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Vapour Breakthrough in Activated Carbon Beds

Article  in  Carbon · December 1993

DOI: 10.1016/0008-6223(93)90033-7

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Curbon. Vol. 31. No. 2, pp. 279-286. 1993 OOLJ8-6223/93 $6.00 + .@I
Printed in Great Britain. Copyright 0 I993 Pergamon Press Ltd.

VAPOUR BREAKTHROUGH IN ACTIVATED CARBON BEDS

ODD BUSMUNDRUD
Norwegian Defence Research Establishment, Division of Environmental Toxicology, P.O. Box 25,
N-2007 Kjeller, Norway

(Received 26 May 1992; accepted in revised&m 1 July 1992)

Abstract-Detailed measurements of vapour breakthrough in activated carbon beds have been made for
dimethyl-methylphosphonate (DMMP) and n-amylacetate. The measurements have been interpreted in
terms of rate constant and adsorption capacity. The breakthrough curve follows the theoretical predictions
at low output concentrations, but deviates at high concentrations. The rate constant is found to be very
dependent on air velocity and grain size of the carbon. In the case of humid carbon and humid aid, the
rate constant decreases, while the adsorption capacity is very little influenced by humidity.
Key Words-Activated carbon, vapour breakthrough, DMMP, n-amylacetate, carbon filters.

1. INTRODUCTION It can be shown[3] that this breakthrough equa-

tion is the same as the equation derived by Bohart
The dynamic behavior of activated carbon beds chal-
and Adams[4] which is the basis for the modified
lenged with air containing vapours is of great interest
Wheeler equation.
in connection with protection against harmful sub-
It can further be shown[3] that:
stances. Although there is a general understanding of
the adsorption mechanisms, still there are many un-
answered questions. As an attempt to increase the
&,I&-
PSW,
knowledge, some detailed measurements of vapour
breakthrough in carbon beds have been undertaken. and
The time dependence of vapour breakthrough in ac-
tivated carbon beds has been measured for dimethyl- r=Eln[exp(F)- 11, (4)
methylphosphonate (DMMP) and n-amylacetate.
The complete breakthrough curves have been mea-
sured, and an analysis in terms of adsorption capacity where L = height of adsorbent bed, VL = superficial
and (first-order) rate constant has been performed. linear velocity.
The analysis of vapour breakthrough in adsorbent Equation (2) can be written:
beds is often done in terms of the modified Wheeler

Ini c,-c,=Ir(t
C
equation[ 1). This gives the breakthrough time as:
) - T).

(1) Inserting eqns (3) and (4) into (5) gives:

C
where fh = breakthrough time, C, = exit concentra-
tion at breakthrough, C, = inlet concentration, Q =
volumetric flow rate, A4 = weight of adsorbent, pB =
Ini * 1
=%I-ln[exp(k,$)- 1] (6)
bulk density of the packed bed, W,. = adsorption ca-
pacity (mass of adsorbed vapour/mass of adsorbent
at concentration C,,), k, = rate constant. Accordingly,
Obviously, this equation can only be valid for
C
small exit concentrations, since the equation predicts
an exponentially increasing exit concentration with
time.
Ini c,-c, 1
Yoon and Nelson[2] have presented a semi-em- plotted versus time should give a straight line. In the
pirical gas adsorption model which gives an equation analysis of the data, this is used to describe the ad-
predicting the whole breakthrough curve. Their sorption process in terms of adsorption capacity and
model gives the exit concentration as rate constant. As the experimental results will show,
this linear relationship is valid only over a limited
1 range of output concentrations.
(2)
cX = Co 1 + exp [K(T - t)] ’ In all practical cases,

where k’ is a rate constant, r = 50% breakthrough

time.

279
280 0. BUSMUNDRUD

Equation (6) can then be written:
t-k+ (7)
L were collected on a personal computer, and processed
2. EXPERIMENTAL PROCEDURE
2.1 Materials
The activated charcoal used for most of the mea-
surements was of the type ASC 12 X 30 TEDA from
Chemviron. This is impregnated with trietylenedi-
amine (TEDA) in addition to copper, chromium and
silver salts, and has a mesh size between 12 and 30.
The bulk density pBwasfound to be 568 kg/m’. A few
tests were made with ASC 12 X 30 carbon which is
not impregnated with TEDA. No significant differ-
ences were found between this and the TEDA car-
bon. Also, some measurements were made with ASC
8 X 20 carbon in order to investigate the influence of
grain size. All carbons were dried in air at a temper-
ature of 120 “C for at least 24 h before being used.
The adsorbates used were dimethyl-methylphos-
phonate (DMMP), 97% from Janssen Chimica, and
n-amylacetate, 99% from Aldrich-Chemie.
2.2 Measurement procedure
The performance of an adsorbent bed is often
given in terms of breakthrough time, which is the
time for the output concentration to reach a certain
level with a fixed input concentration. Other mea-
surements[5] have shown the breakthrough time in
carbon beds to be proportional to the contact time.
Therefore, the contact time has been considered as
one of the parameters studied in this investigation.
The vapour was generated by injecting the liquid
from a syringe pump into the air stream. The air was
either dry (RH < 5%), or had a relative humidity of
80%. To generate air of known relative humidity, air
with a relative humidity of 100% was mixed with dry
air. The humid air was produced by bubbling the air
through a vessel filled with water. In order to give
good contact between the water and air, the vessel
was filled with washed gravel. The relative humidity
was measured with a Vaisala HMI 31 humidity in-
dicator.
The sample holder was a replaceable glass tube
with a diameter of 2.3 cm placed inside a teflon en-
closure. The lower end of the glass tube was closed
with a metal mesh. The carbon was filled into the
sample holder using a funnel with a double wire cross
to effectively spread the carbon granules and ensure
tight packing of the bed. The junctions of a copper-
constantan thermocouple pair were placed above and
below the carbon bed to measure the temperature.dif-
ference across the filter. The measurements were
done at the ordinary laboratory temperature of 22-
24 “C.
The vapour concentration was measured using a
MIRAN A 1 infrared absorption detector. The wave-
length used for detection of DMMP was 12.4 pm and
for n-amylacetate 8.1 pm. The length ofthe light path
was in both cases 20.25 m. The analog data from the
MIRAN and thermocouple were digitised using An-
alog Devices 6B signal conditioning modules. Data
using standard software.
2.3 Data analysis
The data were analyzed in terms of adsorption ca-
pacity (WC)and rate constant (k,) from eqn (7). Since
the plots of
C
(
In c,-c, )
versus time were not linear over the entire break-
through range, the first part (lowest breakthrough
concentration) was used. This part of the break-
through curve was most linear. In addition, for pro-
tection against highly toxic substances, this is the
range of interest. Therefore, the ratios ofinput to out-
put concentrations used for determination of adsorp-
tion capacity and rate constants were between 100
and 100,000. This is different from many other stud-
ies, where ratios of 100 or lower are used.
To find the adsorption capacities and rate con-
stants, a straight line (a . t - b) was fitted to the data
points. From eqn (7), it can be seen that
k,c,
b=k,+ and a=
L PBWC’
Accordingly,
k, = b . $ =b . ?- and W, = z.
L Q . PR
Most of the measurements have been made with a
contact time of 0.15 s. However, some measurements
have been made with other contact times. In most
cases, the concentration was 2.2 mg/l for DMMP and
3 mg/l for n-amylacetate. Some measurements with
other concentrations of DMMP have also been
made.
2.4 Measurements with DMMP
DMMP is often used as a simulant for toxic or-
ganophorphorus compounds. The physical proper-
ties are close to the properties of the nerve agent
Soman. The boiling point of DMMP is 18 1 “C.
Figure 1 shows the breakthrough curves for con-
stant contact time with different superficial linear ve-
locities. This means that the amount of carbon is pro-
portional to the velocity. The output concentration is
plotted as
c
(
In c,-c, 1
versus time. As shown in Fig. 1, the breakthrough
time, especially at low breakthrough concentrations,
 Vapour breakthrough in activated carbon beds 281

Breakthrough of OMMP in ASC 12x30 TEOA Carbon Comporison of measured ond colculoted
Contact time 0.15 s. Concentration 2.2 ma/l rote constants

_2_ 0 V,= 0.06 m/s 1

A V,= 0.10 m/s .d

,’
-‘I-0 V,= 0.20 m/s ,’
/'
? 300- q ,'
3 _6_ = V,= 0.40 m/s /'
I q ,/ q
v)
I-Y #'
\- -8- 9 /
u” 2 zoo- /'
2 -10 q 0 ,,Q
d 0 x B ,'
5 P
-12- d 0 x #'
:: IOO- P'
s !Y'
-14 "I '. 8 "I", "I"""'. 8 ,a.
0 30 60 90 120 150 180 210 240 /'
Time (min.)
0 100 200 300 400
Fig. 1. Time dependence of breakthrough concentration Calculated values (l/s)
for constant contact time and varying superficial linear
velocity. Fig. 2. Comparison between measured rate constants and
values calculated from eon (9) for DMMP in ASC 12 X 30
TEDA carbon.
increases considerably with increasing air velocity.
Also, the breakthrough curve is not linear as should
be expected from eqn (6). The same type of nonlinear
breakthrough curves have been found in other simi- k, = 260 . VLo.43,
lar measurements[5]. In addition, measurements
with different contact times have been made. where VLis in m/s.
As Fig. 1 shows, the slope of the breakthrough By assuming the same dependence on the velocity
curve is clearly dependent upon the air velocity. By for other contact times, and assuming that the com-
using eqn (7) the rate constant k, and dynamic ad- plete expression for the rate constant can be written
sorption capacity W, can be calculated by fitting a as a product of eqn (8) and an exponential function
straight line to the data points for the lowest break- of the contact time, the following expression for k,
through concentrations. Table 1 shows these values can be found using a curve fitting program.
for the measurement with DMMP in dry carbon.
As shown in Table 1, the rate constant increases k, = 370 . L$?’ . (exp( - I%,) + 0.60). (9)
with increasing linear velocity. This is to be expected
if the rate limiting process is the diffusion of vapour A comparison between the measured values for
to the surface ofthe carbon granules[6]. The same de- k, and values calculated from eqn (9) is shown in Fig.
pendence on velocity has been found in other exper- 2.
iments[5]. Theoretically, the rate constant should be Equation (9) should be considered as a convenient
proportional to the square root of the velocity. empirical expression. The reason for the variation of
A closer examination of Table 1 also reveals that the rate constant with contact time is not known.
the rate constant seems to be dependent on the con- The adsorption capacity shows some variations
tact time. However, for constant contact time, a between the individual measurements, and there
power law is closely followed. The data for contact seems to be a small increase in adsorption capacity
time 0.15 s give the following expression for the rate with increasing bed height. Since the bed.height in
constant: most cases increases with air velocity, the adsorption

Table 1. Overview of measurements with DMMP in ASC 12 X 30 TEDA carbon

Linear velocity Weight of carbon Contact Adsorption Rate constant

(m/s) (g) time (s) capacity (s-l)

0.050 3.15 0.31 0.31 68

0.050 1.875 0.15 0.28 77
0.060 2.5 0.17 0.30
0.10 3.75 0.15 0.29 ;:
0.20 7.5 0.15 0.29 132
0.40 15 0.15 0.35 168
0.40 7.5 0.075 0.31 257
0.80 20 0.10 0.33 291
0.80 20 0.10 0.34 255
0.80 10 0.05 0.30 343
282 0. BUSMUNDRUD
Table 2. Adsorption capacity and rate constants for different concentrations
Linear velocity Contact Concentration
(m/s) time (s) (mg/l)
0.40 0.15 2.2
0.40 0.15
0.80 0.10
0.80 0.10
capacity may also increase with air velocity. How-
ever, the data are better correlated with bed height
than with velocity. A best fit of a straight line to the
points gives:
W, = (0.0065 f 0.0016) . L
+ (0.285 f 0.007), (10)
where L is the bed height in cm (found from the car-
bon weight, the area of the sample tube and bulk den-
sity). The correlation coefficient is r = 0.83. (The cor-
relation coefficient for a fit with velocity is only 0.49.)
The static adsorption capacity was found to be 0.38
g/g from the weight increase of a carbon sample ex-
posed to a stream of air containing 2.2-mg/l DMMP
until equilibrium was obtained.
A few measurements with vapour concentrations
of 0.8 and 4.1 mg/l were made. Calculations of rate
constants and adsorption capacity for these cases are
shown in Table 2. As the table shows, variation of va-
pour concentration in this range does not have any
significant influence on the adsorption capacity or
the rate constant. The static adsorption capacity at
0.8 mg/l was found to be 0.34 g/g and was not mea-
sured at 4.1 mg/l.
The grain size of the carbon may have a significant
effect on the dynamic adsorption properties of a car-
bon bed in the case of the adsorption process being
dependent on the mass transfer rate to the granule
surface. For the mass transport being the limiting
process, Wheeler[6] gives the dependence on grain
size as k, = Ka’.s, where a is the diameter of the gran-
ule, and K is a constant. In order to investigate this,
some measurements were made with carbon ASC
8 X 20. Two breakthrough curves for DMMP in ASC
8 X 20 carbon are shown in Fig. 3. The rate constants
and adsorption capacities for the two cases are shown
in Table 3.
As shown, the rate constant is significantly depen-
dent on gram size. Since the carbons in question have
a range of grain sizes, no direct comparison with the-
ory is possible. However, a crude comparison can be
made by assuming an average grain size. In the case
of 12 X 30 carbon, the (arithmetic) average grain size
is l.l4mm,andfor8 X 20carbonitis 1.61 mm(cal-
culated from the sieve openings of the mesh). The ex-
pected ratio of the rate constants from these sizes
should be 1.68. The values found from Table 3 are
I .7 1 and 1.45, respectively, for the two different ve-
locities, with an average of 1.58. This is in reasonable
agreement with the expected dependence of rate con-
Adsorption Rate constant
capacity (s-l)
0.35 168
0.32 166
0.34 255
0.21 256
stant on grain size. The adsorption capacity does not
seem to depend on grain size. The static adsorption
capacity of ASC 8 X 20 carbon was found to be 0.37
g/g at 2.2 mg/l.
2.5 Measurements with n-amylacetate
N-amylacetate was chosen as another test sub-
stance, since its vapour pressure and molecular
weight are close to the values for the nerve agent
Satin. N-amylacetate has a boiling point of 142 ‘C.
(N-amylacetate was chosen in preference to iso-amy-
lacetate because the MIRAN turned out to be more
sensitive to n-amylacetate than to iso-amylacetate.)
The experimental method was the same as for
DMMP, but the concentration was 3 mg/l. The re-
sults for contact time 0.15 s are shown in Fig. 4. A
summary of the results is shown in Table 4.
In this case, there seems to be no variation of the
rate constant with the contact time. The rate constant
is also in this case found to obey a power law. The ex-
ponent is 0.50 f 0,06 s-l. This is the same as the the-
oretical value. The rate constant can be written:
k ” = 296 - vt”. (11)
As in the case of DMMP, the (dynamic) adsorption
capacity seems to be dependent upon the amount of
carbon in the bed. With the bed height, L given in cm,
the adsorption capacity can be written:
w, = (0.011 f 0.003) . L
+ (0.15 f 0.02). (12)
Breakthrough of OWMP in ASC 8x20 carbon
Contact time 0.15 e. Concentration 2.2 ma/l
Fig. 3. Breakthrough of DMMP in ASC 8 X 20 carbon.
Contact time 0.15 s.
 Vapour breakthrough in activated carbon beds 283

Table 3. Comparison of rate constants and adsorption capacities for ASC 12 X 30

TEDA and ASC 8 X 20 carbon

Linear velocity Type of Adsorption Rate constant

(m/s) carbon capacity (s-l)
0.20 12 x 30 0.29 132
0.20 8X 20 0.30 77
0.40 12 x 30 0.35 168
0.40 8x 20 0.33 116

Contact time 0.15 s.

Breakthraugh of n-amyacetate in AX 12x30 TEOA carbon Accordingly, measurements were made with car-
Contact time 0.15 s. dry air bon in equilibrium with air at 80% RH, and the rel-
ative humidity of the air was 80% during the mea-
-2
surements. In order to assess equilibrium, the
-4
temperature across the carbon bed was measured
during the initial adsorption of water vapour. Figure
, -6 5 shows the temperature difference across the filter
4
L? bed for the first part of the water adsorption process.
‘$ -8 There was probably some heat loss across the walls
e 0 v, - 0.10 m/a
c of the filter holder. Accordingly, the temperature in-
- -10 1 V’_ - 0.20 M/E
crease cannot be used to calculate the heat of adsorp-
0 v, - 0.40 m/s
-12 tion of the water vapour. Equilibrium was assumed
3 ~ 0

0
A
-14 ” ” #’ B.
0 30 60 90
Time (min.)
Fig. 4. Breakthrough of n-amylacetate in ASC 12
TEDA carbon.
The correlation coefficient is r = 0.90. (The correla-
tion coefficient with air velocity is 0.80.) The static
adsorption capacity was measured to be 0.29 g/g at 3
mg/l.
2.6 Measurements with humidity
Adsorption of vapours from humid air is a com-
plex process. The influence of water may depend on
the other adsorbate, and on the measurement proce-
dure. Aside from the obvious dependence on temper-
ature and water vapour concentration, one should
expect different results depending on the starting con-
dition of the carbon and on the concentration of the
adsorbate. If the measurements are started with dry
carbon, the results could be quite different from mea-
surements starting with carbon in equilibrium with
the humid air. In order to have the best possibly de-
fined initial state, the carbon should be in equilib-
rium with the air at the onset of adsorbate vapour.
when the temperature increase across the carbon bed
“. was less than 0.5 “C. This took 4-24 h, depending on
120 150
the amount of carbon and air velocity.
Adsorbed water in the pores of activated carbon
x 30 would be expected to reduce the volume available to
other adsorbates, thereby reducing the adsorption ca-
pacity of the carbon bed. However, the adsorption
isotherm for water in activated carbon is quite differ-
ent from the adsorption isotherm for most other va-
pours. Most other vapours are more easily adsorbed
by the carbon than water. Accordingly, already ad-
sorbed water may be expelled from the carbon by
other vapours being adsorbed. One significant differ-
ence between DMMP and n-amylacetate is that
DMMP is water soluble, while n-amylacetate is not.
2.6.1 Measurements with DMMP. Figure 6
shows the breakthrough concentration for DMMP in
carbon equilibrated with air at 80% RH. The relative
humidity of the air was 8096, concentration of
DMMP 2.2 mg/l. For comparison, the breakthrough
in dry carbon beds with dry air is also shown in the
figure.
Table 5 shows the rate constants and adsorption
capacities calculated from the low concentration
breakthrough curves.
As shown in Fig. 6, the humidity has very little in-
fluence on the breakthrough time in this case. Cal-

Table 4. Adsorption capacities and rate constants for measurements with n-amylacetate

Linear velocity Weight of carbon Contact time Rate constant Adsorption

(m/s) (al IS) cs- 9 canacitv

3.15 0.15 97 0.16

:: 7.5 0.15 118 0.17
0:2 15 0.30 131 0.22
0.4 15 0.15 198 0.25
0.6 23 0.15 228 0.24
284 0. BUSMUNDRUD

leqeroture difference during water adsorption Bredrthraugh of MrlP.in ASC 12x30 TEOA carbon
I Dry and humid oir. Contact tine 0.15 s.
G 20 I
c 18
g 16,
f 14,
2 12,
G 10,
2,
3 *
f ::
+- 2.
0 1
0 20 40 60 80 100
Time (min.) ;
-14 - ** .“- .x ” .* -. I’.‘- .’
0 30 60 90 120 150 160 210 240
Fig. 5. Temperature increase across filter bed during water Time (min.)
adsorption. 15-gASC I2 X 30 TEDA carbon. Linear veloc-
ity 0.40 m/s, contact time 0.15 s, 80% relative humidity. Fig. 6. Breakthrough of DMMP in ASC 12 X 30 TEDA
carbon, dry and humid air.

culations of rate constants and adsorption capacities

show that the rate constant is somewhat smaller, but
the adsorption capacity is essentially the same. Other
studies[‘l] have also shown decrease of rate constant
with humidity.
2.6.2 ~easuremenis wick n-amyfacetate.
Figure 7 shows the breakthrough concentration for n-
amylacetate in carbon equilibrated with air at 80%
RH. The relative humidity of the air was GO%,con-
centration of n-amylacetate was 3 mg/l. For compar-
ison, the breakthrough in dry carbon beds with dry air
is also shown in the figure. As shown, the difference
between dry and wet breakthrough curves is greater
than in the case of DMMP.
In Table 6, the corresponding rate constants and
adsorption capacities for dry and wet carbon are
shown.
In this case, the rate constant may be dependent
on contact time, but a sufficient number of measure-
ments to establish a relationship has not been made.
Based on the measurements ,for contact time 0.15 s,
the rate constant can be written:
k, = 270 . Pi?‘.
The adsorption capacity was found to depend on the
bed height as:
W, = (0.022 & 0.001) - L
+ (0.082 5 0.007).
The correlation coefficient was r = 0.996. (The cor-
relation coefficient with velocity was 0.79.)
The small influence of humidity on the adsorption
capacity for water insoluble adsorbates like n-
amylacetate is in contmdi~ion to some other re-
sults[7,8].
2.7 Temperature d@erence during adsorption
During adsorption on activated carbon, the adsor-
bate is giving up its adsorption heat, heating the air
passing through the carbon bed. This may give infor-
mation about the adsorption process, especially in
the case of humid air and humid carbon. The tem-
perature difference across the carbon bed was mea-
sured during the adsorption process, The experimen-
tal setup does not measure the heat of adsorption,
since there is probably an un~ntrolled loss of heat
through the walls of the filter tube.
Figure 8 shows the temperature difference across
the filter bed in the case of DMMP for 7.5-g carbon.
Figure 9 shows the temperature difference in 1S-gear-
bon for n-amylacetate. In both cases, the temperature
increase for dry air is l-2 “C. However, for humid air,
(13) the two cases are different. In the case of DMMP, the
temperature does not change significantly across the
filter bed. This indicates that the released adsorption
heat of DMMP is balanced by the desorption heat of
the water being displaced.
For n-amylacetate, the temperature decreases 2-3
(14) “C. This indicates that the desorption heat of the

Table 5. Comparison of adsorption capacities and mte constants with dry and humid air for DMMP

Humid air Dry air

Linear velocity Rate constant Adsorption Rate constant Adsorption

(m/s) ts- ‘) capacity ts- ‘1 capacity

0.20 105 0.34 132 0.29

0.40 135 0.37 I68 0.357

Contact time 0. IS s.
 Vapour breakthrough in activated carbon he& 285

Breakthrough of n-omyacetote in ASC 12x30 TEOA carbon Temperatureacross filterbed during odsorptron of OHMP
Dry and humid oir. Contact time 0.15 s. Velocitv20 cm/s. Contact tine 0.15 s
2.00
G 1.75
L 1.50
; 1.2s
::b 1.00
G 0.75
3: 0.50
.m 80 F!RH
e 0.25
K
2E 0.00
I
.n 0.10 m/s -0.25 80 % RH -
-12_ a l 0 L-
0 l 0 0.40 m/s O 30 60 90 120 150 180 210 240
0
-14 .9,.'.p.".".' Time (min.)
0 30 60 90 120 150
Time (min. 1 Fig. 8. Temperature difference across the filter bed for
DMMP in dry and humid air. Linear velocity 0.20 m/s, con-
Fig. 7. Breakthrough of n-amylacetate in ASC 12 X 30 tact time 0. I5 s.
TEDA carbon, dry and humid air.

water being displaced is higher than the heat of ad-
sorption of the n-amylacetate.
The dynamic adsorption of vapours in activated
carbon beds in the presence of humidity is a compli-
cated process where the influence of the water may be
very dependent on the specific experimental condi-
tions. However, these experiments clearly indicate
that for the present experimental conditions, the
main effect of the humidity is to reduce the rate con-
stant, while the adsorption capacity is not influenced
by the water. This must necessarily mean that the
water in the pores of the carbon is displaced by the
vapour being adsorbed. This is also clearly shown by
weighting the carbon after it has been brought into
equilibrium with the humid air, and after the whole
experiment. In the case of adsorption of DMMP, the
weight is unchanged, while in the case of n-amylace-
tate, the weight is somewhat reduced. This may be
due to the density of n-amylacetate being less than the
density of the displaced water.
In order to fully understand the processes going
on, more experiments will have to be done with
humid carbon. The concentration of the adsorbate
vapour is expected to be important, since the neces-
sary rate of displacement of water will have to in-
crease with increasing concentration. However, this
rate is limited by the fact that the relative humidity of
the effluent air cannot exceed 100%. Therefore, for
high adsorbate concentrations, the influence of ad-
sorbed water on the adsorption capacity may be
found to be greater.
3. DISCUSSION
Some experiments with dynamic adsorption in
activated carbon have been done. The experimental
conditions have been designed to resemble the con-
ditions for filters designed to protect against highly
poisonous organophosphorus compounds. The re-
sults have been interpreted in terms of the modified
Wheeler equation.
The breakthrough times, especially for low break-
through concentrations, have been found to be very
dependent on air velocity. This is in accordance with
the first-order rate constant being dependent on the
linear velocity. For the experimental conditions used,
influence of adsorbed humidity has been found to be
small in the case of the water soluble adsorbate
DMMP, while it has been somewhat larger in the case
of the water insoluble adsorbate n-amylacetate. The
water content seems to influence the rate constant
more than the adsorption capacity.
The rate constant was found to be dependent on
contact time for adsorption of DMMP, and the ad-
sorption capacity was found to be dependent on bed
height for both adsorbates. This clearly indicates that
existing theory for dynamic adsorption in carbon
beds is insufficient to explain the adsorption process.
However, laboratory measurements of break-
through in carbon beds give values for the rate con-
stant and the adsorption capacity which ought to
make calculations for other filters possible, as long as
the linear air velocities, contact times, and bed
heights are in the same range as during the measure-

Table 6. Adsorption capacities and rate constants for n-amylacetate in dry and humid conditions

Humid air Dry air

Linear velocity Contact time Rate constant Adsorption Rate constant Adsorption
(m/s) w (s-l) capacity W’) capacity

0.1 0.15 54 0.12 97 0.16

0.2 0.15 86 0.15 118 0.17
0.4 0.15 142 0.23 198 0.25
0.2 0.30 64 0.22 131 n 33
 286 0. BUSMUNDRUD

Temp. across filter bed during adsorption of n-omylocetata Accordingly, the error would be on the safe side when
Velocity 40 cm/s. Contact tima 0.15 s safety is concerned.
2.0
Using this type of measurement to predict the per-
formance of carbon filters in the presence of humid-
ity should be done with care. Data from laboratory
experiments should not be used to predict the perfor-
mance of filters where parameters such as adsorbate
concentrations, humidity or temperature are outside
3 -1.0. the range used to determine the constants in the
breakthrough equation.
cg -2.0 -
-2.5' ' ' ' ' '
REFERENCES
0 30 60 90 120 150
L. A. Jonas and W. J. Swirberly, J. C&al. 24,446 ( 1972).
Time (min.) :: Y. H. Yoon and J. H. Nelson, Am. Ind. Hyg. Assoc. J.
Fig. 9. Temperature difference across the filter bed for n- 45, SO9 ( 1984).
amylacetate in dry and humid air. Linear velocity 0.40 m/s, 3. 0. Busmundrud, Am. Ind. Hyg. Assoc. J. 52(4), A216
contact time 0. I5 s. (1991).
4. G. S. Bohart and E. Q. Adams, J. Am. Chem. Sot. 42,
523 ( 1920).
5. G. 0. Wood and E. S. Moyer, Am. Ind. Hyg. ASSOC.J.
ments. Therefore, the performance of filters ought to 50(8), 400 (1989).
be predictable from this type of measurement. As can 6. A. Wheeler, In Catalysis (Edited by P. H. Emmett), Vol.
be seen from all breakthrough curves, using data de- II. Reinhold, New York (1955).
‘. T. H. Hall, P. Breysse, M. Corn, and L. A. Jonas, Am.
rived from low concentration breakthrough to pre-
Ind. Hyg. Assoc. J. 49(9), 462 ( 1988).
diet performance at higher breakthrough concentra- g. M. D. Werner, Am. Ind. Hyg. Assoc. J. 46(10), 585
tions would underestimate the breakthrough times. (1985).

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