Carbon Vol. 36, No. 11, pp.

1557–1566, 1998
© 1998 Published by Elsevier Science Ltd
Printed in Great Britain. All rights reserved
0008-6223/98 $ — see front matter
PII: S0008-6223(97)00137-1

BEHAVIOR OF IMPREGNATED ACTIVATED CARBONS

HEATED TO THE POINT OF OXIDATION
Y. S, L. C. B,* and C. A. LD
U.S. Army, ERDEC, Aberdeen Proving Ground, MD 21010, U.S.A.

(Received 11 September 1996; accepted in revised form 20 June 1997)

Abstract—Activated carbons can be impregnated with metal oxides (Cr, Cu, Ag, Mo, Zn, Co) and/or
organic compounds (triethylenediamine ( TEDA)) to help capture high vapor pressure substances.
However, this process lowers the temperatures of initial oxidation and spontaneous ignition and affects
both the CO and CO effluent concentrations upon heating. This study quantifies the depression of the
2
point of initial oxidation (PIO) and attempts to find the cause of this depression for commercially
available impregnated carbons. PIO and effluent CO and CO concentrations were determined with bed
2
depths and linear flow rates specified by current military filtration parameters. The impregnated carbons
were repeatedly raised to their oxidation points and cooled, upon which it was found that each subsequent
reaction occurred at a slightly higher temperature with the PIO apparently asymptotically approaching
a value that was unique to each impregnant formulation. In order (from lowest to highest initial PIO)
the carbons tested were ASZM-T (Cu, Ag, Mo, Zn, TEDA), ASC (Cr, Cu, Ag), ASZM (Cu, Ag, Mo,
Zn), BPL-T ( TEDA) and, as a reference, unimpregnated BPL carbon (all supplied by Calgon, Pittsburgh,
PA). Thermal gravimetric analysis ( TGA) and differential scanning calorimetry (DSC ) were applied to
study the ignition mechanisms. Exothermic reduction of the chromium and copper oxides was found to
initiate oxidation of ASC and ASZM, respectively. Thermal decomposition of TEDA, followed by
copper oxide reduction, were found to be the initial steps in the ASZM-T ignition process. © 1998
Published by Elsevier Science Ltd. All rights reserved.
Key Words—A. Activated carbon, B. impregnation, C. thermal analysis.

1. INTRODUCTION in the unimpregnated carbon. Hardman [2] reported

that the SIT of a bituminous coal activated carbon
Filters that employ microporous impregnated car-
decreased from 420 to 245°C following impregnation
bons are used either to protect the environment from
with 5% w/w TEDA.
hazardous industrial effluents or for personal or
A second effect associated with carbon impreg-
collective protection in contaminated atmospheres.
nation is the increase in the concentration of CO
During these processes, temperatures may rise sig-
and CO in the effluent from the carbon beds as
nificantly above ambient, making the understanding 2
the temperature approaches the ignition point.
of the thermal behavior of the carbons of great
Hammarstrom [3] and Ehrburger [4] investigated the
operational and safety importance.
thermal deactivation mechanism of ASC whetlerite
Impregnated activated carbons are commonly used
and showed a series of oxidation processes taking
for the adsorption of high vapor pressure toxic gases
place between the carbon and the chromium and
(for example, cyanogen chloride and hydrogen cya-
copper complexes, resulting in CO and CO
nide). Although the composition of the impregnants 2
formation.
and the process of impregnation may vary, typical
The intent of this investigation is to contribute to
impregnants are salts of chromium, copper, silver,
the understanding of bed oxidation for a series of
zinc, cobalt, and molybdenum, and organic com-
commercially available, impregnated, activated car-
pounds such as pyridine and triethylenediamine
bons by measuring their points of initial oxidation
( TEDA).
and the amounts of CO and CO released when
A well known side effect of impregnation is that 2
heated. A further aim is to study ignition initiation
the spontaneous ignition temperature (SIT ) of the
for impregnated carbons by analyzing surface oxida-
carbon matrix is reduced. Dolian [1] reported the
tion processes.
SIT was lowered to 196°C from >283°C for a wood-
based activated carbon when it was impregnated with
chromium, copper, and silver (ASC carbon). When
a coal-based carbon was similarly impregnated, the 2. EXPERIMENTAL
SIT for ASC and ASC+1.5% pyridine carbons was 2.1 Activated carbons
lowered to 220 and 190°C, respectively, from >283°C All commercial activated carbons were supplied by
the Calgon Carbon Corporation. The base carbon
*Corresponding author. used by the manufacturer for the various impregnated
E-mail: lcbuettn@cbdcom.apgea.army.mil products was BPL, a bituminous coal based, steam
1557
1558 Y. S et al.
activated, granular carbon ( US mesh size 12×30).
Physical properties reported by the supplier include:
Total surface area (N BET ) 1050–1150 m g−1
2 intersect. The SIT was defined as the intersection of
Bulk density 0.48 g cm−3
Total pore volume 0.7 cm−3 g−1
Micropore volume 0.35 cm−3 g−1
Ash maximum 8%
The impregnant compositions of the tested carbons
were prepared at ERDEC, and are summarized in
Table 1. The metal carbonates were dissolved in a
water, ammonium hydroxide, and ammonium car-
bonate solution. This solution was added to the
activated carbon using the incipient wetness tech-
nique and dried in excess air. The TEDA was impreg-
nated into the metal carbon product by vapor
deposition. This method of impregnation is similar
to that used in work by Hammarstrom and Sacco
[3,5].
The ash content of the BPL consisted primarily of
silicon (~32%), aluminum (~26%), sulfur (~24%),
iron (~9.0%), calcium (~2.9%), titanium (~2.2%),
and potassium (~1.8%).
2.2 Apparatus for PIO and SIT measurements
and CO and CO emission determination
2 (7) cooling to room temperature.
A modification of ASTM’s ‘‘Standard Test Method
for Ignition Temperature of Granular Activated
Carbon’’ [6 ] was applied and extended to include
CO and CO concentration measurements in the
2
effluent air stream. Three operational changes from
the ASTM were necessary in order to study the
performance of a military filter: carbon samples were
analyzed as received without removing any fines, the
bed was deeper, and the linear flow velocity was
lower. A carbon bed contained inside a glass tube
(31 mm inner diameter, 52 mm bed depth) was
exposed to an ultra high purity mixture of N (80%)
2
and O (20%), flowing at a constant superficial
2
velocity of 22.9 cm s−1. The carbon bed and an inlet
air heat exchanger were placed inside a HP5890 Gas
Chromatograph oven to adequately control the tem-
perature. The pressure drop between the filter exit
and the vent was less than 5 in. of water. The CO
2
and CO concentrations in the effluent gas were
simultaneously recorded using a Wilks, MIRAN-80
Infrared Analyzer.
Table 1. Composition of impregnating ingredients (wt%) in activated carbons
Carbon Lot Copper Chromium oxide
BPL 0325G
ASC 1713 8 3
ASZM 4–6
ASZM-T C01142 4–6
BPL-T
BPL–Mo
BPL–Zn
BPL–Cu 12
2.2.1 Definition of the PIO and SIT. In these
experiments, the PIO was defined as the temperature
where the inlet and outlet temperature profiles
the linearized outlet temperature profiles before and
after ignition. The outlet temperature was obtained
with a thermocouple that was touching the down-
stream side of the carbon bed.
2.3 Temperature profiles for PIO measurement
All experiments for the measurements of the PIO
and the effluent CO/CO concentrations were pro-
2
grammed to include the following temperature
regimes:
(1) a linear temperature increase of 5°C min−1, from
50°C to the starting point (150 or 140°C );
(2) an isothermal equilibration at the starting
temperature;
(3) a linear temperature increase of 2°C min−1, to a
temperature 5–10°C above the PIO;
(4) a fast cooling to the starting temperature;
(5) an isothermal equilibration at the starting tem-
perature, prior to the next run;
(6) repetition of steps 3–5 for each of the four to six
consecutive runs;
2.4 Thermal analysis under N carrier
2
Differential scanning calorimetry (DSC ) and ther-
mal gravimetry (TG) measurements were simulta-
neously performed on a SETARAM instrument
(model TG–DSC 111). For the study of redox reac-
tions between the impregnants and the carbon, the
samples tested were kept in open, cylindrical, plati-
num crucibles, under N flow. The reference side of
2
the TG was balanced using BPL carbon of identical
weight to the impregnated sample that was tested.
Sample sizes were in the range of 18–20 mg, the
temperature range investigated was 150–450°C with
a heating rate 5°C min−1, and the gas flow rate was
set at 16 sccm. To ensure desorption of water vapor
collected during handling, carbon samples were kept
for 30 minutes at the initial temperature of 150°C.
DSC and TG thermograms were computed by
subtracting the respective reference curves obtained
with BPL carbon from the sample data.
Silver Zinc Molybdenum TEDA
<0.1
<0.1 4–6 1–3
<0.1 4–6 1–3 2–4
3
5
5
 Behavior of impregnated activated carbons heated to the point of oxidation 1559

3. RESULTS Table 2. Points of initial oxidation (°C ) for consecutive runs

and CO , CO concentrations (ppm) at these points
2
3.1 PIO measurement from temperature profiles
Figure 1 illustrates the temperature profiles, with Run 1 2 3 4 5 6
six consecutive PIO measurements in a typical experi- ASC PIO 188 205 214 217 220 222
ment with ASC carbon. This figure shows that: 1) in CO 320 350 375 325 385 400
2
the region prior to the PIO, because of the heat CO 95 95 65 30 25 15
capacity of the carbon, the outlet is slightly lower ASZM PIO 230 241 246 250
CO 470 445 420 425
than the inlet temperature; 2) at the PIO the two CO
2
10 5 5 5
temperatures intersect; and 3) after the PIO, the ASZM-T PIO 158 163 171 179 187 195
outlet temperature is greater than that at the inlet CO 270 300 325 400 445 480
2
due to carbon oxidation. Figure 1 also shows that CO 25 25 30 35 40 45
the PIO, indicated by arrows, rises significantly with BPL PIO 360 >375 >375
CO 420 305 270
consecutive runs. Table 2 summarizes the oxidation 2
CO 215 145 130
temperatures and CO/CO concentration (averaged BPL-T PIO 348 375
2
over 2–3 repetitions) obtained with the impregnated CO
2
370 360
activated carbons studied. CO 170 170
The ASTM defined SIT and the PIO are shown
in Fig. 2 for ASC carbon beds for both ASTM
dimensions (25 mm diameter, 25 mm deep, 3.2 CO and CO concentration profiles
2
50 cm s−1 linear flow velocity [6 ]) and military filter The filter effluent was analyzed for CO and CO
2
bed depth and linear flow velocities (31 mm diameter, concentration in one minute intervals. Figures 3 and
52 mm deep, 22.9 cm s−1 linear flow velocity). This 4 illustrate the concentration profiles of the two
figure indicates the effect of operational parameters gases obtained with the various activated carbons.
on the ignition of the carbon and also indicates the To permit a visual correlation between temperature
differences between the SIT and the PIO as reported and gas emissions, profiles of the inlet and outlet
in this paper. temperatures are also shown on these figures.

Fig. 1. Inlet and outlet temperature profiles observed when a sample of ASC activated carbon and the air flowing through it
are heated at a constant rate of 2°C min−1. The PIO is defined as the point where the outlet and inlet temperature profiles
cross, indicated by arrows. Then, the temperature of the sample was lowered to the starting temperature. In successive iterations
the PIO increased for all samples.
1560 Y. S et al.

Fig. 2. Inlet and outlet temperature profiles observed when a sample of ASC activated carbon and the air flowing through it
are heated at a constant rate. See the methods section for complete description of experiment. The SIT is defined as the
intersection of the linearized outlet temperature profile before and after ignition, this is indicated with the arrow and the word
‘‘SIT’’. The PIO is defined as the point where the outlet and inlet temperature profiles cross, indicated by arrows with ‘‘PIO’’
attached.

Figures 3 and 4 show CO off-gassing during the 3.3 Thermal analysis

2
initial stage of heating to the starting temperature
for the metal oxide impregnated carbons (ASC,
ASZM, ASZM-T ). In the same temperature range,
the CO concentration was negligible in the base
2
carbon (BPL) and in the sample that was only
impregnated with TEDA. In all samples, CO emission
is less than 25 ppm in the same temperature range.
These low temperature CO and CO emissions are
2
associated with the thermal decomposition of chemi-
sorbed oxygen complexes and have been observed in
commercial impregnated carbons when heated in air
or a nitrogen atmosphere [7]. These complexes would
have been generated in the impregnation process in
a manner promoted by the added metals.
PIO measurement was terminated at temperatures
5–10°C above the oxidation point, at which point
the CO upper detection limit of 1000±200 ppm was
2
reached. It is worthwhile emphasizing the negligible
CO quantities detected with ASZM and ASZM-T
carbons and the continuous decrease in the peak CO
concentration in the consecutive runs with BPL,
BPL-T, and ASC carbons. Table 2 summarizes the
CO and CO concentrations detected at the oxidation
2
temperature.
Figure 5 shows the ASZM-T thermograms, as an
illustration of typical DSC/TG thermal analysis
curves. The DSC curve in this figure contains two
exothermic peaks, one at 230°C and the other at
300°C. At the same temperature range the TG curve
shows two different regimes of weight decrease, con-
firming the presence of thermal activity. Therefore,
the DSC curves were used for the location of thermal
reactions and calculations of the respective reaction
heats, while TG curves were used to confirm the
temperature range observed by the DSC measure-
ments and for mass balance.
Figure 6 combines the DSC curves of two commer-
cial impregnated carbons. The ASC carbon exhibited
two partially overlapping exothermic peaks, at
210–270°C and 270–350°C, indicating a redox reac-
tion occurring between the carbon and the supported
impregnants. With ASZM carbon only the second
peak appeared, indicating that the origin of that peak
is the component common to the two carbons, copper
oxide. The first exothermic peak of ASC is therefore
probably due to both chromium oxide reduction
from Cr+6 to Cr+3, as previously reported [4,7], and
decomposition of any copper–chromate complexes.
 Behavior of impregnated activated carbons heated to the point of oxidation 1561

Fig. 3. BPL carbon (a) and ASC carbon (b) CO and CO outlet concentration profiles are superimposed on inlet and outlet
2
temperature profiles that were obtained by heating a bed of carbon and the air flowing through it at a constant rate of
2°C min−1.

To test if Mo or Zn oxides of ASZM carbon influence
the location or intensity of the exothermic peak at
300°C and to confirm that copper oxide is responsible
for the second exothermic peak, a series of BPL-
based carbons impregnated with one of the metals
was analyzed. Figure 7 shows that the only exother-
mic peak was seen with the BPL–Cu pattern; no
peak occurred with either the BPL–Mo or BPL–Zn
carbons.
To confirm the peak assignments of the DSC
thermograms for ASC carbon, XPS analysis on three
samples was performed: one sample was heated to
150°C for 40 minutes (serving as a control ); the
second sample was heated from 150 to 225°C at a
rate of 5°C min−1 and immediately cooled (this repre-
sents the low temperature exotherm in the ASC
sample, see Fig. 6); the third sample was heated from
150 to 350°C at 5°C min−1 and then cooled. The
three samples were analyzed with XPS. In the sample
exposed at 150°C, the majority of the copper is
present as copper(II ) and the majority of the chro-
mium is present as Cr( VI ). There was evidence of
Cu(I ) and Cr(III ) (about 30%) in the spectra.
Previous results have demonstrated that the copper
associated with ASC whetlerite is predominantly
Cu(II ) [8]. Upon heating the sample to 225°C, the
fraction of chromium(III ) is increased to approxi-
mately 55–60%. In addition, there is an increase in
the fraction of Cu(I ) oxide, suggesting that a simulta-
neous decomposition of the copper–chromate com-
plex has occurred. When heated to 350°C, the
chromium(III ) increases marginally, but the copper
is almost completely reduced to copper(I ) oxide.
The XPS results indicate that the low temperature
exotherm is due to reduction of the copper–chromate
complex to chromium(III ) oxide and copper(I )
oxide and to chromium( VI ) reduction. The higher
temperature exotherm is due to the reduction of
copper(II ) oxide to copper(I ) oxide.
DSC patterns of ASZM-T and BPL-T carbons are
compared in Fig. 8. The ASZM-T curve demon-
strated two exothermic peaks. The first peak, in the
1562 Y. S et al.

Fig. 4. Effect of adding TEDA to ASZM carbon, as shown on the PIO and the CO emissions. ASZM which does not contain
2
TEDA is shown in (a); its PIO is lower than that of the non-impregnated base carbon but it is significantly higher than that
of the same carbon with the addition of TEDA (b). (c) shows that, although the effect of TEDA addition is significant for
the impregnated carbon, when it is sublimated onto base BPL carbon, it alone does not drastically decrease the PIO.

temperature range of 200–260°C and common to
both TEDA impregnated samples, is consistent with
the exothermal reaction between the TEDA and the
carbon matrix. On the other hand, the second peak
(present in the ASZM-T but not apparent in the
BPL-T ) is consistent with the one expected from the
copper oxide reduction as seen in the ASZM curve.
4. DISCUSSION
4.1 PIO versus ASTM SIT measurements
A comparison between the SIT and the PIO shows
that the PIOs occur at lower temperatures than the
SITs (see Fig. 2). This difference was expected, due
to the difference in the property studied: this study
defines the PIO as the intersection of the inlet and
outlet temperatures, whereas SIT is defined in this
study as the intersection of the slopes of the outlet
temperature before and after ignition. This slope
intersection technique can lead, in some cases, to
significant overestimation of the inlet air temperature
that will ignite a carbon bed [10].
The two sets of operational parameters are respon-
sible for the different SIT and PIO values. In the
high linear velocity regime of 13–50 cm s−1, charac-
terized by large oxygen availability [11], increasing
the carbon bed depth (from 25 to 52 mm) and the
diameter (from 25 to 31 mm) results, for a given
superficial velocity, in lowering the PIO and the SIT.
The larger dimensions create better thermal isolation
and, consequently, lead to lower heat loss. Lowering
the superficial velocity from 50 to 22.9 cm s−1 reduces
 Behavior of impregnated activated carbons heated to the point of oxidation 1563

Fig. 5. DSC and TG thermograms for ASZM-T activated carbon in flowing N are simultaneously graphed. The reference
2
side of the TG was balanced and a reference curve derived from base BPL carbon was subtracted from the data. The TG
curve indicates two regions of weight decrease; this thermal activity is confirmed by the presence of two exothermic peaks of
thermal activity as shown on the DSC curve.

the PIO and the SIT because the particle–gas heat
transfer rate is decreased.
4.2 Effect of impregnants on PIO values
The oxidation points of the various activated car-
bons, as measured by the initial run of each test, are
given below in descending order:
BPL (360°C ) >BPL-T (348°C ) >ASZM (230°C )
>ASC (188°C ) >ASZM-T (158°C )
Comparison between ASZM-T and ASZM carbon
illustrates the effect of surface deposited TEDA on
the PIO: the addition of 3% TEDA resulted in a
70°C reduction of the oxidation point. This result
differs from the findings of Hardman et al. [2] with
UK 207 B carbon (unimpregnated, bituminous coal
based ), who stated that a TEDA concentration of
5% is critical for significant exothermal effects.
However, this TEDA surface concentration does not
suffice to cause the ignition of the base BPL carbon,
as seen by comparing the PIO values of this and the
BPL-T carbons. The metal oxide complexes are,
therefore, a required link in the chain of oxidation
reactions with the surface and the consequent temper-
ature wave formation. This starts with the TEDA
reaction, is amplified by reduction of impregnants,
and terminates with the carbon oxidation by oxygen
in air.
Figures 3 and 4 and Table 2 show that in the
consecutive runs of the samples tested, the PIO
gradually rises to a terminal value. We postulate that
this is caused by matrix heterogeneity, since the most
vulnerable sites would preferentially oxidize at the
lower temperatures. Impregnant concentration
change with consecutive tests cannot be the only
reason for this phenomenon, as the limiting value of
the PIO is far lower than the oxidation temperature
of the base BPL carbon expected if loss of all
impregnants occurred.
Impregnant decomposition is not solely responsible
for the large amounts of CO and CO detected. A
2
mass balance shows that the gas quantities emitted
are larger then those expected by reduction of the
impregnants. This leads to the conclusion that, with
surface oxidation of the impregnants, high local
temperature can cause the nearby carbon to oxidize
in the presence of oxygen supplied by the gas phase.
The heat released from these localized hot spots
expands and moves down the bed until the resulting
temperature is high enough to ignite the bulk carbon.
4.3 CO and CO formation at temperatures
2
below SIT
The formation of carbon monoxide and carbon
dioxide at temperatures below the SIT has been
previously reported for unimpregnated coconut shell
carbons [9,12]. The source for the gas formation in
1564 Y. S et al.

Fig. 6. DSC thermograms for ASZM and ASC carbons in flowing N are simultaneously graphed. The reference side of the
2
TG was balanced and a reference curve derived from base BPL carbon was subtracted from the data. The ASC carbon has
two exothermic peaks, the second of which corresponds to the only peak observed in the ASZM carbon. This indicates that
the second peak is probably the result of the common impregnant between the two samples, copper oxide. As previously
reported [4,7], the first ASC peak is probably the result of Cr+6 to Cr+3 reduction.

this temperature range is the thermal decomposition
of a highly reactive surface layer of oxygen-contain-
ing complexes. It has been previously reported that
the process is not affected by oxygen concentration
in air [7], and is reduced greatly after the samples
were heated to the SIT [9,12].
Oxygen-containing complexes usually cover less
than 1% of the surface [8] and, since the impregnants
are primarily attracted to them, the impregnants are
probably preferentially situated in the mesopores
rather than the micropores of the carbon pore net-
work. Therefore, considering the effect of that surface
layer on carbon properties, we believe that it is of
minor importance concerning physical adsorption
and micropore filling or oxygen diffusion, although
it is of great significance to the adsorption of polar
compounds, such as water vapor.
Figures 3 and 4 show decreasing production of
CO and CO with each subsequent cycle of heating
2
and cooling. One possible reason for the decreasing
subsequent CO and CO production is that a portion
2
of the surface-oxygen complexes thermally decom-
pose during the initial temperature ramp. Since that
emission is reduced during the first heating to the
PIO, a gradual reduction in emissions is witnessed
in the following runs.
In addition, Table 2 indicates that the CO /CO
2
ratio at the PIO for metal oxide impregnated carbons
is greater than for base carbon. It is possible that
this is related to catalytic oxidation of CO to CO
2
over the metal.
4.4 ASC activated carbon ignition
characteristics and mechanism
As shown in Table 2, the first PIO of the ASC
activated carbon is at 188°C and it increases after six
consecutive heatings to 222°C. In the thermal analysis
tests of that carbon (Fig. 6) we observed a large
exothermic peak at 240°C, which is the extreme point
of thermal activity starting at 180–190°C. As pre-
viously shown, that activity originates in the redox
reaction with chromium oxide and, eventually, as
reported by Ehrburger [4] and Hammarstrom [3], in
the reduction of the hexavalent chromium to the
trivalent chromite. Using the heat of this reaction,
DH=−303 kJ mol−1 CrO [4] for a simplified calcu-
3
lation and assuming no heat loss to the gas phase, it
can be shown that the carbon (C =0.15 cal/g °C ),
p
containing 3% w/w CrO in a reacting layer, can
3
reach a temperature of 140°C above the initial tem-
perature. Therefore, in a cylindrical bed of ASC
carbon, heated to temperatures high enough to initi-
 Behavior of impregnated activated carbons heated to the point of oxidation
Fig. 7. DSC thermograms in flowing N of BPL that has been impregnated with Cu, Zn, or Mo are superimposed on the DSC
2
result from the ASZM-T carbon. The only impregnant that generated an exothermal peak is the Cu.
ate chromium reduction, a hot front could be created
and sustained unless the temperature is reduced and
the exothermal reaction quenched. The oxygen in the
air could intensify this local carbon oxidation and
result in a thermal wave that grows hot enough to
eventually ignite the bulk carbon.
In the temperature range above 200°C and with
excess O (that is, with a sufficient flow rate that the
2
oxygen concentration is not measurably decreased
by passing through the bed), the prime oxidation
product observed in these experiments is CO , as
2
seen in Fig. 3. CO concentrations at the PIO for the
2
various runs are consistent for each sample and do
not exceed 400 ppm. On the other hand, the concen-
tration ratio of the two gases, CO and CO, is
2
increased, from 3.5 in the first run to more than 25
in the last. The reason for the decreasing amounts of
CO produced in the PIO range is not clear. It appears
that CO concentration variations in the vicinity of
the consecutive PIO measurements are caused pri-
marily by carbon heterogeneity, rather than by PIO
rise or changes in the active surface area.
4.5 ASZM activated carbon ignition
The first oxidation point found for this carbon is
230°C and it increases in the four consecutive runs
to 250°C. The reaction in this case is triggered by
the thermal activity of the copper oxide, found in the
surface impregnation in the amount of 4–6% w/w.
1565
As seen in the thermogram of ASZM in Fig. 6,
exothermal activity is evident at a temperature of
230°C, with a peak at 290°C. This exothermal reac-
tion is consistent with the reduction of bivalent to
monovalent copper [4,7], with a heat of reaction of
38.5 kJ mol−1 CuO [4]. As seen in Fig. 7, Mo and
Zn oxides do not show any thermal activity in this
temperature range and do not therefore affect the
mechanism of ASZM oxidation.
4.6 ASZM-T activated carbon ignition
The PIO of the ASZM-T activated carbon
increases from 158°C in the first cycle to 195°C in
the sixth one. As seen in the thermal analysis curves
(Fig. 8), this carbon is characterized by two
exotherms. The first is related to the surface decom-
position of TEDA, in the range of 190–250°C, while
the second is similar to the peak encountered in the
ASZM carbon, originating from the reduction of the
copper oxide. These two exothermal reactions act as
the initial steps in the ignition chain mechanism,
namely:
Thermal decomposition of TEDA ————
Reduction of CuO ———— Carbon oxidation at
hot front ———— Temperature rise as a heat
wave ———— Bulk carbon ignition
CO concentration in the effluent increases from
2
270 ppm in the first run to 480 ppm in the sixth. CO
concentration increases proportionally from 25 to
1566 Y. S et al.

Fig. 8. DSC thermograms in N of BPL-T and ASZM-T activated carbons. The first ASZM-T exothermal peak is similar to
2
the first peak in the BPL-T sample, indicating that this peak is probably caused by the addition of the TEDA to the sample.
The second ASZM-T peak is consistent with the Cu peak observed in the BPL–Cu sample.

45 ppm with the concentration ratio of CO to CO of ERDEC, provided carbon samples and physical proper-
2 ties of the materials.
constant at a value of 11.

5. CONCLUSION
The concept of a point of initial oxidation (PIO)
is defined and discussed, this is the temperature where
the outlet temperature of a carbon bed that is being
uniformly and steadily heated exceeds the inlet tem-
perature. This temperature is of importance for sev-
eral reasons: (1) it is an easily measurable point, (2)
it acts as an indicator of chemical surface modifica-
tion, and (3) it can be derived from the current
ASTM method without major modifications.
The ignition mechanisms of activated carbons were
investigated. Using TGA, DSC, and XPS a plausible
ignition scheme for impregnated activated carbons
was covered. For ASC carbon, the initiating sequence
is a combination of chromium reduction and
chromium–copper complex decomposition. In
ASZM carbon, the exotherm is initiated by copper
reduction. For ASZM-T, the initiator was the decom-
position of the TEDA.
Acknowledgements—This work was performed while one of
the authors ( Y. S.) held a National Research Council –
ERDEC Research Associateship. Joseph Rossin and Jeffrey
Campbell of Guild Associates performed the XPS analysis
for this paper. Chris Karwacki and Robert Morrison, both
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