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Adsorption Equilibria of CO
2
on Zeolite 13X and Zeolite X/ActivatedCarbon Composite
Jong-Seok Lee,
†
Jong-Hwa Kim,
‡
Jin-Tae Kim,
†
Jeong-Kwon Suh,
†
Jung-Min Lee,
†
andChang-Ha Lee*
,‡
Department of Chemical Engineering, Yonsei University, Seoul 120-749, Korea, and Applied Chemistry &Engineering Division, Korea Research Institute of Chemical Technology, Taejeon 305-600, Korea
The adsorption equilibria of CO
2
on zeolite 13X and zeolite X/activated carbon composite (Zeocarbon)were measured by a static volumetric method. The equilibrium experiments were conducted at (273.15,293.15, 313.15, 333.15, and 353.15) K and at pressures up to 102.0 kPa for zeolite 13X and 99.7 kPa forZeocarbon. The experimental data obtained were correlated by the Toth, UNILAN, and Sips models,which are generally used for microporous adsorbents such as zeolites and activated carbon. The isostericenthalpies of adsorption were calculated for CO
2
on both adsorbents.
Introduction
The emission of CO
2
from power plants that burn fossilfuels is a major reason for the accumulation of CO
2
in theatmosphere, which causes long-term environmental prob-lems.
1
Recently, much attention has been paid to the globalwarming effect caused by the excessive emission of CO
2
into the atmosphere.
2
Separation can play a key role inalleviating this problem, and the adsorption of gases andvapors by microporous solids has attracted much attentionbecause of its great practical importance in the fields of gas separation, gas purification, and environmental prob-lems. Therefore, adsorption is one of the most effectivemethods for the separation of emitted CO
2
.Information concerning the relevant adsorption equilib-ria is generally an essential requirement for the analysisand design of an adsorption separation process.
3
Forpractical applications, the adsorption equilibria must beknown over a broad range of operation temperatures. Also,the isotherms of pure species are fundamental informationfor the dynamic simulation of adsorbers.
4
Furthermore, itis important to select the proper adsorbent for the designof an efficient adsorption process.Whereas fossil resources are limited, biomass as anadsorbent is an inexpensive, renewable, and environmen-tally friendly additional resource that can be found readilyall over the world.
5
Recently, a zeolite X/activated carboncomposite (Zeocarbon) was synthesized from rice hulls thatcan be used in packed beds in pelletized form. However,little information is available in the literature concerningthe adsorption of any components on Zeocarbon at varioustemperatures.Zeocarbon was selected as an adsorbent in this study,and adsorption isotherms for CO
2
on Zeocarbon weremeasured and compared with those for CO
2
on zeolite 13X,which were measured previously.
6,7
In this study, com-mercial adsorbent pellets of zeolite 13X and Zeocarbon wereused instead of crystals. The experimental data obtainedat various temperatures were correlated with existingadsorption isotherm models such as the Toth, UNILAN,and Sips models.
Experimental Section
Materials.
Spherical zeolite 13X and Zeocarbon pelletswere supplied by Aldrich Co. and Zeobuilder Co., respec-tively. Zeocarbon synthesized from rice hull consists of thefollowing components: 38.5 mass % zeolite X, 35 mass %activated carbon, 10 mass % inert silica, and 16.5 mass %zeolite A and P. The zeolite in Zeocarbon was exchangedwith Ca ion by the supplier. Both adsorbent samples werecrushed to 20
-
30 mesh. The BET surface areas, microporevolumes, and pore diameters of the adsorbents weremeasured with an automatic volumetric sorption analyzer(Micromeritics, ASAP-2010) using nitrogen adsorption at77 K. The measured and supplied physical properties of the zeolite 13X and Zeocarbon samples are listed in Table1. CO
2
with 99.9999 vol % purity was provided by MathesonCo.
Apparatus and Procedure.
The adsorption experi-ments were based on the static volumetric method, and aschematic diagram of the apparatus is shown Figure 1. Inthe method, the total quantity of gas admitted into thesystem and the amount of gas in the vapor phase remainingafter adsorption equilibrium were determined by appropri-ate
P
-
V
-
T
measurements.The system pressure was measured by an absolutepressure transducer (MKS, type 690A13TRA) with a high-accuracy signal conditioner (MKS, type 270D). Its pressurerange is (0
-
133.33) kPa, and its reading uncertainty is
(
0.05% within the usable measurement range. Duringexperiments, the adsorption cell was put in a water bath,and the temperature was maintained constant to within
(
0.02 K by a refrigerating circulator (Haake type F3).To eliminate any trace of pollutants, the zeolite 13X andZeocarbon samples were kept in a drying oven at 543 K
* To whom correspondence should be addressed. Tel.:
+
82-2-2123-2762. Fax:
+
82-2-2123-6401. E-mail: leech@yonsei.ac.kr.
†
Korea Research Institute of Chemical Technology.
‡
Yonsei University.
Table 1. Physical Properties of Zeolite 13X andZeocarbon
property zeolite 13X Zeocarbonbulk density/(kg
‚
m
-
3
) 689 500BET surface area/(m
2
‚
g
-
1
) 726 620micropore area/(m
2
‚
g
-
1
) 678 467micropore volume/(cm
2
‚
g
-
1
) 0.25 0.19BJH desortion average pore diameter/nm 28 27average pore diameter by BET/nm 23 28
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2002,
47,
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-
1242
10.1021/je020050e CCC: $22.00 © 2002 American Chemical SocietyPublished on Web 06/26/2002
for 24 h. After the mass of adsorbent was determined by amicrobalance with an accuracy of
(
10
µ
g, the samples wereintroduced into the adsorption cell. Prior to each isothermmeasurement, the charged adsorbents were regeneratedat 593 K under high vacuum for more than 12 h. An oildiffusion pump and a mechanical vacuum pump in com-bination (Edwards type Diffstak 63/150M) provided avacuum down to 10
-
3
Pa, and the evacuation was moni-tored with a pressure indicator. The volumes of themanifold and adsorption cell in the adsorption system weredetermined by expansion of helium gas at the experimentaltemperature. The total volumes of the manifold andadsorption cell measured by He were 583.03 and 23.62 cm
3
,respectively. Before the experiment, the adsorption systemwas flushed with helium gas three times and evacuatedwith a vacuum pump. Then, the desired amount of CO
2
gas was supplied to the manifold controlled by a valve.When the adsorption cell reached the desired temperature,CO
2
gas was admitted into the adsorption cell. During theexperiments, all of the temperatures and pressures wererecorded automatically on an interfaced computer. Thenumber of moles adsorbed were calculated from the mea-sured pressure, temperature, and gas volume by using idealgas law.
Results and Discussion
Adsorption isotherms for CO
2
on zeolite 13X and Zeo-carbon were obtained at (273.15, 293.15, 313.15, 333.15,and 353.15) K and at pressures up to 102.0 kPa on zeolite13X and 99.7 kPa on Zeocarbon. The adsorption isothermsfor CO
2
on zeolite 13X and Zeocarbon at the varioustemperatures are shown in Figures 2 and 3, respectively.The amount adsorbed on zeolite 13X was higher than thaton Zeocarbon within the experimental range. However, thedifference in the amounts adsorbed on the two adsorbentsdecreased with increasing pressure. The adsorption capac-ity, defined as the amount at the plateau of the isotherm,is higher for Zeocarbon than for zeolite 13X at higherpressures. The more favorable isotherms on zeolite 13Xthan on Zeocarbon at low pressure imply that the affinityof CO
2
is higher for zeolite 13X than for Zeocarbon becauseof the activated carbon in Zeocarbon. That is, the equilib-rium adsorption capacities of zeolite 13X and Zeocarbonat 0.55 kPa and 293 K were 1.07 and 0.77 mol of CO
2
/kg of the adsorbent, respectively, whereas those at 100 kPa and293 K were both about 3.5 mol of CO
2
/kg of the adsorbent.These values for zeolite 13X are similar to the results of aprevious study.
6
However, the results for Zeocarbon as azeolite X/activated carbon composite were higher thanthose for activated carbon, being about 0.2 mol of CO
2
/kgof the adsorbent at 0.55 kPa and 297 K and 2.2 mol of CO
2
/ kg of the adsorbent at 100 kPa and 297 K.
8,9
This differencewas due to the strong adsorption affinity of CO
2
on zeolitein the range of low pressures.The experimental equilibrium data are presented inTables 2 and 3, with the percent deviations DQ calculatedby the following equationwhere
q
exp
and
q
cal
are the experimental and calculatednumbers of moles adsorbed, respectively.
Figure 1.
Adsorption equilibrium apparatus.
Figure 2.
Experimental and correlated isotherms for CO
2
adsorp-tion onto zeolite 13X at various temperatures:
b
, 273 K;
9
, 293K;
2
, 313 K;
1
, 333 K;
[
, 353 K;
s
, Toth equation;
‚‚‚
, UNILANequation;
---
, Sips equation.
Figure 3.
Experimental and correlated isotherms for CO
2
adsorp-tion onto Zeocarbon at various temperatures:
b
, 273 K;
9
, 293 K;
2
, 313 K;
1
, 333 K;
[
, 353 K;
s
, Toth equation;
‚‚‚
, UNILANequation;
---
, Sips equation.
DQ/%
)
100
[
q
j
exp
-
q
j
cal
q
j
exp
]
(1)
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Journal of Chemical and Engineering Data, Vol. 47, No. 5, 2002
The Toth, UNILAN, and Sips models were used tocorrelate the experimental adsorption data for CO
2
onzeolite 13X and Zeocarbon.
Toth Isotherm.
The Toth isotherm
10
is a semiempiricalexpression that effectively describes many systems withsubmonolayer coverage. Because of its simplicity in formand its correct behavior at low and high pressures, the Tothequation is used in many applications as the isothermequation for fitting data for many adsorbates on activatedcarbon as well as zeolites.
11
It is a three-parameter model
Table 2. Adsorption Isotherm Data for CO
2
on Zeolite 13X
DQ DQ
P q
%
P q
%kPa mol
‚
kg
-
1
Toth UNILAN Sips kPa mol
‚
kg
-
1
Toth UNILAN Sips273.15 K0.067 0.95 11.6 32.6 1.87 26.92 3.33
-
1.61
-
1.05
-
0.280.468 1.47
-
1.23 1.42
-
1.63 33.68 3.42
-
2.30
-
1.52
-
1.160.829 1.68
-
2.30
-
1.94
-
1.26 40.95 3.54
-
1.67
-
0.72
-
0.721.598 1.95
-
2.70
-
3.60
-
0.68 47.43 3.64
-
0.95 0.12
-
0.152.980 2.23
-
2.64
-
3.82
-
0.23 54.08 3.70
-
1.13 0.04
-
0.454.336 2.41
-
2.39
-
3.46 0.05 61.08 3.75
-
1.45
-
0.18
-
0.885.748 2.55
-
2.15
-
3.04 0.24 67.95 3.80
-
1.56
-
0.20
-
1.077.071 2.66
-
1.76
-
2.50 0.54 74.67 3.88
-
0.71 0.70
-
0.319.960 2.83
-
1.68
-
2.12 0.44 81.49 3.96 0.20 1.65 0.5213.41 2.99
-
1.26
-
1.40 0.65 88.31 3.99
-
0.08 1.43 0.1716.80 3.15 0.25 0.33 1.95 95.16 4.05 0.46 2.00 0.6520.35 3.20
-
1.25
-
0.98 0.32 101.9 4.11 1.07 2.64 1.20293.15 K0.147 0.77 17.5 37.7 6.17 26.91 2.67
-
2.88
-
3.91
-
2.640.569 1.07 3.54 8.35
-
0.22 33.74 2.82
-
1.59
-
2.24
-
1.580.882 1.20 1.14 2.57
-
0.88 40.46 2.92
-
1.37
-
1.73
-
1.551.626 1.41
-
0.87
-
2.42
-
1.16 47.78 3.03
-
0.58
-
0.68
-
0.932.946 1.65
-
1.39
-
4.23
-
0.71 54.47 3.14 0.74 0.84 0.264.264 1.82
-
1.02
-
4.06
-
0.05 61.12 3.20 0.70 0.97 0.105.771 1.96
-
0.97
-
3.95 0.09 67.90 3.30 2.02 2.44 1.337.045 2.06 0.67
-
3.51 0.38 74.72 3.37 2.56 3.09 1.779.792 2.22
-
0.63
-
3.13 0.34 81.47 3.40 2.07 2.72 1.2013.41 2.38
-
0.44
-
2.52 0.37 88.13 3.42 1.43 2.19 0.4816.90 2.49
-
0.70
-
2.45
-
0.06 95.10 3.44 0.83 1.69
-
0.2020.43 2.59
-
0.56
-
2.01
-
0.08 101.9 3.45 0.06 1.01
-
1.04313.15 K0.226 0.54 14.5 37.9 0.87 27.23 2.23
-
1.02
-
2.44
-
0.430.625 0.76 7.21 16.5 1.44 33.70 2.33
-
1.38
-
2.34
-
1.040.892 0.85 4.77 10.1 0.99 40.73 2.44
-
0.83
-
1.38
-
0.741.706 1.04 1.16 1.17 0.14 47.33 2.54 0.05
-
0.17
-
0.052.997 1.23
-
0.76
-
3.29
-
0.28 54.32 2.63 0.73 0.80 0.445.629 1.47
-
2.14
-
5.67
-
0.85 61.26 2.69 0.58 0.90 0.157.084 1.57
-
2.11
-
5.63
-
0.73 68.21 2.75 0.69 1.22 0.1110.02 1.73
-
1.87
-
5.10
-
0.49 74.85 2.82 1.41 2.12 0.7213.50 1.88
-
1.28
-
4.07
-
0.05 81.49 2.88 1.89 2.77 1.1016.83 1.99
-
1.08
-
3.48
-
0.01 88.43 2.90 1.07 2.11 0.1720.70 2.10
-
0.68
-
2.67 0.20 95.10 2.92 0.43 1.61
-
0.5723.66 2.16
-
0.99
-
2.71
-
0.25 101.9 2.96 0.53 1.84
-
0.55333.15 K0.318 0.37 26.3 51.8 10.8 33.78 1.84
-
1.55
-
3.24
-
0.590.682 0.48 14.7 32.0 5.64 40.53 1.94
-
1.26
-
2.45
-
0.620.912 0.54 11.9 25.4 5.15 47.52 2.02
-
1.47
-
2.21
-
1.111.746 0.68 6.08 11.7 3.56 54.26 2.09
-
1.50
-
1.86
-
1.403.086 0.84 2.39 2.81 2.42 61.28 2.22 1.44 1.44 1.325.775 1.03
-
1.84
-
4.67
-
0.20 67.92 2.28 1.47 1.75 1.167.043 1.11
-
1.71
-
5.03 0.17 74.63 2.38 3.50 4.04 3.0310.04 1.25
-
2.43
-
6.11
-
0.33 81.53 2.42 3.06 3.84 2.4313.44 1.36
-
3.85
-
7.46
-
1.78 88.45 2.44 1.99 3.00 1.2116.94 1.47
-
3.52
-
6.81
-
1.61 95.22 2.45 0.71 1.93
-
0.2220.61 1.56
-
3.67
-
6.60
-
1.96 102.1 2.47
-
0.07 1.35
-
1.1427.00 1.69
-
3.71
-
6.03
-
2.37353.15 K0.353 0.30 38.3 51.8 22.4 27.31 1.38
-
2.23
-
9.30
-
1.200.712 0.36 22.4 29.3 11.3 33.87 1.49
-
1.55
-
7.41
-
0.860.922 0.39 16.9 20.6 7.70 40.69 1.60
-
0.16
-
4.95 0.201.758 0.48 6.92 2.55 2.31 47.55 1.68
-
0.02
-
3.96 0.063.060 0.59 0.66
-
8.81
-
0.85 54.38 1.76 0.66
-
2.52 0.485.839 0.76
-
3.41
-
15.5
-
2.63 61.05 1.83 1.21
-
1.35 0.817.075 0.81
-
4.81
-
17.0
-
3.63 67.79 1.89 1.47
-
0.54 0.879.949 0.94
-
3.83
-
15.4
-
2.26 74.66 1.95 1.91 0.41 1.1213.67 1.06
-
4.32
-
14.9
-
2.67 81.51 1.99 1.55 0.49 0.5916.94 1.17
-
2.24
-
11.7
-
0.71 88.30 2.01 0.41
-
0.26
-
0.7220.65 1.23
-
4.31
-
13.0
-
2.92 95.13 2.04
-
0.07
-
0.37
-
1.3523.85 1.32
-
2.13
-
9.91
-
0.93 102.0 2.09 0.53 0.57
-
0.88
Journal of Chemical and Engineering Data, Vol. 47, No. 5, 2002
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