J. Chem. Eng.

Data 2003, 48, 603-607 603

Adsorption Equilibria of Methane, Ethane, Ethylene, Nitrogen, and

Hydrogen onto Activated Carbon
Byoung-Uk Choi,* Dae-Ki Choi, Young-Whan Lee, and Byung-Kwon Lee
CFC Alternatives Research Center, Korea Institute of Science & Technology, P.O. Box 131,
Cheongryang, Seoul 130-650, Korea

Sung-Hyun Kim
Department of Chemical Engineering, Korea University, Seoul 136-701, Korea

Adsorption equilibria of single components for pure methane, ethane, ethylene, hydrogen, and nitrogen
onto activated carbon adsorbent (Calgon Co.) were measured. The results were obtained with a static
volumetric method at 293.15 K, 303.15 K, and 313.15 K and at pressures up to 2 MPa. Experimental
data were correlated by the Langmuir-Freundlich equation. Isosteric enthalpies of adsorption were
calculated and shown according to surface loading.

Introduction Table 1. Characteristics of Activated Carbon Adsorbent

Recent demands for hydrogen for utilization in such type PCB
nominal pellet size/mesh 6-16
fields as fuel cells, semiconductor processing, and the average pellet size/mm 0.115
petrochemical industry are increasing. Also, hydrogen is BET surface area/m2‚g-1 1150-1250
regarded as an ecologically clean and renewable energy bulk density/g‚cm-3 0.44
total pore volume/cm3‚g-1 0.72
source. Most industrial hydrogen has been produced from
steam reforming of light hydrocarbon, partial oxidation of
heavy hydrocarbon, recovery from coke oven gas, water sary to measure exact single-component adsorption equi-
electrolysis, and so forth. Recently, natural gas pyrolysis librium data.
and plasma reaction processes have been studied to Presented in this paper are the adsorption equilibria of
produce CO2-free hydrogen. Although they do not emit the single components for methane and hydrogen, the main
carbon dioxide, a separation technology to separate high products of natural gas pyrolysis, and the minor products
purity hydrogen is still required, since impurities still for ethane, ethylene, and nitrogen, onto activated carbon
remain in their products. adsorbent. Measurements of adsorption equilibrium data
There are several methods for hydrogen recovery and were made at assorted temperatures and pressures, namely,
purification. The adsorption process has been generally at 293.15 K, 303.15 K, and 313.15 K and at pressures up
recognized as low in energy consumption with the added to 2 MPa. Experimental data were correlated by the
advantage of having very precise (99.999%, H2) component Langmuir-Freundlich equation.
separation using pore size and surface characteristics of
the adsorbent.1,2 Thus, the main advantages of adsorption, Experimental Section
compared with other separation techniques, are the high
Materials. Activated carbon (Calgon Co.) was chosen
selectivity and the relatively high capacity of the adsor-
as an adsorbent. The physical properties, as tabulated in
bents.3 Especially, the pressure swing adsorption technol-
Table 1, were obtained from the manufacturer’s report. Pri-
ogy is attractive for its low energy requirements and low
or to measurement, the adsorbent was maintained at
capital investment costs. Many sophisticated pressure
423.15 K in a drying vacuum oven for more than 12 h to
swing adsorption processes have been developed and com-
remove impurities. The adsorbates, and their purities, were
mercialized since the introduction of the Skarstrom cycle.4
methane (99.9%), ethane (99.5%), ethylene (99%), hydrogen
In fact, there has been a lot of research on separation of
(99.9%), and nitrogen (99.999%).
hydrogen using pressure swing adsorption process.5-8
High-pressure range single-component and multicom- Apparatus and Procedure. The adsorption apparatus
ponent adsorption equilibrium data are needed to separate shown in Figure 1 is based on the static volumetric method.
some components using the pressure swing adsorption There are a reaction cell and a loading cell. Used were 1/8
process. However, due to the substantial amount of time in. tubes and 1/8 in. valves to minimize dead volume as
involved in conducting related experiments, there is scant much as possible. The reaction cell volume was 521.61 (
published data on the mixtures.9 The mixture isotherm 1 mL; the loading cell volume, 522.73 ( 1 mL. The reaction
data are not usually obtained directly, but through cor- cell, loading cell, and dead volumes were measured using
related single-component isotherms.10 Some researchers helium gas. The total amount of vapor introduced and re-
used only single-component adsorption data to predict covered in the system was determined by appropriate pres-
multicomponent adsorption behavior.2,9,11-13 So, it is neces- sure, temperature, and volume measurements. The tem-
perature in each cell was measured by K-type thermocouple
* To whom correspondence should be addressed. E-mail: ares76@ operated within (0.01 K accuracy; the pressure was mea-
kist.re.kr. Fax number: +82-2-958-5809. sured with a pressure transducer. Temperatures and pres-
10.1021/je020161d CCC: $25.00 © 2003 American Chemical Society
Published on Web 03/25/2003
604 Journal of Chemical and Engineering Data, Vol. 48, No. 3, 2003

Table 4. Adsorption Isotherm Data for C2H4 onto

Activated Carbon
293.15 K 303.15 K 313.15 K
P q P q P q
kPa mol‚kg-1 kPa mol‚kg-1 kPa mol‚kg-1
34.730 1.368 54.823 0.972 57.157 0.823
74.133 2.872 166.391 3.431 169.800 3.101
161.678 4.153 277.913 4.305 285.991 3.944
286.600 4.955 406.425 4.849 420.977 4.493
416.454 5.410 533.515 5.199 547.981 4.827
594.993 5.779 668.357 5.451 671.816 5.048
794.171 6.027 799.116 5.623 785.653 5.218
1001.472 6.214 908.520 5.730 906.881 5.359
1208.972 6.295 1009.235 5.812 1022.847 5.455
1404.543 6.357 1161.088 5.919 1169.862 5.550
1674.430 6.376 1333.150 6.026 1351.392 5.638
1514.121 6.081 1522.794 5.700
1623.229 6.088 1617.985 5.734
D D D
0.0167 0.0165 0.0197

Table 5. Adsorption Isotherm Data for N2 onto Activated

Carbon
293.15 K 303.15 K 313.15 K
Figure 1. Schematic diagram of the adsorption apparatus. P q P q P q
kPa mol‚kg-1 kPa mol‚kg-1 kPa mol‚kg-1
Table 2. Adsorption Isotherm Data for CH4 onto
Activated Carbon 123.023 0.325 110.197 0.264 121.062 0.204
221.382 0.592 200.200 0.487 219.513 0.387
293.15 K 303.15 K 313.15 K 324.400 0.823 300.436 0.687 328.548 0.577
427.666 1.011 401.220 0.863 471.747 0.796
P q P q P q 544.902 1.198 517.833 1.039 660.269 1.036
kPa mol‚kg-1 kPa mol‚kg-1 kPa mol‚kg-1 693.258 1.411 692.645 1.266 863.883 1.243
863.266 1.611 950.921 1.531 1081.473 1.419
48.401 0.298 45.697 0.234 60.206 0.188 1050.721 1.791 1239.527 1.769 1342.119 1.583
79.890 0.639 77.272 0.505 88.212 0.423 1294.690 1.980 1542.180 1.966 1629.274 1.722
120.320 1.003 115.194 0.815 130.777 0.684 1574.435 2.171
166.450 1.337 163.991 1.067 170.513 0.950 D D D
217.572 1.633 213.210 1.339 217.192 1.189 0.00882 0.00934 0.0129
270.235 1.902 286.532 1.659 288.153 1.484
324.072 2.114 369.893 1.956 377.285 1.779 Table 6. Adsorption Isotherm Data for H2 onto Activated
398.549 2.385 464.182 2.257 470.148 2.045
484.913 2.653 605.909 2.610 614.711 2.389 Carbon
626.898 3.022 779.190 2.946 784.580 2.712 293.15 K 303.15 K 313.15 K
796.948 3.360 970.694 3.244 971.893 2.996
987.771 3.665 1175.918 3.501 1171.605 3.253 P q P q P q
1188.653 3.913 1377.258 3.707 1379.935 3.464 kPa mol‚kg-1 kPa mol‚kg-1 kPa mol‚kg-1
1381.295 4.110 1568.584 3.877 1560.303 3.611
1549.662 4.256 111.864 0.024 122.837 0.021 123.226 0.021
D D D 222.785 0.085 222.802 0.044 227.066 0.036
0.000 399 0.000 376 0.000 613 346.448 0.106 325.643 0.064 344.167 0.056
463.186 0.126 457.285 0.087 464.898 0.083
Table 3. Adsorption Isotherm Data for C2H6 onto 573.074 0.162 574.316 0.110 615.309 0.107
Activated Carbon 755.186 0.275 933.319 0.182 1049.997 0.185
941.146 0.364 1196.939 0.241 1296.565 0.232
293.15 K 303.15 K 313.15 K 1222.887 1513.418 0.305 1570.848 0.279
D D D
P q P q P q 0.0408 0.0242 0.0214
kPa mol‚kg-1 kPa mol‚kg-1 kPa mol‚kg-1
23.529 1.156 33.009 1.169 33.411 1.071 in the reaction cell, the impurity traces in the reaction cell
51.649 2.788 60.696 2.349 73.655 2.463 were eliminated by vacuum pump for 3 h, similar to the
129.183 4.258 134.519 3.750 160.329 3.604
265.044 5.107 262.477 4.626 292.147 4.387 case of the loading cell. When the temperatures in the
410.275 5.534 409.026 5.076 432.411 4.796 loading and the reaction cells attained required levels, the
592.295 5.802 523.476 5.388 616.031 5.119
797.306 5.948 800.773 5.577 818.093 5.338
experiment was initiated. First, the adsorbate was intro-
999.820 6.031 1067.939 5.695 1026.441 5.421 duced into the loading cell, and then when the temperature
1272.845 6.032 1450.168 5.716 1284.072 5.496 and pressure in the loading cell stabilized, the valve
D D D
0.0217 0.0185 0.0177 between the loading and reaction cells was opened. The
adsorption equilibrium state was considered to be when
sures were recorded at constant time intervals with a mo- the temperatures and the pressures per cell were constant.
bile recorder (MV100, Yokogawa Co.). During adsorption, Temperatures and pressures before and after the adsorp-
the loading cell, the reaction cell, and all lines were im- tion equilibrium state were recorded. The experiment was
mersed in a water bath (SWB-20, Jeio tech.) maintained conducted, on a continuous basis, at pressures up to 2 MPa.
at (0.02 K via a refrigeration circulator (RBC-11, Jeio The amount adsorbed was calculated, from the tempera-
tech.). ture and pressure, before and after the adsorption equi-
Prior to introduction of adsorbate into the reaction cell, librium state using the mass balance given by eq 1.
the adsorbent mass was weighed within (10 mg accuracy
after eliminating impurity traces at 423.15 K and high PV PV PV PV
| + | ) | + | + qM (1)
vacuum for more than 12 h. After the adsorbent was placed ZRT l1 ZRT a1 ZRT l2 ZRT a2
 Journal of Chemical and Engineering Data, Vol. 48, No. 3, 2003 605

Figure 2. Measured and fitted isotherms of CH4 onto activated Figure 4. Measured and fitted isotherms of C2H4 onto activated
carbon: b, 293.15 K; 9, 303.15 K; 1, 313.15 K; s, L-F model. carbon: b, 293.15 K; 9, 303.15 K; 1, 313.15 K; s, L-F model.

Figure 3. Measured and fitted isotherms of C2H6 onto activated Figure 5. Measured and fitted isotherms of N2 onto activated
carbon: b, 293.15 K; 9, 303.15 K; 1, 313.15 K; s, L-F model. carbon: b, 293.15 K; 9, 303.15 K; 1, 313.15 K; s, L-F model.

in which P is pressure, T is temperature, V is volume, R is For each equilibrium datum, rigorous assessments were
the gas constant, M is the molecule weight, Z is the performed and correlated by several pure species equilib-
compressibility factor, and q is the amount adsorbed. 1 rium models. The isotherm equations used in this study
represents the state prior to the adsorption equilibrium; were Langmuir,1 Freundlich,1 Langmuir-Fruendlich,1
2, the final equilibrium state. Toth,16 and Unilan.16 The mathematical forms of these
models are as follows:
Results and Discussion
qmBP
The adsorption data for methane, ethane, ethylene, Langmuir q) (2)
1 + BP
hydrogen, and nitrogen onto activated carbon adsorbent
were obtained at 293.15 K, 303.15 K, and 313.15 K and Freundlich q ) kP1/t (3)
pressures up to 2 MPa. The experimental data are repre-
1/t
sented in Tables 2-6 and are graphically presented in qmBP
Figures 2-6. In these figures, solid lines represent the Langmuir-Freundlich q ) (4)
1 + BP1/t
experimental data.
The methane, ethane, ethylene, hydrogen, and nitrogen qmP
Toth q) (5)
adsorption isotherms resembled the Langmuir isotherm (B + Pt)1/t

[ ]
classified as type-I according to Brunauer et al.15 This type
is characterized by stronger attractive forces between the qm c + P exp(+s)
Unilan q) ln (6)
adsorbate and adsorbent than between the molecules of the 2s c + P exp(-s)
adsorbate in the bulk state.1 In other words, the pore size
of the adsorbent is not very much greater than the where q is the amount adsorbed, P is the equilibrium
molecular diameter of the adsorbate molecule. pressure, and qm, B, k, t, c, and s are isotherm parameters.
606 Journal of Chemical and Engineering Data, Vol. 48, No. 3, 2003

polarizability of the ethane and ethylene molecule. For

nitrogen, the behavior is observed to be similar.
The Langmuir-Freundlich equation was used for all the
systems because this equation showed the minimum value
of the average deviation parameter. Since the Langmuir-
Freundlich isotherm has three adjustable parameters, it
usually gave a more accurate correlation than the Lang-
muir and Fruendlich isotherms, both of which have only
two adjustable parameters. Although the Toth and the
Unilan equations predicted well experimental data at low
pressure, they did not predict well at high pressure,
because they obey Henry’s law at low pressure but the
adsorbed amount approaches saturating loading at high
pressure. Additionally, the L-F model is certainly superior
to the others. The computational load is evidently crucial,
besides the model accuracy, since the ultimate goal of this
study is to determine an appropriate model to develop a
PSA simulation model.14 In other words, for multicompo-
nent equilibria, the simpler extended versions of the single-
component models provide an adequate and numerically
Figure 6. Measured and fitted isotherms of H2 onto activated convenient means of predictions.14 The isotherm param-
carbon: b, 293.15 K; 9, 303.15 K; 1, 313.15 K; s, L-F model. eters for the Langmuir-Freundlich equation were given
in Table 7.
To find the isotherm parameters for each adsorption
Isosteric enthalpies of adsorption can be calculated by
system, two parameter estimation techniques were applied.
the Clausius-Clapeyron equation17 applied to adsorption,
These methods include a least-squares fitting method,
which correlated the Langmuir, Freundlich, and Lang-
qst ln P
muir-Freundlich equations, and the so-called Nelder-
Mead simplex pattern search algorithms, which correlated RT2
) [∂ ∂T ] q
(9)
the Toth and the Unilan equations. In addition, the
following objective functions were used in this study, where P is pressure, T is temperature, R is the gas
constant, and qst is the isosteric enthalpy.
min ∑(N obs
j - Ncal
j )
2
(7) The isosteric enthalpy is a measure of the interaction
j between adsorbate molecules and adsorbent lattice atoms
and may be used as a measure of the energetic heterogene-
where Nobsj are the experimental data of the amount ity of a solid surface. Usually, the isosteric enthalpy of
adsorbed and Ncalj are the correlation results. Also, the adsorption varies with surface coverage. Therefore, the
deviation parameter on the amount adsorbed, D, was relation between isosteric enthalpy and coverage explains
utilized to compare the correlation results with experimen- the surface structure.17,18 For homogeneous surfaces, as
tal data, coverage increases, lateral interactions increase; thus, the
isosteric enthalpy of adsorption increases. Vertical interac-
1 n Nobs - Ncal tions do not depend on coverage and are determined from
∑
i i
D) | | (8) limiting isosteric enthalpy at zero coverage.18 Thus, the
n i Niobs
isosteric enthalpy versus surface coverage relation cannot
be determined a prior for heterogeneous surfaces. However,
where n is the number of data. The average deviation a decreasing isosteric enthalpy with increasing surface
parameters for each component were represented in Tables coverage usually indicates a heterogeneous surface. A
2-6. constant value would indicate either a homogeneous sur-
For all the systems, the isotherms showed nonlinearity, face with no lateral interactions or a heterogeneous surface
except for hydrogen. One of the main reasons for isotherm where the change in lateral interactions exactly cancels the
nonlinearity stems from adsorbent surface heterogeneity. change in vertical interactions.17 According to the ideal
This is generally the case for activated carbon. Also, surface Langmuir model, the enthalpy of adsorption should be
heterogeneity depends on the relative sizes of the adsorbate independent of coverage, but this requirement is seldom
and active sites.14 The amount adsorbed of methane, fulfilled in real systems because the effects of surface
ethane, and ethylene increased significantly at low pres- heterogeneity and adsorbate-adsorbate interaction are
sure, under 0.3 MPa. Especially, at the same pressure and generally significant.
temperature, the adsorbed amount of ethane and ethylene As shown in Figure 7, the isosteric enthalpies of adsorp-
is always higher than that for methane, due to the higher tion varied with the surface loading on activated carbon

Table 7. Langmuir-Fruendlich Adsorption Isotherm Parameters for CH4, C2H6, C2H4, N2, and H2 onto Activated Carbon
293.15 K 303.15 K 313.15 K
qm B qm B qm B
adsorbate mmol‚g-1 MPa-1 t mmol‚g-1 MPa-1 t mmol‚g-1 MPa-1 t
CH4 5.154 1.757 0.848 4.944 1.471 0.870 4.316 1.194 0.748
C2H6 6.148 16.600 0.737 5.837 11.685 0.722 5.681 9.662 0.771
C2H4 6.594 9.455 0.826 6.302 5.280 0.722 5.890 3.869 0.651
N2 3.317 0.878 0.905 3.161 0.839 0.924 2.579 0.681 0.824
H2 12.344 0.0197 0.995 10.146 0.0197 0.948 9.719 0.0197 0.954
 Journal of Chemical and Engineering Data, Vol. 48, No. 3, 2003 607

by the Clausius-Clapeyron equation, allowing the conclu-

sion that the activated carbon has an energetically het-
erogeneous surface.

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Received for review August 21, 2002. Accepted February 3, 2003.
dlich equation, which showed remarkable quality assess-
ments. The isosteric heats of adsorption were calculated JE020161D