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CO, Adsorption Techniques On High Surface Area Activated Carbons.
Mark L. Stewart and John M. Stencel.

Center for Applied Energy Research
University of Kentucky
Lexington, Kentucky
4051 1-8433
1. INTRODUCTION
For years the subject of CO, adsorption on activated carbons has been both
challenged and supported. The question remains whether or not CO, is a valid
adsorbate for characterizing pore structures of activated carbons. The predominance
of nitrogen adsorption as a routine experimental technique for BET surface area
approximations has more or less overshadowed the limitations of this technique in
terms of activated diffusion phenomena[l]. As a result, it is thought that nitrogen
adsorption at 77K generally underestimates the surface area of coals[l]. In some
super-activatedcarbons, CO, is an attractive adsorbate for characterization due to its
small molecular diameter and it's access to supermicropores. Although CO, adsorption
models are not completely understood, for particular cases in which N, adsorption may
be problematic or inconclusive, CO, adsorption may offer additional pore structure
i?formation.
The purpose of this communicationis to address the concept of CO, adsorption
phenomena experimentally and conceptually. Experimental data are comparedfor CO,
adsorbed onto very high surface area activated carbons. From this information,
optimal experimental conditions are theorized on the basis of ease and understanding.
It is hoped that an adsorption procedure involving the benefits of N, and CO, together
will provide insight into the pore structures of very high surface area activated
carbons.
2. EXPERIMENTAL
Materials used:
Two activated carbons were used in the experiments; they were supplied by
Amoco Research and Developement, and Norit N.V. Activated Carbon. They are
classified as Arnoco Super-A and Norit A-8982. The surface areas, as measured by
nitrogen BET method(21, were 1500-1800 m2/g for Norit A-8982 and 2500-2800 m2/g
for Amoco Super-A.
Experimental methods:
Adsorption analysis was performed on a Coulter Omnisorp lOOCX Automated
Gas Sorption System. Approximately 0.25 grams of sample was weighed prior to
outgassing. All samples were outgassed at 250°C and sealed under vacuum prior to
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analysis. Static volumetric mode was used for all CO, and N, adsorption
measurements. N, was adsorbed at 77K in the relative pressure range (P/Po) of 0.001
to 0.98. CO, was adsorbed at three different temperatures and relative pressure
ranges(P/Po) as follows:
195K: 0.0001 to 0.48

273K: 0.0001 to 0.027
298K: 0.0002 to 0.015
CO, saturation vapor pressures for each temperature were taken as follows:
195K: 1,410 torr[3]

273K: 26,068 torr
298K: 45,041 torr
Molecular diameters used for N, and CO, were 3.64 and 3.3 angstroms,
respectively. All surface areas were calculated from the BET equation[2] and pore
volumes were approximated using the Dubinin-Radushkevich equation[4].
3. RESULTS AND DISCUSSION
The CO, adsorption isotherms for the A-8982 and the Amoco Super-A carbons
at 195K, 273K, and 298K are plotted in Figures 1 and 3, respectively. Upon initial
examination for the Norit carbon, the CO, uptake at 195K in this low pressure region
is markedly higher than in the other two temperature cases. At 273K and 298K, the
isotherms are virtually identical with very little deviation in CO, uptake. The Amoco
Super-A carbon exhibits similar characteristics in this region but with a noticable
difference in the 273K and 298K temperature cases. These results suggest that, at
195K, complete micropore filling may occur giving higher potential for CO, adsorption.
It is likely that incomplete micropore filling occurs at temperatures of 273-298K since
the saturation vapor pressure of CO, is extremely sensitive to temperature changes
and is very high. However, it seems reasonable to assume that, at 195K, a better
estimate of internal pore uptake can be obtained.
The CO, DR plots for A-8982 and Amoco Super-A are indicated in Figures 2
and 4, respectively. In estimating pore volumes, a comparable range for each
temperature was taken for extrapolation to the y-axis. The pore volumes are as
follows:
Norit 195K = 1.22 cc/g Amoco 195K = 2.00 cc/g

At an adsorption temperature of 195K the pore volumes are the highest which
relates to the increased uptake observed in the adsorption isotherms in figures 1 and
3. Pore volume calculations from N, adsorption are slightly less than the 195K CO,
case but higher than 273K and 298K CO, cases. Results obtained from BET surface
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area calculations for the 195K CO, case yield higher surface areas than N, BET
estimates.
4. CONCLUSIONS
C0,adsorption at 195K appears to be a valid technique for approximating pore

volumes of high surface area activated carbons if complete micropore filling is
assumed. Experimentally,due to instrumental limits, a larger relative pressure range
can be analysed for 195K due to the temperature and vapor pressure sensitivities
present at 273K and 298K. Because of this fact, CO, and N, surface areas can be
compared. Since the relative pressure ranges for 273K and 298K are so low,
(maximum p/po = 0.02-0.03). the micropore filling is incomplete, giving pore volumes
that are underestimated. Although a strict comparison between CO, and N, needs to
be investigated further, molecular size differences may still give some insight on the
possible presence of any super microporosity.
1202
5. REFERENCES
1. Om P. Mahajan, Carbon Vol. 29 No. 6. pp. 735-742. 1991.
2. Brunauer S., Emmett P.H., Teller E. J.A.M. CHEM. SOC.. pg 6309. 1938.
3. H. Marsh, D. Crawford. T.M. O'Grady. and A. Wennerberg. Carbon Vol. 20 No 5, pp.

419-426, 1982.
4. Dubinin M.M., and Radushkavich L.V. Proc. acad. Sci. USSR Vol. 55 pg 331 1947.
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I
--
.,...
19%
273K
- 2981(
0.00 0.01 0.02

PIP0
Fig. 1. C02adsorption isotherms on Norit activated carbon at 195K. 273K. and 298K.
In v
600 -
500 .-
400
300 --
--
- 19y(
. . . . . 273K
-298K
zoo -
100 --
(000 J I
5 00 10 00 1500 20 00
I InlPolPI"2
Fig. 2. C02 DR plots corresponding to isotherms in Fig. 1
1204
0 00 p.01 0.02
PiPo
Fig. 3. C0,adsorption isotherms on Amocu Super-A activated carbon at 195K. 273K.

and 298K.
600""
500 -~
4 0 0 -~
300 --
--
.....
195K
273K
-298K
z o o --
100 --
1
1000 15 00 20 00
I I"(P0IP)~Z
Fig. 4. CO, DR plots corresponding 10 isotherms in Fig 3.
1205

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CO, Adsorption Techniques On High Surface Area Activated Carbons.

Mark L. Stewart and John M. Stencel.

195K: 0.0001 to 0.48

195K: 1,410 torr[3]

3. RESULTS AND DISCUSSION

Norit 195K = 1.22 cc/g Amoco 195K = 2.00 cc/g

C0,adsorption at 195K appears to be a valid technique for approximating pore

1. Om P. Mahajan, Carbon Vol. 29 No. 6. pp. 735-742. 1991.

3. H. Marsh, D. Crawford. T.M. O'Grady. and A. Wennerberg. Carbon Vol. 20 No 5, pp.

0.00 0.01 0.02

Fig. 2. C02 DR plots corresponding to isotherms in Fig. 1

Fig. 3. C0,adsorption isotherms on Amocu Super-A activated carbon at 195K. 273K.

Fig. 4. CO, DR plots corresponding 10 isotherms in Fig 3.

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