
further facilitate discussion, it is useful to provide a
brief description of some pertinent aspects of wood
structure. Essentially, wood is a complex fibers matrix
composite material formed of natural polymers in
which the fiber framework consists of crystalline
cellulose microfibrils of 225 nm diameter. The matrix
between the microfibrils is composed mostly of hcmi-
cellulose, and lignin provides the strengthening mate-
rial that solidifies the surrounding cell wall. Fig. 9
[14]. Typical ranges for the biopolymer content of
hardwoods are: 42250% cellulose, 19 25% hemicellu-
lose and 16625% lignin [ 151. The molecular structures
of lignin, hemicellulose and cellulose are shown in
Fig. 10. The microfibrils in the ccl1 walls are formed
from cellulose chains that are aligned and held
together by hydrogen bonding between the hydroxyl
groups on the repeating glucose units. Groups of
1 Wgg$
Hemicellulose
H& OH
I
I;
nc
OC",
0
bH
$20
I
f
0
OH
l,ig. IO. Chemical structures of cellulose, lignin and
hemicellulosc.
Lignin
microlibrils are connected by amorphous cellulose
(about 10 20% of the total cellulose) and hemicellu-
lose, and the array is surrounded by lignin and some
hemicellulose. The space between the microfibrils in
an array is of the order of a few nm, and in the same
size range as larger micropores and mesopores.
3.5.1 Reaction at low temperature. The reac-
tion of wood with phosphoric acid probably begins
as soon as the components are mixed. Certainly.
after heat treatment to 50C there is evidence of
Activated carbons from yellow poplar and white oak 1091
Table 2. Summary of phenomena relating to reaction of hardwoods with H&PO, (sources: present study and refs. [ 1,2])
Conditions or
analysis method
H,PG,
Thermal
Below 150C
Elemental
13C NMR
FTIR
Gas analysis
Above 150C
Microscopy
Gas adsorption
Gas analysis
Yield determination
r3C NMR
FTIR
Early elimination of H, 0 that continues to - SOOC-
net effect dehydration leading to lower carbon yield
below 300C
Loss of carboxyl and methyl groups from hemicellu-
lose even at 50C and changes to lignin composition;
by lOOC, substantial reaction of cellulose and forma-
tion of ketones--intense peak by 150C; increase in
ratio of crystalline to amorphous cellulose; increase in
aromaticity and loss of aliphatic, carboxyl and car-
bony1 groups; onset of crosslinking
Increasing aromaticity, loss of aliphatic character; loss
of CO-C, C-O-H, C=O groups; appearance of
ketone groups, evidence for formation of phosphate
esters (cellulose phosphates)
Evolution of CO, CO,, CH, begins at - 100C
Evidence for partial depolymerization of biopolymers
and redistribution of material-emphasis on amor-
phous polymers (lignin)
Continuous contraction in radial direction up to
- lWC, and in thickness of secondary cell walls
(primary cellulose) up to -250C: even at high
HTT, morphological features of wood structure
retained
Dilation in radial direction from 150C to maximum
between 300-45OC, and of secondary cell wall thick-
ness from 250C to maximum at -450C
Secondary contraction > -450C for radial dim. and
secondary cell wall
Correspondence between porosity development and
structural dilation: micropore volume increases from
150C to max. at -350C relating to overall dimen-
sional expansion and reflecting an average effect of
constituent biopolymers; mesopore volume increase
from 250C to max. at -500&55oC inferring link with
conversion of cellulose
Loss of porosity at higher HTT corresponds to second-
ary structural contraction
Maxima in CO, CO2 evolution at -200C; maximum
in CH, evolution at -250C second maximum at
- 500C; -4OOC, onset of H, evolution rising to
maximum at 550C
Higher carbon yield > 300C-attributed to crosslink-
ing reactions and retention of altered cellulose
>45OC, dramatic increase in aromatic cluster size,
indicative of reduction in crosslinking and structural
rarrangement
>45OC, significant reduction in intensity of cellulose
phosphate bands, and disappearance of bands due to
ketones and esters
Maximum retention of phosphorus in char at -450C
Negligible change
No equivalent changes until - 250C
No equivalent changes until > 250C
CO, CO, evolution begins at - 150C
Contraction of secondary cell wall and in radial
direction starts -150C and continues mono-
tonically with HTT: -350C most of second-
ary cell walls have disappeared with major loss
of wood structure morphology
Negligible porosity in thermal chars
Maxima in CO, CO, evolution at 250-350C;
CHI evolution low and only evident >3OOC;
H, evolution very low, slight increase > 450C
Equivalent change starts - 550C
1092
M JAG I oym and F. DERHYSHW
chemical and physical change. It appears that the
acid first attacks hemicellulose and lignin, possibly
because of easier access to these amorphous biopoly-
mers than to the crystalline cellulose. Elsewhere,
cellulose has been reported to be more resistant to
acid hydrolysis than other polysaccharides [ 161, and
the results obtained in this and previous work further
indicate that cellulose does not experience the same
degree of degradation, since the general integrity of
the cell structure is retained after reaction with
H,P04, even to elevated HTT [ I]. The primary effects
of acid attack are to hydrolyze glycosidic linkages in
polysaccharides (hemicelhtlose and cellulose) and to
cleave aryl ether bonds in lignin. These reactions arc
accompanied by further chemical transformations
that include dehydration, degradation and condensa-
tion [ 161. The primary reactions can lead to a reduc-
tion in molecular weight, principally of hemicellulose
and lignin, which is consistent with the observed
redistribution of woody material and with the ability
to form extrudable mixtures of wood and phosphoric
acid [5]. Further. it is known that the acid-catalyzed
hydrolysis of ether linkages in lignin can lead to the
formation of ketones [ 161, whose appearance was
observed by FTIR and 13C NMR [2].
These and other bond cleavage reactions that
proceed through ionic mechanisms can explain the
release of CO, CO, and CH,. The low temperature
evolution of CO and CO, is consistent with the
observed reduction in C-O functionality that is
accounted in part by esters and carboxylic acid
groups in the parent wood (mostly present in hemicel-
lulose and lignin). The substantial release of CH, at
similar temperatures suggests that the cleavage 01
aliphatic side chains is relatively facile, and is consis-
tent with a loss of aliphatic character and a corrc-
sponding increase in aromaticity.
3.5.2 Reuction ut intermediutr trmperutures.
The liberation of gases and volatile products during
reaction, and the removal upon leaching of any
water-soluble products that are formed by depolym-
erization, each contributes to the accelerated weight
loss and volumetric contraction that is observed for
the water-insoluble char up to about 15OC. Upon
going to higher temperatures, the rate of weight loss
slows appreciably and the structure begins to dilate.
The stabilization and dilation of the wood structure
correspond to the development of porosity. In this
regime. crosslinking reactions, that first become
apparent at lower HTT [2], begin to dominate over
bond cleavage and depolymerization reactions, as
indicated by the findings that CO and CO, evolution
peak at 200C. and the first maximum in CH,
evolution occurs at 250C. The greater yield of
carbon obtained by acid treatment above about
3OO.C is attributed to a high incidence of structural
crosslinking that serves to retain relatively low molec-
ular weight species in the solid phase
There is evidently a direct connection between
porosity development and the process of structural
dilation. In attempting to interpret the mechanisms
of dilation, a wealth of relevant information exists
on the use of phosphorus compounds as flame retar-
dants for wood and cellulose [ 17-191 and in other
work on the chemical modification of wood [20].
The origins of flame retardant properties that are
introduced by phosphorylation are the same as those
found in phosphoric acid activationvolumetric dila-
tion or intumescence (providing a thermal barrier)
and reduced loss of volatiles due to crosslinking
(raising the ignition temperature). Research on the
use of phosphoric acid as a flame retardant for
cellulose has shown that phosphorus compounds can
form ester linkages with -OH groups on cellulose at
temperatures below 200C [21], helping to crosslink
the polymer chains. Reaction with phosphoric acid
also stabilizes the cellulose structure by inhibiting the
formation of levoglucosan which otherwise offers a
route to the substantial degradation of cellulose
through its decomposition to volatile products,
Fig. I I [ 19,221. Other work has shown that phos-
phates can function as effective flame retardants for
synthetic polymers [23,24]. In studies of the fire
retardance of the system ammonium polyphosphate
and pentaerythriol. it was found that a swollen or
intumescent char is produced between 280 and 350C.
A particular distinction of this system from the
present work is that the experiments were performed
in a Row of air. At 28OC, the structure is considered
to consist of relatively small polyaromatic units that
are connected mostly by phosphate and polyphos-
phate bridges that can include polyethylene linkages
[ (CH,), 1. As the temperature is increased, cycliza-
tion and condensation reactions lead to an increase
in aromaticity and in the size of the polyaromatic
units, enabled by the scission of PPO- C bonds,
Between 350 to 500C the char is considered to be
stable, but at 430C and above, the continued cleav-
age of crosslinks leads to a very extensive growth in
the size of the aromatic units. It was proposed that.
at lower temperatures, the formation and persistence
of organic phosphocarbonaceous esters limits depo-
lymerization and inhibits the development of con-
densed polyaromatic structures. In the present
research. the appearance of an absorption band that
is attributed to phosphate esters is first observed by
FTIR at about 150C. It persists with increasing
HTT, although its intensity is reduced above about
450 c.
Studies of the modification of wood by reaction
with various other chemicals have also shown that
there is often a volumetric expansion that accompa-
nies chemical reaction [20]. The major types of
reaction involve bonding chemicals to biopolymer
hydroxyl groups to form esters, acetals and ethers.
One of the criteria used to indicate successful reaction
within the cell wall and chemical bonding to the
biopolymers is a volume expansion of the wood that
IS equivalent to the volume of chemical added; the
volume increase may be of the order of 10%.
Activated carbons from yellow poplar and white oak 1093
Formation of levoglucosan
A
\
H3PO4
H OH
levoglucosan(volatlle)
Esterification would block formation of cyclic levoglucosan
6CH,O-P-O,H,
S&----Q
Fig. Il. Reaction mechanism for flame retardance of phosphoric acid impregnated cellulose (adapted from Barker and Hendrix
[ 191 and Lyons [22]).
Dimensional stability is achieved in cases where the
bulking chemical crosslinks the cell wall polymers.
Thus phosphoric acid appears to be able to func-
tion in two ways: as an acid catalyst in promoting
bond cleavage reactions and the formation of cros-
slinks via such processes as cyclization, and condensa-
tion; and by being able to combine with organic
species to form phosphate linkages, such as phos-
phate and polyphosphate esters, that can serve to
connect and crosslink biopolymer fragments t24].
The formation of phosphate esters by reaction of
cellulose with phosphoric acid is shown in Fig. 12.
The addition or insertion of phosphate groups sepa-
rates the organic species and effects a dilation of the
structure. An important distinction between phos-
phoric acid activation and the chemical modification
of wood by phosphoric acid or other chemicals is
that, in the latter case, the added reagent is retained
in the expanded wood structure. In the synthesis of
activated carbons, the phosphoric acid is removed
after reaction by leaching to recover the reagent. For
this reason, the phosphorus content of the recovered
carbons only indicates the amount of residual mate-
rial that is present, either combined with the organic
structure, in the form of insoluble metal phosphates,
or physically entrapped.
To examine the stability of the structure after
removal of the acid, a short series of additional
experiments was performed. Samples of white oak
were activated with H3P0, to a given HTT, leached,
and then reheated to a HTT that was 50C higher
than the first. The yield and porosity of the products
were compared with those of carbons that had been
heat treated in the presence of acid to the same upper
temperature. It is found that the additional 50C of
thermal treatment reduces the yield of carbon,
Fig. 13, and that the biggest reduction in yield occurs
between about 250-400C; that is, over the temper-
ature range where there is the greatest dilation, and
where it is expected that a high concentration of
phosphate linkages will have been formed. There are
also significant accompanying reductions in micro-
pore volume, and increases in mesopore volume,
Table 3. These observations are consistent with the
proposition that phosphate linkages make a consider-
able contribution to the total crosslink density. Upon
leaching, due to their strong affinity for water, these
crosslinks are readily broken by hydrolysis which
allows almost complete recovery of the acid (see
Fig. 12, eqn (2)). When condensed phosphoric acids
are dissolved in water, hydrolysis to orthophosphoric
acid takes place in a matter of minutes at 100C [25].
As a consequence of the removal of the phosphate
linkages and a reduction in crosslink density, the
structure is metastable. Further heat treatment then
increases the loss of volatile constituents that are no
longer strongly bonded into the solid phase, reduces
the carbon yield, and may lead to pore widening.
The overall structural dilation begins at about
150C and that of the secondary cell walls at about
250C. Up to 250C the dilation can be ascribed to
Table 3. Effect of acid removal for last 50C
Micropore volume Mesopore volume
(cm g-l) (cm3 g-r)
no H,PO, no H,PO,
HTT (C)
H,P0,
last 50C
H,P0,
last 50C
250 0.11 0 0.03 0.01
300 0.42 0.20 0.06 0.05
350 0.68 0.30 0.10 0.05
450 0.67 0.59 0.36 0.74
500 0.64 0.53 0.55 0.70
550 0.61
_
0.37
600
_
0.46 0.72
Micropore and mesopore volume for carbons produced
at a certain HTT compared to runs where the acid was
removed before the last 50C of the heat treatment
(H,PO,:white oak = 1.45 g g-l, acid solution strength =
28%, precursor: white oak sections and powder).
1094
M. JAC;TOYI:N and F. ~kKHYSHIKI
T< 450C: Formation of phosphate esters on cellulose side chains and crosslinking
CH20H
0
lclr
OH
I
OH
+OH-p=O T==t
OH
0
I
OH
OH
CH20H
0
0
OH
1- H20
OH
P
OH -P=O
OH
?
Q
OH
H20H
Esters can be derivatives of ortho-, pyro- and meta-phosphoric acids:
OH-r=O
OH
orthophosphoric acid
It
A
0
0
II
II
OH-P-O-p -OH +H20
I
OH
OH
pyrophosphoric acid
T>450C: Elimination of H3P04
CH20H
t--s
0
OH--P=0
b
OH-P=0
0
OH
OQ
+ -P=
OH
OH-&O
I
OH
Fig. 12. Mechanisnr of phosphate cstcr formation by phosphorylation of cellulose.
changes in the structure of the amorphous biopoly-
mers, including amorphous cellulose. Micropore
development also begins at IWC, which suggests
that a proportion of the micropores that are ulti-
mately developed arises from a combination of acid-
promoted reactions and the formation of phosphate
esters with the amorphous biopolymers. The insertion
of the phosphate esters drives a process of expansion
that, after removal of the acid, leaves the matrix in
an expanded state with an accessible pore structure.
The simultaneous removal of carbon in the form of
CO. CO, and light hydrocarbon gases must also
contribute to the pore structure.
At 250C a thickening of the secondary cell walls
becomes apparent, adding to the total dilation of the
structure, and also marking the beginning of meso-
pore development. The expansion of crystalline cellu-
lose is attributed to essentially the same causes as
that of the amorphous biopolymers. Namely, reaction
with phosphoric acid promotes chemical change that
includes the stabilization of the cellulose chains,
crosslinking through the formation of etheric and
0 200 400 600 600
H-IT (C)
Activated carbons from yellow poplar and white oak
1095
ing total micropore volume, and the volume occupied
by mesopores also increases steadily. By about 350C
the extent of dilation of the crystalline cellulose is
such that the existing micropores are widened to
approach mesopore dimensions, and the latter
begin to increase at the expense of the former. Hence,
while the micropore volume passes through a maxi-
mum, the mesopore volume continues to rise.
Interestingly, over the temperature range 350-550C
the total pore volume remains constant, indicating
that new pores are not created to any significant
extent, and that the principal change is in the pore
size distribution. By the time that the mesopore
volume attains a maximum at 550C the micropore
volume has fallen to about the same value as it was
at 250C. These observations support the proposition
that activation of the amorphous polymers produces
mostly micropores, while activation of crystalline
cellulose produces a mixture of pore sizes. The pore
size distribution obtained from crystalline cellulose
can be altered by increasing the HTT and/or the
ratio of acid to precursor such that, eventually, the
structure is dominantly mesoporous.
Fig. 13. Yield of carbon as a function of HTT for carbons
produced with phosphoric acid compared to runs where the
acid was removed before the last 50C of the heat treatment
(H,PO,:white oak = 1.45 g g-l, acid solution strength =
28%, precursor: white oak sections and powder).
other linkages, and crosslinking through the forma-
tion of phosphate and polyphosphate esters. The
potential for the dilation of crystalline cellulose is
believed to be much greater than for the amorphous
polymers due, among other factors, to its higher
density and its chemical structure that allows for a
more extensive degree of combination with phospho-
ric acid, and hence bulking of the cell walls. The
average density for wood is 1.53 g cmm3, for lignin
1.40gcm-3 and for cellulose 1.60 g cme3 [26].
From Fig. 12, it is easy to visualize how a chemical
such as phosphoric acid can insert between the
cellulose chains, disrupt the existing hydrogen bonds,
replace them with other chemical linkages, and simul-
taneously separate the chains and dilate the structure.
Dilation can continue as more acid is progressively
incorporated, and the phosphate crosslinks may
become more bulky at higher HTT due to polymer-
ization of the acid to form polyphosphates. The fact
that the mesopore volume is found to increase with
the ratio of phosphoric acid to wood is also consistent
with this proposition, since at higher ratios, more of
the acid can be incorporated. Although the swelling
of the secondary cell walls was measured directly, it
is difficult to estimate the extent of swelling of the
amorphous regions by subtraction from the overall
dimensional change, since there are many large open
vessels that could accommodate some of the expan-
sion. However, as a rough indication of the total
dilation that is experienced between 150 and 450C
approximately one third occurs up to 250C and two
thirds above this temperature, which is when the
secondary cell wall dilates. Moreover, the extent of
dilation expressed as a percentage of the original
dimensions is about 15% for the overall change while
it is about 25% for the secondary cell walls.
The above findings and inferences are consistent
with some of those reported in the published litera-
ture. Cameron and MacDowall [27] proposed that,
upon phosphoric acid activation, the acid serves to
swell the wood structure allowing the cellulose
microfibrils to separate. Upon carbonization, the
altered microfibrils form an open mesoporous struc-
ture of loosely packed rods of carbonized cellulose
with pores of lo-30 nm in diameter. These authors
did not attempt to account for the mechanism of
micropore formation. However, their proposal is
generally consistent with the present results. Other
studies have shown that the reaction of phosphoric
acid with cellulose, even at low temperatures, pro-
duces considerable intercrystalline and intracrystal-
line swelling [28,29]. Pandey and Nair [ 281 examined
the reaction of phosphoric acid with cotton at temper-
atures of 10, 29 and 40C for 0.5 hours using varying
concentrations of phosphoric acid (O-81% acid con-
centration with a constant cotton to liquor ratio of
1 : 100). They found that the degree of cellulose
polymerization decreased with an increase in either
variable:acid concentration or temperature. This and
the other published research [29] shows that phos-
phoric acid begins to interact with cellulose at temper-
atures as low as 10C producing swelling in both
crystalline and intercrystalline regions and causing a
breakdown of the cellulose polymer chains.
Around 250C it is considered that the porosity
contributed by the modified secondary cell walls is
mostly microporous, with some wider pores present.
As dilation progresses with increasing HTT, the
micropores from this source contribute to the grow-
3.5.3 Reaction at high temperature. At HTT
above about 450C the structure begins to contract,
as determined both by the overall dimensions and by
the thickness of the secondary cell walls. However,
while the micropore volume decreases steadily with
HTT above 350C there is no apparent effect on the
mesopore volume until about 550C when it starts
to decrease quite steeply. It is possible that between
450 and 550C the structural contraction is accom-
1096 M. _iAGTOY1:N and F. hUJYSHlKli
modated by a narrowing of pore diameters without
causing an appreciable shift between pore size ranges.
Above 550C a sharp decline in mesopore volume is
paralleled by the secondary contraction of the cell
walls. Between 450.-650C the cell wall thickness is
reduced by about 30% of the original dimension.
while the overall contraction in the radial direction
is only about 11%. The extent of the collapse of the
secondary cell walls is such that their thickness at
650C is less than at any lower HTT. while the
overall structure is still dilated relative to the extent
of contraction experienced at 15OC.
The contraction of the altered crystalline cellulose
mirrors its previous extensive dilation. Just as dilation
has been explained by the formation of bulky phos-
phate linkages. its reversal is consistent with their
breakdown, due to their attaining the limit of thermal
stability at about 450C [ 19,23,24]. Since the phos-
phate bridges are considered to be more highly
concentrated in the altered cellulose, it is logical that
their decomposition would exert the greatest effect
on this structure, Relatedly. we reported earlier that
FTIR analysis showed a reduction in the intensity of
bands attributed to phosphate esters above 450 C.
There is also a dramatic increase in the aromatic
cluster size above 450C (as estimated by C NMR).
indicative of a substantial structural rearrangement
that would require a reduction in crosslink density
[2]. These findings are in close agreement with the
results of research on flame retardance [23,24]. The
peak in hydrogen evolution at 550C is an expected
consequence of aromatic condensation. The corrc-
sponding decrease in porosity is also consistent with
the occurrence of major structural reordering. whcrc
the increased size and alignment of clusters would
result in a more densely packed (and possibly more
anisotropic) structure. Over this same range of tem-
perature, the elimination of residual aliphatic and
oxygen-containing groups is consistent with the
observed secondary evolution of CH, and the disap-
pearance of infrared absorption bands due to ketones
and esters.
4. CONCLUSIONS
Phosphoric acid appears to function both as an
acid catalyst to promote bond cleavage reactions and
the formation of crosslinks via processes such as
cyclization, and condensation, and to combine with
organic species to form phosphate and polyphosphatc
bridges that connect and crosslink biopolymer frag-
ments. The addition or insertion of phosphate groups
drives a process of dilation that, after removal of the
acid, leaves the matrix in an expanded state with an
accessible pore structure. It is considered that activa-
tion of the amorphous polymers produces mostly
micropores, while activation of crystalline cellulose
produces a mixture of pore sizes. The different
response of crystalline cellulose is attributed to a
much greater potential for structural expansion than
IS possible with the amorphous polymers due, among
other factors, to its higher density and its chemical
structure that allows for a more extensive degree of
combination with phosphoric acid, and hence bulk-
ing of the cell walls. The pore size distribution
obtained from crystalline cellulose can be altered by
increasing the HTT and/or the ratio of acid to
precursor such that, eventually, the structure is domi-
nantly mesoporous. At temperatures above 450C a
secondary contraction of the structure occurs when
the phosphate linkages become thermally unstable.
The reduction in crosslink density allows the growth
and alignment of polyaromatic clusters, producing a
more densely packed and less porous structure.
I
2
i
3
3
6
7
x
Y.
IO.
I I
I?.
Ii.
14.
IS.
16.
17.
IX.
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