Carbon Dioxide Adsorption Isotherms On Activated Carbons
Carbon Dioxide Adsorption Isotherms On Activated Carbons
Carbon Dioxide Adsorption Isotherms On Activated Carbons
pubs.acs.org/jced
ABSTRACT: This paper presents adsorption isotherm data of CO2 onto two different types of highly porous activated carbons
(ACs) for temperatures ranging from (18 to 80) °C and pressures up to 10 MPa. The assorted adsorbents are activated carbon
fiber (ACF) of type A-20 and activated carbon powder of type Maxsorb III. Adsorption isotherm data have been obtained using a
volumetric technique and fitted to the DubininAstakhov (DA), Toth, Langmuir, and modified DA equations. The latter
considers the pseudosaturation pressure of CO2 that plays an important role for supercritical gas adsorption, and the
pseudosaturation pressure was determined from the experimental data. The Toth and modified DA isotherms correlate with
the experimental data within 5 % root-mean-square deviation (rmsd) and present a better fitting than that of the Langmuir and the
DA equations. The isosteric heat of adsorption data were derived from the Toth and modified DA isotherm equations and the
correlation proposed by Chakraborty et al., and the average heat of adsorption values were found to be comparable. These data are
essential for designing CO2-based adsorption cooling, refrigeration, and gas storage systems.
’ INTRODUCTION data are not available in the open literature. Experimental data
Physical adsorption on carbonaceous adsorbents has been were correlated with the DA, modified DA, Toth, and
extensively studied for the separation and purification of gases,13 Langmuir isotherm models. The isosteric heat of adsorption
gas storage,46 and adsorption cooling711 applications. For the data are also evaluated.
adsorption cooling and adsorbed gas storage applications, it is
essential to estimate correct isotherms and isosteric heat of
’ EXPERIMENTAL SECTION
adsorption of the assorted adsorbentadsorbate pairs for design-
ing adsorption systems. Using these key data, the numerical Materials. The adsorbents used in this study are ACF of type
modeling of the processes of chiller operation and gas storage A-20 and activated carbon powder of type Maxsorb III, and these
performance can be performed with a high level of confidence. activated carbons were developed by AD’ALL Co. Ltd., Japan,
As one of the countermeasures against global warming and and Kansai Coke & Chemicals Co. Ltd., Japan, respectively. The
energy conservation problems, Saha et al.8 and El-Sharkawy microporus ACF (A-20) has a large surface area of 2000 m2 3 g1,
et al.12 investigated experimentally the adsorption characteristics micropore volume (vμ) of 1.03 cm3 3 g1, and average pore
of ethanol and methanol, respectively, onto activated carbon diameter of 21.6 Å.7 It is suitable for physical adsorption and
fiber and Maxsorb III. However, these adsorbentrefrigerant easy to pack. On the other hand, Maxsorb III has a surface area as
pairs work on subatmospheric pressures, and thus the system high as 3150 m2 3 g1, micropore volume of 1.7 cm3 3 g1, and
footprint becomes large. Accordingly, it is inevitable to develop mean pore diameter of 2 nm.14 Samples of CO2 and helium were
adsorption cooling systems based on natural working pairs which supplied by Asahi Sanso Shokai Ltd. Japan having a purity of
work above atmospheric pressure. Among natural refrigerants, 99.995 %.
CO2 has the advantage of having no problems related to Experimental Apparatus. Measurements of the adsorption
flammability and toxicity as opposed to ammonia and thus has equilibrium of CO2 onto Maxsorb III and ACF (A-20) have been
received considerable attention especially in the field of auto- conducted using a volumetric technique. Figure 1 shows the
motive air conditioners. schematic diagram of the experimental apparatus which com-
Himeno et al.13 reported a systematic study of the adsorption prises: (i) adsorption and load cells, and these cells are designed
of carbon dioxide onto five different activated carbons using the to stand a pressure of 12 MPa; (ii) two water baths of type
static volumetric method. Experiments were performed at tem- Advantec TBN402DA connected with two water circulators of
peratures ranging from (0 to 50) °C and pressures up to 6 MPa. type Eyela CTP-3000 and CTP-6000; and (iii) a 25.8 μm mesh is
However, CO2-based transcritical adsorption cooling systems attached at the center of the adsorption cell. The adsorption cell
can go up to 10 MPa. From the above perspective, the adsorption
isotherms of CO2 on two different types of highly porous Received: September 27, 2010
activated carbons for temperatures ranging from (18 to Accepted: February 25, 2011
80) °C and pressures up to 10 MPa were determined as these Published: March 15, 2011
r 2011 American Chemical Society 1974 dx.doi.org/10.1021/je100973t | J. Chem. Eng. Data 2011, 56, 1974–1981
Journal of Chemical & Engineering Data ARTICLE
Figure 3. Adsorption isotherm of CO2 on ACF (A-20) with ( 5 % error Figure 4. Adsorption isotherm of CO2 on Maxsorb III with ( 5 % error
bars in uptake and ( 0.02 MPa horizontal error bars in pressure: 0, bars in uptake and ( 0.02 MPa horizontal error bars in pressure: 0,
18.8 °C; 9, 10 °C; , 0 °C; O, 10 °C; b, 20 °C; /, 30 °C; Δ, 40 °C; 17.6 °C; 9, 10 °C; , 0 °C; O, 10 °C; b, 20 °C; /, 30 °C; Δ, 40 °C;
2, 50 °C; þ, 60 °C; ), 70 °C; (, 80 °C; solid lines are from the 2, 50 °C; þ, 60 °C; ), 70 °C; (, 80 °C; solid lines are from the
Toth model. Toth model.
Table 1. Raw Adsorption Data of CO2 onto ACF (A-20) for Adsorption Temperatures of (10, 10, 30, 50, and 70) °C
measurement number Tl/°C Pl/MPa Ta/°C Peq/MPa Δmload/g Δmvoid/g mn/g C/kg 3 kg1
Table 2. Raw Adsorption Data of CO2 onto Maxsorb III for Adsorption Temperatures of (10, 10, 30, 50, and 70) °C
measurement number Tl/°C Pl/MPa Ta/°C Peq/MPa Δmload/g Δmvoid/g mn/g C/kg 3 kg1
adsorption equation (eq 12) by introducing an extra term (second The shape of the adsorption isotherms of CO2 in the assorted
term of the RHS of eq 14), which accounts for the heat of adsorbed microporous materials is monotonically concave and therefore can
mass with respect to pressure and temperature changes during be classified as type I in the IUPAC classification.22 The raw data for
adsorption, and the modified equation is expressed by CO2 adsorption on ACF (A-20) and Maxsorb III are presented in
Table 1 and Table 2, respectively.
D ln P DP The experimental data are fitted with the Langmuir, Toth,
ΔHads ¼ RT 2 þ Tvg ð14Þ
DT C DT DubininAstakhov (DA), and modified DA isotherm equa-
tions. A nonlinear optimization routine is used to optimize the
Accordingly, the corrected heat of adsorption employing the mod- parameters of these models to fit the experimental data for multiple
ified DA equation reduces to temperatures.15 The root-mean-square deviation (rmsd) between
R n 1n DP the calculated values (cal) and experimental data (exp) is defined as
ΔHads, DA ¼ kRT þ A þ TE A þ Tvg ð15Þ vffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
n DT u !2
uN C C
u∑ exp cal
u 100
t0 Cexp 3
’ RESULTS AND DISCUSSION rmsd ¼ ð16Þ
N
The experimental uptake curves of CO2 onto ACF (A-20) and
Maxsorb III for temperatures ranging from (18 to 80) °C and As can be seen from Figures 3 and 4, the maximum uptake of
pressures up to 10 MPa are shown in Figures 3 and 4, respectively. CO2 onto ACF (A-20) near the saturation pressure is 1 kg of
1978 dx.doi.org/10.1021/je100973t |J. Chem. Eng. Data 2011, 56, 1974–1981
Journal of Chemical & Engineering Data ARTICLE
Figure 7. (a) Characteristic curve for the ACF (A-20)CO2 pair and
(b) adsorption isotherms of CO2 onto ACF (A-20) using the modified
DA equation for k = 3.86: 0, 18.8 °C; 9, 10 °C; , 0 °C; O, 10 °C;
b, 20 °C; /, 30 °C; Δ, 40 °C; 2, 50 °C; þ, 60 °C; ), 70 °C; (, 80 °C. Figure 8. (a) Heat of adsorption for the ACF (A-20)CO2 pair and (b)
heat of adsorption for the Maxsorb IIICO2 pair: ---, ΔHCC derived
from the Toth isotherm; O, ΔHCC derived from the modified DA
Table 4. Fitting Parameters of DA and Modified DA equation (eq 13); Δ, corrected heat of adsorption derived from the
Models for CO2 Adsorption onto ACF (A-20) and Maxsorb modified DA equation (eq 15).
III
adsorbent model k W0/cm3 3 g1 E/J 3 mol1 n rmsd and are almost the same during relatively higher loading where C
is above 0.5 kg 3 kg1 for ACF (A-20) and above 0.8 kg 3 kg1 for
A-20 DA 2 1.002 4468.22 1.14 6.61 Maxsorb III.
modified DA 3.86 1.03 4549.92 1.18 3.58
Maxsorb III DA 2 1.727 3983.24 1.12 9.58
’ CONCLUSIONS
modified DA 4.49 1.759 4159.89 1.18 4.53
Adsorption isotherm data for CO2 onto ACF (A-20) and
reduces the rmsd as low as 3.58 % and 4.53 % for ACF (A-20) and Maxsorb III have been obtained through a volumetric technique.
Maxsorb III, respectively. The adsorption uptake measurements cover the temperature
The plots of the heat of adsorption versus the adsorbed ranging from (18 to 80) °C and pressures up to 10 MPa. The
amount for ACF (A-20)CO2 and Maxsorb IIICO2 pairs data have been successfully correlated to popular isotherm
are shown in Figures 8(a) and 8(b), respectively. The Clausius equations within ( 5 % uncertainty. For the measured adsorp-
Clapeyron heats of adsorption (ΔHCC) derived from the Toth tion isotherm data, an improvement in accuracy has been
isotherm equation are constant, and these are equal to (19.23 and observed in the present study over that of an earlier method
20.37) kJ 3 mol1 for ACF (A-20)CO2 and Maxsorb IIICO2 for the similar adsorbentadsorbate pairs. Adsorption uptake of
pairs, respectively. On the other hand, the isosteric heat of CO2 on Maxsorb III is about 1.7 times higher than that of ACF
adsorption (ΔHads) proposed by Chakraborty et al.21 yields (A-20). The isosteric heat of adsorption data have been extracted
higher isosteric heat of adsorption values than those obtained from the experimental measurements, which appear to be well
from ΔHCC,DA. It is noteworthy to mention that for both interpreted from that derived from the modified DA equation.
adsorbentadsorbate pairs the values of ΔHads,DA are higher The average heats of adsorption of CO2 in Maxsorb III and ACF
than those obtained from the Toth equation during low loading (A-20) are found to be (20.37 and 19.23) kJ 3 mol1, respectively.
1980 dx.doi.org/10.1021/je100973t |J. Chem. Eng. Data 2011, 56, 1974–1981
Journal of Chemical & Engineering Data ARTICLE