Hefti2015 Ali

Accepted Manuscript
Adsorption Equilibrium of Binary Mixtures of Carbon Dioxide and Nitrogen on Zeolites

ZSM-5 and 13X
Max Hefti, Dorian Marx, Lisa Joss, Marco Mazzotti
PII: S1387-1811(15)00321-2
DOI: 10.1016/j.micromeso.2015.05.044
Reference: MICMAT 7153
To appear in: Microporous and Mesoporous Materials
Received Date: 18 November 2014

Revised Date: 25 February 2015
Accepted Date: 29 May 2015
Please cite this article as: M. Hefti, D. Marx, L. Joss, M. Mazzotti, Adsorption Equilibrium of Binary
Mixtures of Carbon Dioxide and Nitrogen on Zeolites ZSM-5 and 13X, Microporous and Mesoporous
Materials (2015), doi: 10.1016/j.micromeso.2015.05.044.
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ACCEPTED MANUSCRIPT
Zeolite 13X at 45°C
8
CO 2
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n [mol/kg]
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4
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2
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0 N2
1
C
0
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0.5 5
10
0 P [bar]
y CO [−]
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1 Adsorption Equilibrium of Binary Mixtures of Carbon

2 Dioxide and Nitrogen on Zeolites ZSM-5 and 13X
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3 Max Heftia , Dorian Marxa , Lisa Jossa , Marco Mazzottia,∗
a
4 ETH Zurich, Institute of Process Engineering, Sonneggstrasse 3, CH-8092 Zurich,
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5 Switzerland
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6 Abstract
An investigation of the adsorption equilibrium of carbon dioxide (CO2 ) and
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nitrogen (N2 ) and their mixtures on zeolites ZSM-5 and 13X is presented.
Pure component isotherms are measured at five different temperatures in
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the range of 25 ◦C to 140 ◦C and pressures up to 10 bar, and the resulting
data are described with an appropriate isotherm equation. Adsorption equi-
librium of CO2 /N2 mixtures was measured at two temperatures (25 ◦C and
45 ◦C) and three pressure levels (1.2 bar, 3 bar and 10 bar) using three feed
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gas compositions on both materials tested. The isotherms obtained from
the pure component measurements are used to predict the binary data us-
ing two approaches: An empirical extension of the Sips isotherm and the
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application of ideal adsorbed solution theory (IAST). In the context of the

binary CO2 /N2 adsorption, it was found that for ZSM-5 the system behaves
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close to ideal over the whole range of pressure and temperature investigated
here and thus is well described by the IAST prediction. On the other hand,
our results demonstrate non-ideal behavior in the adsorbed phase with in-
creasing pressure for zeolite 13X, thus motivating the use of real adsorbed
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solution theory (RAST) to accurately describe the binary adsorption data.

7 Keywords: zeolites, carbon dioxide, nitrogen, binary adsorption
8 equilibrium, RAST
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∗
Corresponding author: phone +41 44 632 2456; fax +41 44 632 11 41.
Email address: marco.mazzotti@ipe.mavt.ethz.ch (Marco Mazzotti)
Preprint submitted to Microporous and Mesoporous Materials February 24, 2015

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9 1. Introduction
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10 A number of process options have been proposed in order to separate the
11 CO2 from the flue gas by means of post-combustion capture technology 1 .
12 While amine based liquid absorption processes are the most advanced ones 2 ,
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13 adsorption-based processes have recently received significant attention due
14 to their potentially smaller energy requirement per ton of CO2 avoided and
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15 the stability and non-volatility of the solid sorbent material 3 . Mainly two
16 cyclic adsorption processes have been proposed for the seperation of CO2 .
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17 They differ in the method of sorbent regeneration, namely pressure/vacuum
swing adsorption (PSA/VSA) 4 and temperature swing adsorption (TSA) 5 .
18
19
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The heat content of the flue gas may be exploited for the regeneration of
20 the sorbent in a TSA process. However, the heat transfer is limited and
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21 therefore long heating and cooling times are required that ultimately lead
22 to low productivity 6 .
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23 A key component of the evaluation of a cyclic adsorption process is the

24 adsorbent material. To quantitatively evaluate such a process accurate ad-
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25 sorption equilibrium data is required. Frequently, only pure component equi-

26 librium data is available because of the experimental difficulties encountered
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27 in measuring multi-component adsorption. Ideally, the sorbent features a

28 large cyclic capacity, stability and regenerability and fast kinetics 7 . The
most widely used materials are activated carbon (PSA) and zeolites (TSA).
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29
30 While experimental efforts to develop novel materials are underway in many

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31 groups, in this work we would like to focus on the characterization of two

32 commercial zeolites, namely on the 13X and ZSM-5.
33 The adsorption of CO2 and N2 is studied in detail. First, the single
34 component adsorption of each of the gases is measured over a range of tem-
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35 perature from 25 ◦C to 140 ◦C, and described with an appropriate isotherm.

36 Second, binary adsorption equilibrium measurements are performed at
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37 two temperatures, 25 ◦C and 45 ◦C, on both sorbents and for a number of
38 different gas compositions. Ideally, a model used for the design of processes
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39 should be capable of predicting the competitive adsorption of the two com-
40 ponents by using only data obtained from pure gas isotherms. The measured
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41 equilibrium adsorption is compared to predictions by adsorption models: an
42 extended Sips and the application of ideal adsorbed solution theory (IAST)
43 to pure component Sips isotherms. Moreover, real adsorbed solution the-
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44 ory (RAST) is used to describe non-ideal behavior where necessary. The
45
46
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reader is referred to Table 1 for a compilation of available literature about
adsorption of the same gases on the same adsorbents.
It should be noted that in this work, we would like to focus on the
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47
48 description and interpretation of the adsorption behavior only. A detailed

49 discussion of the heat of adsorption both for the pure as well for the binary
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50 systems will be the subject of a follow-up work.

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51 2. Experimental setup and methods

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52 2.1. Materials
53 Two types of zeolites are studied in depth with regards to their ad-
sorption capacity and selectivity: ZSM-5 and 13X in the form of spherical
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54
55 pellets of diameters ranging from 1.2–2mm and 1.6–2mm, respectively; both

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56 manufactured by ZeoChem (Uetikon, Switzerland). According to the man-

57 ufacturer the pellets for both zeolites contain an unknown binder content
58 between 15% and 25% (on a mass basis).
59 The ZSM-5 used in this study has a silica to alumina ratio (Si/Al) of
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60 200. The porous structure is identical to silicalite (MFI type), and it consists
61 of a three dimensional framework structure defined by 10-membered ring
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62 openings 8;9 . The framework itself contains two channel systems that run
63 perpendicular to one another 9 . One of them is straight with ring openings
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64 of 5.4×5.6 Å2 while the other channel system is sinusoidal with openings of
65 5.1×5.5 Å2 .
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66 The framework structure of 13X zeolite is a tetrahedral lattice of sodalite
67 units that are connected through six-membered oxygen bridges and form
68 large cavities with 14 Å in diameter 10;11 . The resulting channel system
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69 consists of cages that are connected to four other cages through twelve-
70
71
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membered oxygen rings with a diameter of approximately 7.4 Å 10 .
The gases used were obtained from Pangas (Dagmarsellen, Switzerland)
with purities higher than 99.9 % for the pure gases; the gas mixtures were
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72
73 produced by Pangas with a relative error of ± 1 %.

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74 2.2. Interpretation of adsorption data

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75 In practice and for rigorous thermodynamic calculations, it is often de-

76 sirable to know the absolute amount adsorbed 12;13 . Using the gravimetric
77 method employed in this study, or any other method, this quantity is not
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78 directly accessible. Adsorption is determined as an incremental quantity

79 rather than an absolute one, thus it is associated with a reference state 14;15 .
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80 A set of assumptions is required to convert the raw data to an absolute

quantity. There are two frameworks that can be used to perform this con-
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81
82 version, namely excess adsorption and net adsorption, that will be briefly
83 presented and compared in the following.
84 The definitions associated to the two approaches are based on the follow-
85 ing quantities: the volume of the adsorbent, V s ; the volume of the adsorbed
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86 phase, V a ; the bulk density, ρb , i.e. the density of the fluid phase far from
87 the adsorbent surface; the total absolute mass adsorbed, mabs , i.e. the mass
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88 of the adsorbate(s) that occupies the volume V a .
89 Within the excess adsorption framework, the excess mass adsorbed, mex ,
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90 is defined as
mex = mabs − ρb V a , (1)
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91 which is the difference between the absolute mass adsorbed and the mass
92 that would occupy the same volume V a at the density of the bulk fluid ρb .
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93 In the scope of the net adsorption framework, the net mass adsorbed,
mnet , is defined as:
94
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mnet = mabs − ρb (V s + V a ) (2)
which can be seen to be “the total amount of gas present in the container
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95
96 with the adsorbent minus the amount that would be present in the empty
97 container (without the adsorbent) at the same temperature and pressure”,
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98 as defined by Gumma and Talu 16 .

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99 It is worth noting that both mex and mnet can be negative, and that:
mnet = mex − ρb V s (3)

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100 From both definitions and the obvious value of ρb , mabs can be obtained
provided one can measure either mex and V a or mnet and V a + V s .
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101
102 Though both frameworks have their merits, the excess adsorption has
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103 so far been used more frequently 13 . It has been consolidated in numerous
104 studies 17;18;19;20;21;22 while at the same time, the underlying assumptions
105 have been challenged and their validity has been thoroughly analyzed and
106 discussed 23 . In spite of this, the excess adsorption framework is still the
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107 defacto standard method to determine the absolute amount adsorbed, and in
108 this work, as in our previous studies 24;25;12;26 this framework is also used. For
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109 a more detailed overview and discussion of the ways to interpret adsorption
110 data the reader is referred to contributions by Gumma and Talu 16 , Talu 14 ,
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111 Pini 15 , Myers and Monson 13 and the references therein.
2.3. Single component adsorption equilibrium
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112
113 All equilibrium adsorption measurements were done with a gravimetric

114 method using a Magnetic Suspension Balance (MSB) by Rubotherm (Ger-
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115 many), as it is described in Ottiger et al. 27 . This balance is capable of
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117
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operating at pressure and temperature levels of up to 450 bar and 400 ◦C,
and allows for the direct measurement of the bulk density ρb of the gas,
118 eliminating the need for an equation of state. In addition, the measurement
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119 cell is equipped with an electrical heater that allows regeneration of the
120 sample at temperatures of up to 400 ◦C. The measuring principle for pure
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121 gases (CO2 and N2 ) and more information on the measuring principle of a
MSB have been described in detail elsewhere 28;12;29 .
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122
123 The sample was regenerated before the measurement of each new isotherm
124 by heating it to 400 ◦C for four hours while applying vacuum. This ensures
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125 the removal of any moisture that adsorbed during the handling of the sam-
126 ple. Isotherms were measured at five temperatures for each sample, at 25 ◦C,
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127 45 ◦C, 65 ◦C, 100 ◦C and 140 ◦C, and for pressures up to 10 bar for both CO2
and N2 . A number of points on the first isotherm measured (CO2 at 25 ◦C)
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128
129 were repeated after all pure gas measurements were completed to verify that
130 repeated thermal cycling did not alter the equilibrium adsorption character-
131 istics of the sorbent.
132 To convert the molar excess amount, nex , to the molar absolute amount,
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133 nabs , via the excess adsorption framework an additional assumption about
134 the nature of the adsorbed phase is required 19 . A widely used approach is
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135 based on the observation that nex decreases linearly with the bulk density
136 once the sorbent has been saturated, i.e. where the change of volume and
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137 density in the adsorbed phase can be assumed negligible. Then, a linear
138 regression allows the estimation of the volume of the adsorbed phase and
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139 its density ρa 20;12;21;22;25 . For the conversion it is then assumed that the
140 estimated value for ρa is valid for the whole isotherm, and thus for the
141 whole pressure range 12;26 ; nabs and nex are then related by:
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−1
ρb

n abs
AN
=nex
1− a
ρ
(4)
142 To determine ρa of CO2 on each sample, the CO2 isotherm at a tem-

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143 perature of 45 ◦C was measured up to approximately 170 bar, which is well
144 into the linear region described above. The data is reported in the sup-
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145 porting information (SI). For N2 our experimental setup does not allow to
reach the required conditions so as to determine ρa as described above. As
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146
147 is common when it is not experimentally accessible, the adsorbed phase

148 density of N2 was assumed to be equal to the liquid density at the boiling
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149 point 30;31;32;26;15 , i.e. ρa = 28.8 ± 0.4 mol/L. The same relative error as
150 for the 13X/CO2 system was assumed to allow proper error propagation
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151 calculations.
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152 2.4. Binary adsorption equilibrium
153 The binary adsorption measurements were performed with the same
154 setup as the single component measurements. A schematic of the setup
155 used is shown in Figure 1. The core principle of the binary adsorption mea-
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156 surements relies on the fact that the void volume of the system is known.
157 The method of measurement is described in detail in Ottiger et al. 12 . Key
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158 differences to the methods used in Ottiger et al. 12 and Schell et al. 26 are
159 summarized below.
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160 The secondary adsorption cell as indicated in Figure 1 provides a means
161 to add additional sample to induce a more pronounced compositional change
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162 in the gas phase due to adsorption, which is then detected by the GC. The
163 part of the setup, as surrounded by the dashed frame shown in Figure 1,
164 is submerged in a Huber Polystat (Renggli, Rotkreuz, Switzerland) 27 . It is
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165 operable up to 200 ◦ C. To ensure complete regeneration of the sample, we
166
167
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didn’t make use of the secondary adsorption cell. Instead, to minimize the
dead volume in the system a stainless steel cylinder of known volume was
used to occupy the secondary adsorption cell. In this way, sorbent is only
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168
169 present in the MSB, and thus can be regenerated at 400 ◦ C. A number of
170 test points were measured to make sure that the compositional change due
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171 to adsorption in the gas phase was sufficiently large to be detected by the
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172 GC.
173 There is minor leakage present in this setup, which may lead to accu-
mulation of one component in the gas phase. Thus, there is a small penalty
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174
175 in letting the system equilibrate over an extended period of time. It was
176 observed that a suitable indicator to define equilibrium was when the weight
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177 change was less than 0.3 mg per hour. This criterion was used in all binary
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178 adsorption experiments in this work. A maximum number of three subse-

179 quent equilibrium points were measured before regenerating the system.
180 At every measurement point at least four GC measurements were per-
181 formed to ensure a representative gas phase composition. Each of the GC
182 measurements requires a minor interference with the system since a small
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183 volume is expanded in the sampling loop as shown in Figure 1. This was
184 accounted for in the evaluation of the data by a mass balance over the sys-
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185 tem:
Nm
X NX
m −1
meff
i = wifeed mfeed − wi ∆msample (5)
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i=1 i=1
186 This expression yields the corrected amount of component i in the system,
meff
i . m
feed is the amount of fluid fed to the system with weight fraction
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187
188 wifeed . ∆msample

i is the mass difference before and after the GC measure-
189 ments and is obtained by the weight response of the MSB. wi is the weight
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190 fraction of the fluid phase as determined by the GC measurements. Finally,
Nm indicates the number of preceding measurements and ranges in our mea-
191
192
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surements from 1 to 3. It is worth noting that for the first measurement
193 point meff
i =m
feed w feed .
i
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194 3. Modeling
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195 3.1. Single component

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196 The data obtained for pure component adsorption were described with
197 a Sips isotherm 33;34 . The Sips model expands the standard Langmuir by
introducing a third parameter that accounts for a distribution of affinity of
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198
199 the surface sites towards the sorbate molecules as follows:
ci
n∞i (bi P )
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ni = (6)
1 + (bi P )ci
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200 where i indicates component i (i.e. CO2 or N2 ), P the pressure, n∞

i repre-
201 sents the saturation capacity, bi the affinity constant and ci the heterogeneity
202 parameter, which is bounded by 0 < ci ≤ 1. The larger the deviation of ci
203 from unity, the larger is the non-uniformity of the surface for component i.
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204 Note that for ci = 1 the Langmuir isotherm is obtained.
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205 3.1.1. Temperature dependence
206 According to Do 35 the temperature dependent saturation capacity can
take the following form:
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207

T
n∞
i (T ) = n∞
ref,i exp χi −1 (7)
Tref
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208 where T is the temperature, n∞
ref,i is the saturation capacity at reference
temperature Tref and χi is a dimensionless fitting parameter.
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209
210 The temperature dependence of the affinity parameter bi is commonly

211
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described by an Arrhenius type equation, that is

Qb,i
bi (T ) = b0,i exp (8)
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RT
212 where R is the universal gas constant, b0,i is the pre-exponential factor and
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213 Qb,i the characteristic energy for the affinity constant bi (T ) 35 .

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214 The temperature dependence of the heterogeneity parameter ci is essen-

215 tially empirical. A form proposed in Do 35 is
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T
ci (T ) = cref,i + αi −1 (9)
Tref
where cref,i is the heterogeneity parameter at the reference temperature Tref

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216
217 and α is a dimensionless fitting parameter.

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218 3.1.2. Henry’s constant

219 The Henry’s constant H is the slope of the tangent to the adsorption
220 isotherm at the zero pressure limit. Henry’s constants are useful indicators
221 to compare the adsorption strength between different sorbate-sorbent pairs.
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222 A drawback of using the Sips isotherm is the incorrect Henry’s region
223 limit. To circumvent this, a virial isotherm based method to evaluate the
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224 Henry’s constants is used 36 . The virial isotherm equation is derived on the
225 basis of a general formulation of an equation of state of the virial form for
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226 the adsorbed phase 36;10 . It can be shown that the Henry’s constant is given
227 by:
n 3
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2
H = exp 2D1 n + D2 n + ... (10)
P 2
228 where the D’s are the virial coefficients. We truncated (10) after the first
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229 term in the exponent and fitted the resulting expression to the adsorption
data at each temperature for the sorbent-sorbate pair. In this way, H is
230
231
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found directly from the parameter estimation. Alternatively, H may be
232 found by a plot of ln (n/P ) against n and extrapolating to the limit of zero
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233 adsorbed phase concentration 36 .
3.2. Binary system

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234
235 To convert the individual excess adsorbed amount nex

i in the mixture
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236 to the absolute quantity nabs

i a similar method as for the pure component
237 case, equation (4), applies. The relationship between nex
i and the absolute
quantity nabs
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238
i is given by:
−1
ρyi
nabs
i = nex
i 1− a (11)
ρ xi
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239 where yi is the mole fraction of component i in the bulk phase. It is worth
240 noting that this expression reduces to equation (4) for the case of a pure
241 component. While the pure component adsorbed phase densities can be es-
242 timated via the method described in section 2.3, an assumption with regard
243 to the mixture adsorbed phase density, ρa , must be made. Since an inher-
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244 ent assumption of IAST is ideal behavior in the adsorbed phase, an obvious
245 approximation for ρa is provided by applying the volume additivity 20;26 rule:
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1 xN xCO
a = a2 + a 2 (12)
ρ ρN2 ρCO2
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246 This assumption is mad in the following, and it is critically discussed in
section 4.2.6.
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247
248 3.2.1. Extended Sips isotherm

An empirical extension of the pure component Sips isotherm is given
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249
250 by 37 :
ni =AN n∞
1+
i (bi Pi )
N
P C
ci
(bj Pj )cj
(13)
j
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251 where NC denotes the number of components (in the following the upper
252 limit for the sum, NC , is omitted for the sake of clarity). The advantages of
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253 this equation are (i) that only pure component parameters are required and
(ii) that it is explicit, which is convenient to use in a dynamic process model.
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254
255 When all the heterogeneity parameters are unity, equation (13) reduces to
256 the multicomponent Langmuir isotherm.
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257 3.2.2. Adsorbed Solution Theory

258 In their revolutionary contribution Myers and Prausnitz 38 presented
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259 a thermodynamically consistent framework to predict multicomponent ad-

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260 sorption equilibria based on pure component parameters.

261 The variation in the molar Gibbs free energy g at constant temperature
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262 T and spreading pressure Π is given by 38 :
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X
g (T, Π, x) = RT xi ln xi γi (Π, T, x) (14)
i
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263 where xi is the mole fraction of component i in the adsorbed phase, x the
264 corresponding adsorbed phase composition vector and γi the activity coef-
ficient. At the same chemical potential of the gas and the adsorbed phase,
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265
266 the equilibrium relation for mixed-gas adsorption for an ideal gas phase is:
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P yi = Pi0 (Π) xi γi (Π, T, x) (15)
267
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where P is the system pressure and yi the mole fraction of component i
268 in the gas phase. Pi0 is the hypothetical equilibrium pressure of the pure
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269 component at the same Π and T of the mixture and is obtained from:
0
ZPi
D
ΠA ni (Pi )
z= = dPi (16)
RT Pi
0
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270 where z is the reduced surface potential, A the specific surface area of the
271 sorbent and ni (Pi ) is the adsorption isotherm equation for component i.
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272 The left hand side of this expression must be the same for all components.
273 For the Sips isotherm model used in this work, the reduced surface potential
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274 can be expressed in closed form as:

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ci
n∞ log 1 + bi Pi0
z= i (17)
ci
275 To obtain the total amount adsorbed, nt , an expression as derived from the
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276 definition of the molar area of mixing is used 38;39 :

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1 X xi X ∂ ln γi
= + xi (18)
ni Pi0

nt ∂z T,x
i i
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277 This equation complies with the Gibbs-Duhem relation 39 .
278 Finally, the number of moles of each component adsorbed is:
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n i = xi n t (19)
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279 In the case where the adsorbed phase is assumed ideal and thus γ = 1 for
all components, the ideal adsorbed solution theory is obtained (IAST); in
280
281
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this case the second term in equation (18) vanishes 40 . Only pure component
282 parameters and no binary data is required for IAST.
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283 In general, the activity coefficients are not unity; in this case the so-
284 called real adsorbed solution theory is obtained (RAST). For the activity
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285 coefficients two thermodynamic constraints must be fulfilled 41;35 :

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286 (i) γi approaches unity when the composition of i approaches unity:
lim γi = 1 (20)
xi →1
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287 (ii) At infinite dilution the ideal solution behavior is approached:

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lim γi = 1 (21)
π→0
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288 A variety of models for the activity coefficients in the adsorbed phase
289 have been proposed 42;43;41;44;45 . Many of those models are derived from their
290 analogue models used for liquid-vapor systems. In this work, a modified
291 expression adopted from the Wilson model for vapor-liquid equilibrium 46
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292 as proposed by Karavias and Myers 42 is used. The activity coefficients are
293 given by:
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  !
x Λ
P k ki
X X
ln γi = 1 − ln  xj Λij  − (22)
j k j xj Λkj
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294 Due to the second thermodynamic constraint as listed above, the activity
295 coefficents for the adsorbed phase are a function of z. An empirical relation
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296 fulfilling the constraints was proposed by Karavias and Myers 42 and is also
297 used in this work:
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Λij = Λ0ij − 1 (1 − exp (−ωz)) + 1

(23)
298
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In the original formulation of Wilson 46 Λij has a temperature dependency
299 that arises from the semi-empirical derivation and thus has at least an ap-
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300 proximate theoretical basis 47 . In this work, two binary adsorption data sets
301 at different temperatures (25 ◦ C and 45 ◦ C) are used to estimate the activity
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302 coefficients. Therefore, in line with Suwanayuen and Danner 48 we propose

to use the original definitions developed by Wilson 46 for Λ0ij so as to include
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303
304 the temperature dependence:

vj λij − λii vj λi
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Λ0ij = exp − = exp − (24)

vi RT vi RT
305 where λij is the i, j-interaction energy and vi is the molar volume of species
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306 i 47 . For the parameter estimation one fits directly the difference (λij − λii )
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307 denoted here by λi .

308 Thus, for a two component system there are three parameters to be fitted
309 to the binary adsorption equilibrium data, namely λ1 , λ2 and ω.
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310 3.3. Parameter estimation
311 To estimate the set of Sips parameters, i.e. the parameter vector θ =
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312 [θ1 , θ2 , . . . , θj , . . . , θNθ ] of length Nθ , the following objective function was
313 minimized:
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T XN Nj
1 X
Φp (θ) = ln (nexp (Tj , pjk ) − n (θ, Tj , pjk ))2 (25)
Nd
j=1 k=1
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314 where Nd is the number of experimental points of all experiments for a given
315 sorbate-sorbent pair, NT is the number of temperatures, Nj the number of
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316 experimental points at temperature Tj . In this way, θ∗ is obtained as the si-
317
318
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multaneous fit of the experimental data sets at all temperatures. We impose
three assumptions on the measurement errors: (i) they are independent, (ii)
in each experiment they are distributed with the same covariance matrix
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319
320 and (iii) they are uncorrelated for different experiments 49 . With these as-
321 sumptions, minimization of equation (25) yields the maximum likelihood
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322 estimate, i.e. the values of the set of parameter θ∗ that have maximum
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323 probability of producing the measured adsorption data 50 .

324 The minimization of equation (25) is a nonlinear optimization problem
and is bounded in the parameter domain. The built-in Matlab local opti-
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325
326 mization routine fmincon using a sequential quadratic programming algo-

327 rithm was employed in combination with GlobalSearch to cover a large set
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328 of initial points in order to find the optimum. Whether the attained θ∗ is
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329 indeed a global minimizer of Φ remains unknown 51 .

330 Only the minimum number of parameters were fitted to obtain a rea-
331 sonable agreement between experiment and model. In particular, whenever
332 possible the temperature invariant reference values for the saturation ca-
333
ref,i , and for the heterogeneity parameter, cref,i , were used. This is
pacity, n∞
16
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334 equivalent to having zero values for χ and α in equations (7) and (9), respec-
335 tively. The reference temperature Tref was defined as the lowest temperature
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336 at which the adsorption experiments were performed and thus Tref = 25 ◦ C.
337 The reference values were then defined as the values obtained from a fit to
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338 the data set at the reference temperature only, i.e.
n∞ ∞
ref,i = ni (Tref )
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(26)
cref,i = ci (Tref )
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339 The objective function to estimate the activity coefficient parameters is
340 given by the maximum likelihood estimate, i.e. the logarithmic quantity:
1
N
XT XN
P Xk N
AN
Φb (θ) = ln (nexp (Tj , Pjkl ) − n (θ, Tj , Pjkl ))2 (27)
Nbin
j=1 k=1 l=1
M
341 where Nbin is the number of data points, NP the number of pressures (in
D
342 our case NP = 3, namely 1.2 bar, 3 bar and 10 bar) and Nk the number of
343 experimental data points at the kth pressure level. Here, n (θ, Tj , pjkl ) is
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344 determined by solving the RAST model at the values contained in θ.

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345 4. Results and discussion
346 4.1. Pure component isotherms

C
347 The pure component (absolute) adsorption data of CO2 and N2 on ZSM-
5 at 25 ◦ C, 45 ◦ C, 65 ◦ C, 100 ◦ C and 140 ◦ C on ZSM-5 and 13X are shown in
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348
349 Figure 2 and 3, respectively. This specific temperature range was motivated
350 by the thinkable operating conditions in a post-combustion CO2 capture
351 process.
17
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352 The experimental excess amount was transformed into absolute adsorp-
353 tion by using equation (4) assuming a constant adsorbed phase density. For
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354 CO2 on 13X a density of ρa = 26.58 ± 0.36 mol/L was obtained, while for
355 CO2 on ZSM-5 an adsorbed phase density of ρa = 21.76 ± 0.71 mol/L was
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356 determined. Because of the smaller pore size of ZSM-5 as compared to 13X
357 a lower ρa for CO2 on ZSM-5 is expected because of the constrained packing
SC
358 of the adsorbed CO2 molecules. Assuming negligible surface adsorption, an
359 estimate of the pore volume of the zeolite may be extracted: For ZSM-5
360 it is 0.155 ± 0.004 cm3 /g and for 13X 0.270 ± 0.003 cm3 /g. Comparison
U
361 with literature data is worth the while. First, there is limited data available
362
363
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regarding the pore volume, as seen in Table 1. Second, it is difficult to pre-
dict the effect of the binder (type and content) on the pore volume. Olson
et al. 52 list a value of 0.18 cm3 /g for (binderless) HZSM-5 with a Si/Al ratio
M
364
365 of 150. If the binder were to reduce the pore volume proportionally to its
366 amount, this would result in a range of pore volume of 0.135–0.153 cm3 /g
D
367 for a binder content ranging between 25 % and 15 %. Our value is slightly
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368 above this range, but lower than the other values reported in Table 1. As to
369 zeolite 13X the values of the pore volumes in Table 1 exhibit also significant
variations. Our value is between the lowest as reported by Park et al. 53
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370
371 and Lee et al. 54 , i.e. 0.250 cm3 /g, and the highest reported by Rother and
372 Fieback 55 , i.e. 0.306 cm3 /g. We refer to Pini 15 for a critical discussion on
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373 the techniques to determine the pore volume.

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374 In Figures 2 and 3 the experimental data (symbols) is shown with the
375 corresponding best fits of the Sips isotherm (lines). The resulting parameter
376 estimates with the corresponding uncertainties are reported in Table 2. As
377 seen from Figures 2 and 3 the adsorption data could be well described by
378 the Sips isotherm. Moreover, the uncertainty intervals for all the parame-
18
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379 ters are indeed small; well-determined parameters have been obtained. As
380 recognized from Table 1, the Sips isotherm is, amongst others such as the
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381 Toth and the Langmuir models, a frequently used isotherm model to de-
382 scribe adsorption equilibrium of N2 and CO2 in ZSM-5 and zeolite 13X. Lee
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383 et al. 54 compared the Sips, the Toth and the UNILAN models and observed
384 that the Sips isotherm gave the best description of their CO2 data on zeolite
SC
385 13X. The same result comparing the Langmuir, Sips and Toth models was
386 found for N2 data on zeolite 13X by Park et al. 53 .
387 All of the isotherms are of type I characterized by a rather steep increase
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388 in the low pressure region and a subsequent flattening of the adsorption
389
390
AN
toward 10 bar. The initial increase is more pronounced for CO2 on both
zeolites as compared to N2 , as recognized from the zooms given in Figures
2(b), 2(d) and Figures 3(b), 3(d). For the 13X/CO2 system the isotherms up
M
391
392 to 100 ◦ C are only gradually increasing at 10 bar indicating that the system
393 is close to the saturation limit. In contrast, for the other systems considered
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394 here, namely 13X/N2 , ZSM-5/CO2 and 13X/N2 , the saturation limits are
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395 well above 10 bar. In a recent modeling study by Newsome et al. 56 it is

396 reported that the adsorbed amount of N2 on ZSM-5 is still increasing at
300 bar. On the other hand, CO2 adsorption on ZSM-5 is close to saturation
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397
398 at 20 bar 56 . It is also worth noting that the adsorption for CO2 at 10 bar
399 on 13X is around 6 mol/kg, which is about the 2.5-fold of the amount of
C
400 CO2 adsorbed on ZSM-5 at the same pressure. A major contribution to the
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401 higher adsorption capacity of 13X is the micropore volume per unit mass of
402 sorbent. As reported above, for 13X it is about 45 % larger than for ZSM-5.
403 We note that our values for the adsorbed amounts lie well within the values
404 reported in the literature as seen in Table 1.
405 To compare the affinities of the different systems the Henry’s constants
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406 were determined according to a Virial isotherm based method as described in

407 section 3. The resulting Henry’s constants plotted against temperature are
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408 reported in Figure 4, and their numerical values are summarized in Table 3.
409 The Henry’s constants for all systems decrease linearly from 25 ◦ C to 100 ◦ C.
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410 At the highest temperature of 140 ◦ C the decrease in the Henry’s constant is
411 slightly less. The Henry’s constants for the 13X/CO2 and 13X/N2 systems
SC
412 are remarkably different and thus indicate a high CO2 /N2 selectivity. A
413 much lower CO2 /N2 selectivity is expected for ZSM-5.
414 It is noteworthy how pronounced the difference in the Henry’s constants
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415 is for the 13X/CO2 and the ZSM-5/CO2 systems. To understand this obser-
416
417
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vation, it is worth comparing the interactions between the sorbate molecule
and the structural features of these two zeolites in more detail. It has been
shown that the interaction of CO2 and the zeolite is a superposition of pore
M
418
419 wall interactions and of interactions with the extra-framework cations 57 ,

420 Na+ in our case. The latter are in turn classified as repulsion-, polarization-
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421 and quadrupole-interactions 58;59 and have been found to be much stronger
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422 than the CO2 -pore wall interaction 58 .

423 From the chemical formulas of the zeolites, the maximum Na+ -concentration
per unit mass can be determined: 13X zeolite has a maximum Na+ -concentration
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424
425 of 4.8–5.4 mmol/g while for ZSM-5 the range is 0.06–0.07 mmol/g. Note that
426 the main uncertainty is due to the unknown binder content of the samples
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427 used in this work. Thus, there are roughly two orders of magnitude differ-
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428 ence in the Na+ -concentration. As a consequence, the interaction energy

429 and thus the affinity between CO2 and 13X is much higher than between
430 CO2 and ZSM-5.
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431 4.2. Binary isotherms
432 The binary CO2 /N2 data on ZSM-5 and 13X at the system pressures of
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433 1.2 bar, 3 bar and 10 bar at the temperatures of 25 ◦ C and 45 ◦ C is shown
434 in Figures 5 and 6. As for the pure components, the adsorption data is
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435 reported in absolute adsorption. For the conversion from excess to absolute
436 adsorption the mixture density ρa was approximated by equation (12). The
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437 validity of this assumption is critically discussed below (section 4.2.6).
438 From Figure 6 it is clear that the selectivity between CO2 and N2 on
13X is high; as is expected from the pure component data. In particular,
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439
440 for the lowest system pressure of 1.2 bar, i.e. Figures 6(a) and 6(d), there
441
442
AN
is considerable enrichment of the less adsorbing component N2 in the bulk
phase. Therefore, the data points are shifted towards lower CO2 mole frac-
M
443 tions in the bulk phase as compared to the nominal feed compositions (on
444
f
molar basis: yCO = 0.25, 0.5, and 0.75, with the balance being N2 ). To
2
visualize this effect, the nominal feed compositions are indicated as vertical
D
445
446 dashed lines in Figures 6(a) and 6(d). The enrichment of the gas phase in N2
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447 is less pronounced for the higher pressures because the relative importance
448 of the adsorbed phase in the system is reduced at higher bulk densities.
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449 4.2.1. Extended Sips

450 In Figures 5 and 6 the extended Sips predictions are shown as dotted
C
451 lines. For both ZSM-5 and 13X, at the system pressures of 1.2 bar and 3 bar
and both temperature levels the adsorption data is well predicted by the
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452
453 extended Sips isotherm. At 10 bar and both temperatures, some deviations
454 of the extended Sips predictions and the data are observable. CO2 adsorp-
455 tion is underpredicted while the amount of N2 adsorbed is overpredicted. A
456 close look to the lower pressures indeed reveals that this trend is also true
21
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457 for those pressures; however, to a much less pronounced extent. Thus, the
458 extended Sips isotherm underestimates the extent of competition between
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459 CO2 and N2 on both zeolites.
4.2.2. IAST
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460
461 The IAST predictions for ZSM-5 and 13X are reported as dashed lines
also in Figures 5 and 6, respectively. For ZSM-5 the IAST prediction de-
SC
462
463 scribes the data well for all the conditions investigated here. In particular,
464 it is apparent that the data are well described by the IAST also at the 10 bar
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465 pressure level, i.e. the conditions at which the extended Sips isotherm fails
466
467
to accurately predict the data.
AN
For 13X zeolite the IAST predicts the data reasonably well for the pres-
468 sure levels of 1.2 bar and 3 bar for both temperatures. As opposed to the
M
469 extended Sips model, the IAST overpredicts the CO2 adsorption while the
470 amount of N2 is underpredicted. This is apparent in particular for the 10 bar
D
471 pressure level as seen in Figures 6(c) and 6(f). The experimental data at
10 bar lies somewhere in between the two predictive models. Thus the de-
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472
473 gree of competition of CO2 and N2 on 13X is overestimated by IAST.

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474 4.2.3. RAST

475 The deviations from ideal behavior as predicted by the IAST observed
476 in the binary CO2 /N2 data on 13X zeolite is rather low. Nevertheless, they
C
477 are significant at the 10 bar pressure level. In addition, it is worth pointing
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478 out that the success of the prediction of binary data based on the IAST by
479 and large depends on the quality of the pure component description 60;61 .
480 As shown in section 4 the Sips isotherm does indeed give an accurate de-
481 scription of the pure component data. Therefore, it may be concluded that
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482 the deviations of the data from the IAST predictions are not experimental
483 artifacts, but indeed they stem from the non-ideal behavior of the adsorbed
PT
484 phase on 13X.
485 To obtain a better description of the binary adsorption data on 13X ze-
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486 olite, a modeling study using the RAST formulation has been undertaken.
487 For this purpose, the activity coefficients in the adsorbed phase were de-
SC
488 scribed by a modified Wilson model as described in section 3, referred to
489 here as the 3-parameter Wilson model. The parameters λ1 , λ2 and ω were
490 fitted to the whole binary CO2 /N2 data set on 13X. It is worth noting that
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491 the molar volumes vi and vj required for the calculation of Λ0ij were taken as
492
493
AN
the inverse of the molar adsorbed phase density of the corresponding pure
component. The values of the best fit parameters along with the confidence
intervals and the value of the objective function Φb at the optimum are
M
494
495 reported in Table 4.

496 Close scrutiny of the confidence intervals reveals that the parameter ω
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497 is particularly ill-determined and thus is probably redundant. Furthermore,

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498 an interdependency of the Wilson parameters in the context of non-ideal

499 adsorbed phase behavior has been reported in the monograph by Ruthven 10 ,
suggesting that it is possible to correlate the remaining two parameters λ1
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500
501 and λ2 as shown below.

502 Based on this analysis, we propose a simplification to the model used
C
503 above by imposing two assumptions. The term exp (−ωz) for the value of
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504 ω estimated becomes significant only at pressures below any studied in this
505 work. This indicates that the dependence of the activity coefficient on Π
506 can be neglected within the range of operating conditions investigated here.
507 Therefore, our first assumption is that Λij = Λ0ij .
508 Secondly, we assume that the interaction energy between CO2 and N2
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509 is given by the arithmetic mean of the interaction between the individual
510 species:
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1
λ12 = (λ11 + λ22 ) (28)
2
511 In that case we have that λ1 = −λ2 and thus Λ12 Λ21 = 1.
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512 Under these assumptions, there is one parameter left to estimate for
513 the RAST model, that is λ1 . We refer to this simplified model as the 1-
SC
514 parameter Wilson model, the best fit of which is shown as solid lines in
515 Figure 6. The resulting numerical value for λ1 and its confidence interval is
U
516 reported in Table 4 alongside with the value of the objective function Φb at
the optimum.
517
518
AN
From Figure 6 it is evident that the RAST accurately describes the
519 experimental data at all conditions. Comparing the values for Φb at the
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520 corresponding optimum for the 3- and 1-parameter Wilson models it is clear
521 that the quality of the fits are similar; in fact, the difference in Φb is in the
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522 second digit.

523 The success of the 1-parameter Wilson model suggests that (i) the ap-
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524 proximation of using the arithmetic mean of the interaction between CO2
525 and N2 in the adsorbed phase is a valid assumption, (ii) the effect of the
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526 spreading pressure Π on the activity coefficients is negligible and (iii) a single
527 parameter is sufficient to describe the non-ideal behavior of the the binary
mixture of CO2 /N2 on 13X. Based on these results, we underline the impor-
C
528
529 tance of determining at least approximate confidence intervals for the best
AC
530 fit parameters used in activity coefficient models as it provides a means to

531 identify ill-determined parameters.
532 A similar result as ours has been found by Gamba et al. 44 , who inves-
533 tigated binary adsorption data of ethylene/propane/ethane on 5 Å zeolite.
24
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534 They obtained significant parameters for their activity coefficients model by
535 fixing some parameters and neglecting the influence of Π on the activity
PT
536 coefficients. The same authors point out that for a quantitative estimate
537 of the effect of Π on the activity coefficients a wider range of pressures, i.e.
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538 including pressures as low as 10 mbar and less, would have to be investigated.
4.2.4. Effect of temperature
SC
539
540 An interesting behavior of the adsorption with respect to the variation

541 of temperature is observed for the IAST/RAST predictions. The IAST
U
542 predictions between 25 ◦ C and 140 ◦ C at a system pressure of 10 bar of the
543
544
AN
CO2 /N2 mixture on ZSM-5 are shown in Figure 7(a). The RAST simulations
of the CO2 /N2 mixture over the same temperature range on 13X are shown
545 in Figure 7(c). Figures 7(b) and 7(d) show the corresponding zooms of the
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546 N2 adsorption in the mixture on ZSM-5 and 13X, respectively. It should
547 be emphasized that the RAST simulations at temperatures above 45 ◦ C are
D
548 extrapolated, i.e. the same value for λ1 for the 1-parameter Wilson model
as reported in Table 4 was used. Note that the drop in N2 adsorption on
TE
549
550 zeolite 13X (Figure 7(d)) is substantial even at very low CO2 concentration.
551 Though not clearly visible on linear scale, the correct pure component N2
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552 limits are approached.

553 The notable behavior seen in the model predictions for binary adsorption
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554 with increasing temperature stems from the fact that the presence of a com-
555 peting species affects the adsorption of each gas to some degree. However,
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556 CO2 is affected only very slightly by the presence of N2 , to the point that
557 the dependence on temperature of CO2 adsorption in the binary system is
558 very similar to that of pure component adsorption. This is clearly visible in
559 Figures 7(a) and 7(c).
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560 The N2 adsorption, on the other hand, is determined to a large degree

561 by the competition of CO2 for the adsorption sites. As higher temperatures
PT
562 lead to lower adsorption of CO2 , more of the pore space becomes available,
563 counteracting the effect that the increased temperature would have on N2
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564 by itself. Which of these effects prevails is largely determined by the values
565 of Qb of the two species. The values obtained for ZSM-5 result in the cross-
SC
566 ing isotherms seen in Figure 7(b) with no clear trend for a wide range of
567 compositions, while those obtained for 13X result in N2 adsorption increas-
568 ing with temperature for almost any composition. In fact, a wider range of
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569 compositions with N2 adsorption increasing with temperature on ZSM-5 is
570
571
AN
obtained by simulating the binary CO2 /N2 adsorption with a hypothetical,
larger value of Qb,CO2 than the real one found in this work.
It is worth noting that the variations in the amount of N2 adsorbed in the
M
572
573 binary system is quite low over the whole temperature range; as a result the
574 experimental data is not sufficiently precise to verify or refute experimentally
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575 whether the temperature effect predicted by IAST and RAST is indeed
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576 consistent with the physical reality.
577 4.2.5. Thermodynamic consistency

EP
578 We have verified for both CO2 and N2 that both the IAST and the
579 RAST models yield the correct amount adsorbed as the composition of the
C
580 gas phase approaches unity. This is illustrated in Figure 5 and 6, where the
581 pure component limits are indicated with an open symbol at yN2 = 1 and
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582 yCO2 = 1. Thermodynamic consistency of the binary adsorption data

583 requires that the experimental data at constant pressure and temperature
584 coincide or exhibit an intersection with the IAST prediction 62 in the x,y-
585 plane, i.e. where the adsorbed phase composition, x, is plotted against the
26
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586 gas phase composition, y.

587 In the case of ZSM-5, the IAST predictions follow the experimental data
PT
588 closely. In fact, with the exception of two data points, the difference between
589 the IAST prediction and the experimental data lies within the experimental
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590 uncertainty. These results are shown in the SI, Figure S2. We conclude that
591 the binary data on ZSM-5 are consistent.
SC
592 In the case of zeolite 13X, when comparing the IAST prediction with
593 the RAST prediction, one indeed observes an intersection between the two
594 curves at a very low value of the CO2 mole fraction (yCO2 ≃ 10−4 ) (Figure
U
595 S3). We do not have such a high resolution in the experimental data, there-
596
597
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fore we cannot prove that IAST prediction and experimental data exhibit a
crossover in the x,y-plane (Figure S4). Nevertheless, since the RAST model
describes well the available experimental points, we can conclude that the
M
598
599 experimental data on zeolite 13X are not inconsistent.

D
600 4.2.6. Discussion of the assumptions

With reference to the comparison between model predictions and ex-
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601
602 perimental data, there is an important point that is worth discussing. On

603 the one hand IAST and RAST, i.e. the adsorption solution theory models
EP
604 used both in the literature and in this work, assume a two-dimensional ad-
605 sorbed phase, which is characterized by a spreading pressure and a molar
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606 surface, but not by a pressure and a specific volume, or density. On the
607 other hand, measuring adsorption data and interpreting such measurements
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608 require considering the adsorbed phase as a three-dimensional condensed

609 phase with a volume, V a , i.e. characterized by a pressure and a density.
610 The adsorbed phase volume is needed to convert measured quantities into
611 absolute amounts adsorbed (using both the excess adsorption framework
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612 (equation (1)) or the net adsorption framework (equation (2)); it is indeed
613 responsible for the buoyancy effect observed in gravimetric measurements.
PT
614 This issue, which is neither mentioned nor discussed in the literature,
615 appears even more serious when the adsorbed phase has to be treated as
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616 non ideal and RAST is used to model adsorption, as in the case of the bi-
617 nary adsorption equilibrium of CO2 /N2 on zeolite 13X, while at the same
SC
618 time additivity of volumes is applied through equation (12), which implies
619 an assumption of ideal mixture behavior, to estimate the adsorbed phase
620 density and convert measured data into absolute amounts adsorbed. While
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621 on the one hand we believe that there is no fundamental inconsistency here
622
623
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that is more troublesome than the contradictory fact that the same phase
is treated as two-dimensional in the model and as three-dimensional in the
interpretation of the experiments, on the other hand we consider it mean-
M
624
625 ingful to try and demonstrate that the effect of a violation of the volume
626 additivity rule of equation (12) has a negligible impact on the quantitative
D
627 data that we extract from the measurements.

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628 Let us consider the application of RAST and the Wilson model to de-
629 scribe the two-dimensional adsorbed phase for CO2 /N2 mixtures on zeolite
13X. As shown in Figure 6 the effect on the adsorption isotherms is signif-
EP
630
631 icant and leads to a notable improvement with respect to the use of IAST.
632 However, the corresponding correction to the total amount adsorbed due
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633 to the excess area (the area change of mixing), i.e. the second term in
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634 the sum on the right hand side of equation (18), is for all our data never
635 larger than 10−5 % of the whole sum. In other words, the excess area due
636 to the non-ideality, which is so important to fit well the adsorption equi-
637 librium data, is effectively negligible. Note that this also explains why the
638 1-parameter Wilson model succeeds almost equally well as the 3-parameter
28
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639 Wilson model.

640 Let us now consider the three-dimensional adsorbed phase description
PT
641 and the required estimate of the adsorbed phase density provided by equa-
642 tion (12), which is based on the assumption of volume additivity, i.e. no
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643 excess volume (volume change of mixing). Although in principle there are
644 different ways to calculate the density of a liquid mixture, namely using an
SC
645 equation of state or correlations such as those by Chueh and Prausnitz 63
646 and Li 64 , in practice all these have been developed for liquid phases, i.e.
647 are applicable below the mixture critical point. The adsorbed phase is in-
U
648 deed a condensed phase, but due to the interaction with the adsorbent it
649
650
AN
exists in a liquid-like state at conditions above those of the mixture critical
point. Therefore, we do not consider these approaches applicable here. In
fact, there is no mixing model for adsorbed phases, which explains why in
M
651
652 the literature the assumption of volume additivity is always used 20;26 . We
653 have therefore decided to make a sensitivity analysis by perturbing the value
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654 of the adsorbed phase density obtained from equation (12) by adding and
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655 subtracting up to 5% of its value. We have verified that such error does not
656 propagate significantly on the calculated values of the absolute amount ad-
sorbed. In fact, the variation with respect to the absolute amounts adsorbed
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657
658 calculated using equation (12) is well within the experimental uncertainty
659 of the measurements, i.e. at maximum it is less than 26 % of the uncertainty
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660 range. Based on the consideration above, we consider therefore the applica-
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661 tion of the volume additivity assumption and the use of the corresponding
662 equation (12) accurate and legitimate.
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663 5. Concluding remarks
PT
664 In the first part of this paper pure component CO2 and N2 adsorp-
665 tion isotherm data at five temperatures between 25 ◦ C and 140 ◦ C on two
666 zeolites, ZSM-5 and 13X, are reported and described with the tempera-
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667 ture dependent Sips model. Henry’s constants were determined by a Virial
668 isotherm based method.
SC
669 In the second part, binary CO2 /N2 adsorption data at two tempera-
670 tures, 25 ◦ C and 45 ◦ C , and three different pressure levels (1.2 bar, 3 bar
U
671 and 10 bar) on both zeolites are presented. Two predictive multicompo-
nent isotherm models, namely the extended Sips isotherm and the IAST,
672
673
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have been used to describe the binary adsorption data via pure component
674 isotherm parameters. In addition, the RAST formulation complemented
M
675 with the Wilson model for the determination of the activity coefficients was
676 applied to account for non-ideal effects in the adsorbed phase on 13X. The
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677 computation of confidence intervals of the fitting parameters of the Wil-

678 son model enabled the identification of redundant parameters and lead to a
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679 proposition of a simplified Wilson model for the activity coefficients.

680 The data and parameters will be used in a future work where the po-
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681 tential of these materials is evaluated in detail to perform adsorption based

682 CO2 /N2 separation with a TSA process.
C
683 Acknowledgments: This research has received funding from the Swiss Na-
tional Science Foundation under grant NF 200021-130186.
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684
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685 References
[1] A. a. Olajire, CO2 capture and separation technologies for end-
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686
687 of-pipe applications A review, Energy 35 (6) (2010) 2610–

688 2628, ISSN 03605442, doi:10.1016/j.energy.2010.02.030, URL
RI
689 http://linkinghub.elsevier.com/retrieve/pii/S0360544210000848.
690 [2] A. J. Reynolds, T. V. Verheyen, S. B. Adeloju, E. Meuleman, P. Feron,
SC
691 Towards Commercial Scale Postcombustion Capture of CO(2) with Mo-
692 noethanolamine Solvent: Key Considerations for Solvent Management
693 and Environmental Impacts., Environ. Sci. Technol. ISSN 1520-5851, doi:
U
694 10.1021/es204051s, URL http://www.ncbi.nlm.nih.gov/pubmed/22324566.
695
696
[3] A.
ment
Sayari,
via
Y.
CO2
AN
Belmabkhout,
adsorption,
R.
Chem.
Serna-Guerrero,
Eng. J.
Flue
171
gas
(3)
treat-
(2011)
760–774, ISSN 13858947, doi:10.1016/j.cej.2011.02.007, URL
M
697
[4] C. Voss, CO2 removal by PSA: an industrial view on opportunities and chal-
D
699
700 lenges, Adsorption (2013) 1–5ISSN 0929-5607, doi:10.1007/s10450-013-9574-8,

TE
701 URL http://link.springer.com/10.1007/s10450-013-9574-8.
702 [5] J. Merel, M. Clausse, F. Meunier, Experimental Investigation on CO2 Post-

Combustion Capture by Indirect Thermal Swing Adsorption Using 13X and
EP
703
704 5A Zeolites, Ind. Eng. Chem. Res. 47 (2008) 209–215.
705 [6] M. Clausse, J. Merel, F. Meunier, Numerical parametric study on CO2

C
706 capture by indirect thermal swing adsorption, Int. J. Greenh. Gas Control
AC
707 5 (5) (2011) 1206–1213, ISSN 17505836, doi:10.1016/j.ijggc.2011.05.036, URL

708 http://linkinghub.elsevier.com/retrieve/pii/S175058361100096X.
709 [7] S. Choi, J. H. Drese, C. W. Jones, Adsorbent materials for carbon

710 dioxide capture from large anthropogenic point sources., ChemSusChem
31
ACCEPTED MANUSCRIPT
711 2 (9) (2009) 796–854, ISSN 1864-564X, doi:10.1002/cssc.200900036, URL

712 http://www.ncbi.nlm.nih.gov/pubmed/19731282.
PT
713 [8] G. Kokotailo, S. Lawton, D. Olson, W. Meier, Structure of synthetic zeolite
714 ZSM-5, Nature 272 (1978) 437–438.
RI
715 [9] D. Olson, G. Kokotallo, S. Lawton, W. Meier, Crystal Structure and Structure-
716 Related Properties of ZSM-5, J. Phys. Chem. 85 (1981) 2238–2243.
SC
717 [10] Ruthven, Principles of Adsorption and Adsorption Processes, John Wiley &
718 Sons, Inc., 1984.
U
719 [11] J. A. Dunne, M. Rao, S. Sircar, R. J. Gorte, A. L. Myers, Calorimetric Heats
of Adsorption and Adsorption Isotherms . 2 . O2 , N2 , Ar , CO2 , CH4 , C2H6
720
721
AN
, and SF6 on NaX , H-ZSM-5 , and Na-ZSM-5 Zeolites, Langmuir 12 (1996)
722 5896–5904.
M
723 [12] S. Ottiger, R. Pini, G. Storti, M. Mazzotti, R. Bencini, F. Quattroc-
724 chi, G. Sardu, G. Deriu, Adsorption of pure carbon dioxide and methane
D
725 on dry coal from the sulcis coal province (SW Sardinia, Italy), Environ.
726 Prog. 25 (4) (2006) 355–364, ISSN 02784491, doi:10.1002/ep.10169, URL
TE
727 http://doi.wiley.com/10.1002/ep.10169.
728 [13] A. L. Myers, P. a. Monson, Physical adsorption of gases: the

EP
729 case for absolute adsorption as the basis for thermodynamic anal-
730 ysis, Adsorption ISSN 0929-5607, doi:10.1007/s10450-014-9604-1, URL
731 http://link.springer.com/10.1007/s10450-014-9604-1.
C
732 [14] O. Talu, Net Adsorption of Gas/Vapor Mixtures in Mi-

AC
733 croporous Solids, J. Phys. Chem. C 117 (25) (2013)

734 13059–13071, ISSN 1932-7447, doi:10.1021/jp4021382, URL
735 http://pubs.acs.org/doi/abs/10.1021/jp4021382.
736 [15] R. Pini, Interpretation of Net- and Excess Adsorption Isotherms in

737 Microporous Adsorbents, Microporous Mesoporous Mater. 187 (2014)
32
ACCEPTED MANUSCRIPT
738 40–52, ISSN 13871811, doi:10.1016/j.micromeso.2013.12.005, URL

PT
740 [16] S. Gumma, O. Talu, Net adsorption: a thermodynamic framework
741 for supercritical gas adsorption and storage in porous solids., Langmuir
RI
742 26 (22) (2010) 17013–23, ISSN 1520-5827, doi:10.1021/la102186q, URL
743 http://www.ncbi.nlm.nih.gov/pubmed/20886890.
SC
744 [17] A. M. Michels, P. G. Menon, C. A. Ten Seldam, Adsorption of Nitrogen on
745 Alumina at High Pressure, Recl. Trav. Chim. Pays-Bas 80 (1961) 483–501.
U
746 [18] S. Sircar, Excess properties and thermodynamics of multicom-
747 ponent gas adsorption, J. Chem. Soc. Faraday Trans. 1 81 (7)
748
749
(1985) 1527–1540, ISSN AN
0300-9589,
http://xlink.rsc.org/?DOI=f19858101527.
doi:10.1039/f19858101527, URL
M
750 [19] O. Di Giovanni, W. Dörfler, M. Mazzotti, M. Morbidelli, Adsorption of Super-
751 critical Carbon Dioxide on Silica, Langmuir 17 (2001) 4316–4321.
D
752 [20] M. Sudibandriyo, Z. Pan, J. E. Fitzgerald, R. L. R. Jr, K. A. M. Gasem,

753 Adsorption of Methane, Nitrogen, Carbon Dioxide, and Their Binary Mixtures
TE
754 on Dry Activated Carbon at 318.2 K and Pressures up to 13.6 MPa, Langmuir
755 19 (8) (2003) 5323–5331.
EP
756 [21] K. Murata, M. El-Merraoui, K. Kaneko, A new determination method of

757 absolute adsorption isotherm of supercritical gases under high pressure
758 with a special relevance to density-functional theory study, J. Chem.
C
759 Phys. 114 (9) (2001) 4196, ISSN 00219606, doi:10.1063/1.1344926, URL
AC
760 http://scitation.aip.org/content/aip/journal/jcp/114/9/10.1063/1.1344926.
761 [22] J. Moellmer, a. Moeller, F. Dreisbach, R. Glaeser, R. Staudt, High pressure

762 adsorption of hydrogen, nitrogen, carbon dioxide and methane on the met-
763 alorganic framework HKUST-1, Microporous Mesoporous Mater. 138 (1-3)
33
ACCEPTED MANUSCRIPT
764 (2011) 140–148, ISSN 13871811, doi:10.1016/j.micromeso.2010.09.013, URL

PT
766 [23] S. Gumma, O. Talu, Gibbs dividing surface and helium adsorption, Adsorption
767 9 (2003) 17–28, ISSN 09295607, doi:10.1023/A:1023859112985.
RI
768 [24] O. Di Giovanni, W. Dörfler, M. Mazzotti, M. Morbidelli, Adsorption of Super-
769 critical Carbon Dioxide on Silica, Langmuir 17 (2001) 4316–4321.
SC
770 [25] T. Hocker, A. Rajendran, M. Mazzotti, Measuring and Modeling Supercritical
771 Adsorption in Porous Solids . Carbon Dioxide on 13X Zeolite and on Silica
U
772 Gel, Langmuir (17) (2003) 1254–1267.
773
774
[26] J. Schell,
sorption of CO2, H2,
AN
N. Casas, R. Pini,
and N2
M. Mazzotti,
on activated
Pure and binary ad-
carbon, Adsorption
775 18 (2012) 49–65, ISSN 0929-5607, doi:10.1007/s10450-011-9382-y, URL
M
776 http://www.springerlink.com/index/10.1007/s10450-011-9382-y.
777 [27] S. Ottiger, R. Pini, G. Storti, M. Mazzotti, Competitive adsorp-

D
778 tion equilibria of CO2 and CH4 on a dry coal, Adsorption 14 (4-
779 5) (2008) 539–556, ISSN 0929-5607, doi:10.1007/s10450-008-9114-0, URL
TE
781 [28] F. Dreisbach, H. Lösch, P. Harting, Highest Pressure Adsorption Equilibria

EP
782 Data : Measurement with Magnetic Suspension Balance and Analysis with a
783 New Adsorbent / Adsorbate-Volume, Adsorption 8 (2002) 95–109.
C
784 [29] R. Pini, S. Ottiger, A. Rajendran, G. Storti, M. Mazzotti, Reliable measure-

785 ment of near-critical adsorption by gravimetric method, Adsorption 12 (5-
AC
786 6) (2006) 393–403, ISSN 0929-5607, doi:10.1007/s10450-006-0567-8, URL

787 http://www.springerlink.com/index/10.1007/s10450-006-0567-8.
788 [30] NIST Chemistry WebBook, URL webbook.nist.gov/chemistry/, 2013.
34
ACCEPTED MANUSCRIPT
789 [31] F. Dreisbach, R. Staudt, J. U. Keller, High Pressure Adsorption Data of

790 Methane , Nitrogen , Carbon Dioxide and their Binary and Ternary Mixtures
PT
791 on Activated Carbon, Adsorption 5 (1999) 215–227.
792 [32] C. a. Grande, F. V. S. Lopes, A. M. Ribeiro, J. M. Loureiro, A. E. Ro-
RI
793 drigues, Adsorption of Off-Gases from Steam Methane Reforming (H2 , CO2
794 , CH4 , CO and N2 ) on Activated Carbon, Sep. Sci. Technol. 43 (6)
(2008) 1338–1364, ISSN 0149-6395, doi:10.1080/01496390801940952, URL
SC
795
796 http://www.tandfonline.com/doi/abs/10.1080/01496390801940952.
797 [33] R. Sips, On the Structure of a Catalyst Surface, J. Chem. Phys.
U
798 16 (5) (1948) 490–495, ISSN 00219606, doi:10.1063/1.1746922, URL
799
800
AN
http://link.aip.org/link/JCPSA6/v16/i5/p490/s1&Agg=doi.
[34] R. Sips, On the Structure of a Catalyst Surface. II, J. Chem. Phys.

801 18 (8) (1950) 1024–1026, ISSN 00219606, doi:10.1063/1.1747848, URL
M
802 http://scitation.aip.org/content/aip/journal/jcp/18/8/10.1063/1.1747848.
[35] D. Do, A new model for the description of adsorption kinetics

D
803
804 in heterogeneous activated carbon, Carbon N. Y. 36 (10) (1998)

TE
805 1539–1554, ISSN 00086223, doi:10.1016/S0008-6223(98)00145-6, URL

[36] R. M. Barrer, J. a. Davies, Sorption in Decationated Zeolites. I. Gases in

EP
807
808 Hydrogen-Chabazite, Proc. R. Soc. A Math. Phys. Eng. Sci. 320 (1542)
809 (1970) 289–308, ISSN 1364-5021, doi:10.1098/rspa.1970.0210, URL
C
810 http://rspa.royalsocietypublishing.org/cgi/doi/10.1098/rspa.1970.0210.
AC
811 [37] R. T. Yang, Adsorbents Fundamentals and Applications, Imperial College

812 Press, 1 edn., 1987.
813 [38] A. L. Myers, J. M. Prausnitz, Thermodynamics of mixed-gas adsorption,

814 AIChE J. 11 (1) (1965) 121–127, ISSN 0001-1541, doi:10.1002/aic.690110125,
815 URL http://doi.wiley.com/10.1002/aic.690110125.
35
ACCEPTED MANUSCRIPT
816 [39] O. Talu, Thermodynamics of Multicomponent Gas Adsorption Equilibria of

817 Nonideal Mixtures, Ph.D. thesis, Arizona State University, 1984.
PT
818 [40] O. Talu, J. Li, A. L. Myers, Activity coefficients of adsorbed mixtures, Ad-
819 sorption 1 (2) (1995) 103–112, ISSN 0929-5607, doi:10.1007/BF00704999, URL
RI
820 http://link.springer.com/10.1007/BF00704999.
821 [41] O. Talu, I. Zwiebel, Multicomponent adsorption equilib-
SC
822 ria of nonideal mixtures, AIChE J. 32 (8) (1986) 1263–
823 1276, ISSN 0001-1541, doi:10.1002/aic.690320805, URL
824 http://doi.wiley.com/10.1002/aic.690320805.
U
825 [42] F. Karavias, A. L. Myers, Isosteric heats of multicomponent adsorp-
826
827
tion:
(1991) 3118–3126, ISSN
AN
thermodynamics and computer simulations,
0743-7463,
Langmuir 7 (12)
doi:10.1021/la00060a035, URL
828 http://pubs.acs.org/doi/abs/10.1021/la00060a035.
M
829 [43] E. Costa, J. L. Sotelo, G. Calleja, C. Marrón, Adsorption Of Binary And
830 Ternary Hydrocarbon Gas Mixtures On Activated Corbon: Experimental De-
D
831 termination And Theoretical Prediction Of The Ternary Equilibrium Data,

AIChE J. 27 (1) (1981) 5–12.
TE
832
833 [44] G. Gamba, R. Rota, M. Morbidelli, S. Carra, Adsorbed Solution Theory Mod-
834 els for Multicomponent Adsorption Equilibria, AIChE J. 35 (6).
EP
835 [45] R. Rota, G. Gamba, M. Morbidelli, On the use of the adsorbed solu-
836 tion theory for designing adsorption separation units, Sep. Technol. 3 (4)
C
837 (1993) 230–237, ISSN 09569618, doi:10.1016/0956-9618(93)80022-J, URL

http://linkinghub.elsevier.com/retrieve/pii/095696189380022J.
AC
838
839 [46] G. M. Wilson, Vapor-Liquid Equilibrium. XI. A New Expression for the Excess
840 Free Energy of Mixing, J. Am. Chem. Soc. 86 (2) (1964) 127–130.
841 [47] R. Orye, J. M. Prausnitz, Multicomponent Equilibria with the Wilson Equa-
842 tion, Ind. Eng. Chem. 57 (5) (1965) 18–26.
36
ACCEPTED MANUSCRIPT
843 [48] S. Suwanayuen, R. P. Danner, Vacancy Solution Theory of Adsorption From

844 Gas Mixtures, AIChE J. 26 (1) (1980) 76–83.
PT
845 [49] Y. Bard, Nonlinear Parameter Estimation, Academic Press, 1974.
[50] L. T. Biegler, J. J. Damiano, G. E. Blau, Nonlinear param-
RI
846
847 eter estimation: A case study comparison, AIChE J. 32 (1)

848 (1986) 29–45, ISSN 0001-1541, doi:10.1002/aic.690320105, URL
SC
850 [51] D. R. Ochsenbein, S. Schorsch, T. Vetter, M. Mazzotti, M. Morari, Growth
U
851 Rate Estimation of β L Glutamic Acid from Online Measurements of Multi-
852 dimensional Particle Size Distributions and Concentration, Ind. Eng. Chem.
853 Res. . AN
854 [52] D. H. Olson, W. Haag, R. M. Lago, Chemical and Physical Properties of the
M
855 ZSM-5 Substitutional Series, J. Catal. 61 (1980) 390–396.
856 [53] Y.-J. Park, S.-J. Lee, J.-H. Moon, D.-K. Choi, C.-H. Lee, Ad-
D
857 sorption Equilibria of O 2 , N 2 , and Ar on Carbon Molec-

858 ular Sieve and Zeolites 10X, 13X, and LiX, J. Chem. Eng. Data
TE
859 51 (3) (2006) 1001–1008, ISSN 0021-9568, doi:10.1021/je050507v, URL

860 http://pubs.acs.org/doi/abs/10.1021/je050507v.
EP
861 [54] J.-S. Lee, J.-H. Kim, J.-T. Kim, J.-K. Suh, J.-M. Lee, C.-
862 H. Lee, Adsorption Equilibria of CO2 on Zeolite 13X and Zeo-
863 lite X/Activated Carbon Composite, J. Chem. Eng. Data 47 (5)
C
864 (2002) 1237–1242, ISSN 0021-9568, doi:10.1021/je020050e, URL

AC
865 http://pubs.acs.org/doi/abs/10.1021/je020050e.
866 [55] J. Rother, T. Fieback, Multicomponent adsorption measurements on acti-

867 vated carbon, zeolite molecular sieve and metalorganic framework, Adsorp-
868 tion (2013) 1065–1074ISSN 0929-5607, doi:10.1007/s10450-013-9527-2, URL
37
ACCEPTED MANUSCRIPT
870 [56] D. Newsome, S. Gunawan, G. Baron, J. Denayer, M.-O. Coppens, Ad-

871 sorption of CO2 and N2 in NaZSM-5: effects of Na+ and Al con-
PT
872 tent studied by Grand Canonical Monte Carlo simulations and experi-
873 ments, Adsorption ISSN 0929-5607, doi:10.1007/s10450-013-9560-1, URL
http://link.springer.com/10.1007/s10450-013-9560-1.
RI
874
875 [57] R. Barrer, R. M. Gibbons, Zeolitic Carbon Dioxide: Energetics and Equilib-
ria in Relation to Exchangeable Cations in Faujasite, Trans. Faraday Soc. 61
SC
876
877 (1965) 948–961.
878 [58] T. Yamazaki, M. Katoh, S. Ozawa, Y. Ogino, Adsorption of CO2
U
879 over univalent cation-exchanged ZSM-5 zeolites, Mol. Phys. 80 (2)
880
881
AN
(1993) 313–324, ISSN 0026-8976, doi:10.1080/00268979300102281, URL
http://www.tandfonline.com/doi/abs/10.1080/00268979300102281.
[59] S. K. Wirawan, D. Creaser, CO2 adsorption on silicalite-1 and

M
882
883 cation exchanged ZSM-5 zeolites using a step change response

884 method, Microporous Mesoporous Mater. 91 (1-3) (2006) 196–
D
885 205, ISSN 13871811, doi:10.1016/j.micromeso.2005.11.047, URL

TE
887 [60] E. Richter, W. Schotz, A. L. Myers, Effect of Adsorption Equation on Predic-

888 tion of Multicomponent Adsorption Equilibria by the Ideal Adsorbed Solution
EP
889 Theory, Chem. Eng. Sci. 44 (8) (1989) 1609–1616.
890 [61] X. Hu, D. D. Do, Comparing various multicomponent ad-

C
891 sorption equilibrium models, AIChE J. 41 (6) (1995) 1585–

892 1592, ISSN 0001-1541, doi:10.1002/aic.690410623, URL
AC
894 [62] O. Talu, A. L. Myers, Rigorous thermodynamic treatment of gas ad-

895 sorption, AiChE J. 34 (11) (1988) 1887–1893, ISSN 1547-5905, doi:
896 10.1002/aic.690341114, URL http://dx.doi.org/10.1002/aic.690341114.
38
ACCEPTED MANUSCRIPT
897 [63] P. Chueh, J. Prausnitz, Vapor-Liquid Equilibria at High Pressures . Vapor-

898 Phase Fugacity Coefficients in Nonpolar and Quantum-Gas Mixtures, I&Ec
PT
899 Fundam. 6 (1967) 492–498, ISSN 0196-4313, doi:10.1021/i160024a003.
900 [64] C. Li, Critical temperature estimation for simple mixtures, Can. J. Chem.
RI
901 Eng. 49 (1971) 709–710, ISSN 00084034, doi:10.1002/cjce.5450490529, URL
902 http://onlinelibrary.wiley.com/doi/10.1002/cjce.5450490529/abstract.
SC
903 [65] A. L. Pulin, A. A. Fomkin, V. A. Sinitsyn, A. A. Pribylov, Adsorption and
904 adsorption-induced deformation of NaX zeolite under high pressures of carbon
905 dioxide, Russ. Chem. Bull. 50 (1) (2001) 60–62.
U
906 [66] S. Cavenati, C. a. Grande, A. E. Rodrigues, Adsorption Equi-
907
908
librium
olite 13X
of Methane,
at High
AN
Carbon
Pressures,
Dioxide,
J. Chem.
and Nitrogen
Eng. Data
on
49
Ze-
(4)
909 (2004) 1095–1101, ISSN 0021-9568, doi:10.1021/je0498917, URL
M
910 http://pubs.acs.org/doi/abs/10.1021/je0498917.
[67] P. J. Harlick, F. H. Tezel, An experimental adsorbent screening study

D
911
912 for CO2 removal from N2, Microporous Mesoporous Mater. 76 (1-3)
TE
913 (2004) 71–79, ISSN 13871811, doi:10.1016/j.micromeso.2004.07.035, URL

[68] A. Khelifa, L. Benchehida, Z. Derriche, Adsorption of carbon dioxide by X

EP
915
916 zeolites exchanged with Ni2+ and Cr3+: isotherms and isosteric heat.pdf, J.
917 Colloid Interface Sci. 278 (2004) 9–17.
C
918 [69] Y. Wang, M. D. LeVan, Adsorption Equilibrium of Carbon Dioxide and Water
AC
919 Vapor on Zeolites 5A and 13X and Silica Gel: Pure Components, J. Chem.
920 Eng. Data 54 (10) (2009) 2839–2844, ISSN 0021-9568, doi:10.1021/je800900a,
921 URL http://pubs.acs.org/doi/abs/10.1021/je800900a.
922 [70] H. Deng, H. Yi, X. Tang, Q. Yu, P. Ning, L. Yang, Adsorp-

923 tion equilibrium for sulfur dioxide, nitric oxide, carbon diox-
39
ACCEPTED MANUSCRIPT
924 ide, nitrogen on 13X and 5A zeolites, Chem. Eng. J. 188

925 (2012) 77–85, ISSN 13858947, doi:10.1016/j.cej.2012.02.026, URL
PT
927 [71] M. Mofarahi, F. Gholipour, Gas adsorption separation of CO2/CH4
RI
928 system using zeolite 5A, Microporous Mesoporous Mater. 200 (2014)
929 1–10, ISSN 13871811, doi:10.1016/j.micromeso.2014.08.022, URL
SC
930 http://linkinghub.elsevier.com/retrieve/pii/S138718111400448X.
931 [72] P. Harlick, F. Tezel, Adsorption of carbon dioxide, methane and

932 nitrogen: pure and binary mixture adsorption for ZSM-5 with
U
933 SiO2/Al2O3 ratio of 280, Sep. Purif. Technol. 33 (2) (2003) 199–
934
935
210, ISSN 13835866,
ANdoi:10.1016/S1383-5866(02)00078-3,
http://linkinghub.elsevier.com/retrieve/pii/S1383586602000783.
URL
[73] A. Zukal, J. Mayerová, M. Kub, Adsorption of Carbon Dioxide on High-

M
936
937 Silica Zeolites with Different Framework Topology, Top. Catal. 53 (19-
938 20) (2010) 1361–1366, ISSN 1022-5528, doi:10.1007/s11244-010-9594-5, URL
D
TE
940 [74] G. Sethia, G. P. Dangi, A. L. Jetwani, R. S. Somani, H. C. Bajaj, R. V. Jasra,

941 Equilibrium and Dynamic Adsorption of Carbon Monoxide and Nitrogen on
942 ZSM-5 with Different SiO2/Al2O3 Ratio, Sep. Sci. Technol. 45 (February 2015)
EP
943 (2010) 413–420, ISSN 0149-6395, doi:10.1080/01496390903417990.
944 [75] J. B. Rawlings, S. M. Miller, W. R. Witkowski, Model Identification and Con-

C
945 trol of Solution Crystallization Processes: A Review, Ind. Eng. Chem. Res 32
946 (1993) 1275–1296.
AC
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xx
PI
MSB
TI
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vacuum
PI
vent
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water bath
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adsorption
secondary
cell
TI
PI
U
circulation
pump
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compressor
vacuum
gas
sampling
loop
vent
M
chromatograph
gas
CO2 CO2
He
N2
D N2
Ar
Figure 1: Experimental setup. The pipes highlighted in bold are kept at constant temper-
TE
ature. They also indicate the known, calibrated volume. The dashed frame indicates the
Huber Polystat while the grey-shaded area around the MSB indicates the temperature
control by a second thermostat (Julabo, Germany).
C EP
AC
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2.50 (a) CO /ZSM−5 (b) CO /ZSM−5

2 2
25°C
45°C
PT
adsorption [mol/kg]
2.00
adsorption [mol/kg]
65°C 1.00
1.50
100°C
1.00 140°C 0.50
RI
0.50
0 0
0 2.5 5.0 7.5 10.0 0 0.5 1.0
pressure [bar] pressure [bar]
SC
1.00 (c) N /ZSM−5 (d) N /ZSM−5
2 2
25°C 0.20
adsorption [mol/kg]
adsorption [mol/kg]
0.75
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45°C
65°C
0.50
0.10
0.25
0
AN100°C
140°C
0
0 2.5 5.0 7.5 10.0 0 0.5 1.0
M
Figure 2: Adsorption of pure CO2 and N2 over the whole pressure range (a) and (c) and
zoom up to 1 bar (b) and (d) on ZSM-5. The symbols are the experimental values; the
lines are the fits with Sips isotherm. 25 ◦ C – ◦, 45 ◦ C – , 65 ◦ C – △, 100 ◦ C – ×, 140 ◦ C
D
–⋄
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(a) CO /13X 5.0 (b) CO /13X

2 2
25°C
6 45°C
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65°C
adsorption [mol/kg]
adsorption [mol/kg]
100°C
140°C
4
2.5
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2
0 0
0 2.5 5.0 7.5 10.0 0 0.5 1.0
SC
(c) N2/13X (d) N2/13X
2.00 25°C
0.40
adsorption [mol/kg]
adsorption [mol/kg]
45°C
1.50
U
65°C
1.00 0.20
0.50
0
AN100°C
140°C
0
0 2.5 5.0 7.5 10.0 0 0.5 1.0
M
Figure 3: Adsorption of pure CO2 and N2 over the whole pressure range (a) and (c) and
zoom up to 1 bar (b) and (d) on 13X. The symbols are the experimental values; the lines
are the fits with Sips isotherm. 25 ◦ C – ◦, 45 ◦ C – , 65 ◦ C – △, 100 ◦ C – ×, 140 ◦ C – ⋄
D
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10.0
CO
2
7.5
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5.0
ln(H ) [−]
i
2.5 CO 13X
2
0.0
N2 ZSM−5
−2.5
RI
13X
ZSM−5
−5.0
25 45 65 100 140
temperature [°C]
SC
Figure 4: Henry’s constants for CO2 (filled symbols) and N2 (empty symbols) on the two
zeolites ZSM-5 and 13X in the form ln (Hi ) vs. temperature.
U
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2.5 2.5 2.5

(a) ZSM−5 (b) ZSM−5 (c) ZSM−5
CO
2.0 25°C | 1.2bar 2.0 25°C | 3bar 2.0 25°C | 10bar 2
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adsorption [mol/kg]
adsorption [mol/kg]
adsorption [mol/kg]
CO
2
1.5 1.5 1.5
CO
2
1.0 1.0 1.0
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0.5 0.5 0.5
N2 N N
2 2
0 0 0
0 0.25 0.50 0.75 1 0 0.25 0.50 0.75 1 0 0.25 0.50 0.75 1
y [−] y [−] y [−]
CO CO CO
2 2 2
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2.5 2.5 2.5
(d) ZSM−5 (e) ZSM−5 (f) ZSM−5
2.0 45°C | 1.2bar 2.0 45°C | 3bar 2.0 45°C | 10bar
CO
adsorption [mol/kg]
adsorption [mol/kg]
adsorption [mol/kg]
2
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1.5 1.5 1.5
CO2
1.0 1.0 1.0

CO
0.5
0
0 0.25 0.50
N
0.75
2
2
1
0.5
0
0
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0.25 0.50
N
0.75
2
1
0.5
0
0 0.25 0.50
N
0.75
2
1
y [−] y [−] y [−]
CO CO CO
2 2 2
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Figure 5: Binary adsorption equilibria of the CO2 and N2 mixture on ZSM-5. The symbols
are the experimental values; also shown are the predictions according to IAST (dashed
lines) and the extended Sips isotherm (dotted lines). Adsorption at the pure component
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limits yCO2 = 0 and yCO2 = 1 are indicated with open circles.

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8 8 8
(a) 13X (b) 13X (c) 13X
pure CO2
25°C | 1.2bar 25°C | 3bar pure CO 25°C | 10bar
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2
adsorption [mol/kg]
adsorption [mol/kg]
adsorption [mol/kg]
6 pure CO2 6 6 CO2

CO2
CO2
4 4 4
pure N2
2 2 2
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pure N2
pure N2
N2 N2 N2
0 0 0
0 0.25 0.50 0.75 1 0 0.25 0.50 0.75 1 0 0.25 0.50 0.75 1
yCO [−] yCO [−] yCO [−]
2 2 2
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8 8 8
(d) 13X (e) 13X (f) 13X
45°C | 1.2bar 45°C | 3bar 45°C | 10bar pure CO2
adsorption [mol/kg]
adsorption [mol/kg]
adsorption [mol/kg]
6 6 pure CO2 6
pure CO CO2
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2
CO2
CO2
4 4 4
0
0
pure N
2
0.25 0.50
N2
0.75 1
2
0
0
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pure N2
0.25 0.50
N2
0.75 1
2
0
0
pure N2
0.25 0.50
N2
0.75 1
yCO [−] yCO [−] yCO [−]
2 2 2
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Figure 6: Binary adsorption equilibria of the CO2 and N2 mixture on 13X zeolite. The
symbols are the experimental values; also shown are the predictions according to IAST
(dashed lines) and the extended Sips isotherm (dotted lines); the RAST complemented
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with the 1-parameter Wilson model fits are shown as solid lines. In subfigures (a) and (d)
the nominal feed compositions are shown as vertical dashed lines. Adsorption at the pure
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component limits yCO2 = 0 and yCO2 = 1 are indicated with open circles.
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2.5 1
(a) ZSM−5 (b) ZSM−5
2.0 10bar 10bar
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0.75
adsorption [mol/kg]
adsorption [mol/kg]
25°C
1.5
0.50
1.0
CO2 25°C
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0.25
0.5 140°C
N N2
2 140°C
0 0
0 0.25 0.50 0.75 1 0 0.25 0.50 0.75 1
yCO [−] yCO [−]
2 2
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8 1
(c) 13X (d) 13X
10bar 25°C 10bar
adsorption [mol/kg]
0.75
adsorption [mol/kg]
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4 0.50
CO2
0
0 0.25
140°C
0.50
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0.75
N2
1
0.25
0
0
25°C
0.25
140°C
0.50 0.75
N2
1
yCO [−] y [−]
CO
2 2
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Figure 7: Temperature effect on the IAST predictions (dashed lines) on ZSM-5 and on
the RAST complemented with the 1-parameter Wilson model (solid lines) of the CO2 /N2
mixture on ZSM-5 (a) and 13X (c), respectively. Zooms for better visualization of the
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behavior of the N2 adsorption are shown in (b) and (d).

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Table 1: Literature overview of available adsorption equilibrium data for CO2 or N2 on zeolites ZSM-5 and 13-X were measured
experimentally. T indicates the temperature (range) of the measurements; Pmax indicates the highest pressure at which data was
gathered; nmax indicates the highest values reported for the adsorbed amount. Abbreviations used: CBK: Chemiewerke Bad Köstritz;
NU: Nankai University; CU: Chemie Uetikon; MSL: multisite Langmuir; VST: Vacancy Solution Theory; GCMC: Grand Canonical
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Monte Carlo.
reference type of zeolite Si/Al gas T Pmax nmax isotherm model used pore volume
(supplier) ratio [K] [bar] [mol/kg] [cm3 /g]
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Dunne et al. 11 13X (Linde) 1.23 CO2 304 0.7 5.4 none
N2 296 1.1 0.4 none
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Pulin et al. 65 13X (unknown) – CO2 195 – 423 54 8.5 none
54
Lee et al. 13X (Aldrich) – CO2 273 – 353 1.2 4.1 Sips, Toth, UNILAN 0.250
66
Cavenati et al. 13X (CECA) – CO2 298 – 323 50 7.4 Toth, MSL
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N2 298 – 323 50 4.2 Toth, MSL
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Harlick and Tezel 67 13X (UOP) 2.2 CO2 295 2.0 5 Toth
68
Khelifa et al. 13X (CECA) 1.21 CO2 273 – 393 0.6 5.9 Sips
53
Park et al. 13X (Baylith) – N2 293 – 313 0.8 0.26 Sips, Toth, Langmuir 0.250
M
69
Wang and LeVan 13X (Aldrich) – CO2 228 – 448 1.0 4.5 Sips, Toth
48
70
Deng et al. 13X (NU) – CO2 323 – 363 0.6 1.2 Toth 0.290
N2 323 – 363 0.7 0.05 Toth
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55
Rother and Fieback 13X (CBK) – CO2 298 20 6.9 Langmuir 0.306
N2 298 30 3.1 Langmuir
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15
Pini 13X (Zeochem) 1.23 CO2 273, 325 142.0 ∼9 Statistical (Ruthven) 0.261
Mofarahi and Gholipour 71 13X (Zeochem) – N2 273 – 343 10 2.1 Toth
58 3
Yamazaki et al. ZSM-5 (Tosoh) 23.3 CO2 273 – 473 0.7 68 cm /g none
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11
Dunne et al. ZSM-5 (CU) 30 CO2 297 0.7 1.9 none 0.174
N2 295 1.1 0.4 none
72
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Harlick and Tezel ZSM-5 (synthesized) 280 CO2 313 1.0 1.1 Langmuir, Freundlich, VST
N2 313 1.0 0.2 Langmuir, Freundlich, VST
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Wirawan and Creaser ZSM-5 (Eka Chemicals) 27 CO2 323 – 473 0.8 1.7 MSL
73
Zukal et al. ZSM-5 (Eka Chemicals) 35 CO2 1.0 2.1 none 0.163
74
Sethia et al. ZSM-5 (Zeochem) 400 N2 288, 303 1.1 2.5 Sips, Langmuir
Newsome et al. 56 ZSM-5 (Süd-Chemie) 13 CO2 273 – 308 1.0 unknown Virial
N2 273 – 308 1.0 unknown GCMC
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Table 2: Pure component parameter estimates for CO2 and N2 on ZSM-5 and 13X.
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CO2 N2
n∞
i [mol/kg] ref [mol/kg]
n∞ 2.775 ± 1e-3 2.027 ± 3e-3
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χi [–] 0 0
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bi [bar−1 ] b0,i [bar−1 ] 1.6969e-5 ± 2e-9 6.843e-5 ± 1e-8
ZSM-5
Qb,i [kJ/mol] 26.9802 ± 3e-4 17.3146 ± 5e-4
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ci [–] cref,i [–] 0.79189 ± 5e-5 0.91411 ± 8e-5
α [–] AN 0 0
n∞
i [mol/kg] n∞
ref [mol/kg] 7.268 ± 1e-3 4.051 ± 2e-3
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χi [–] -0.61684 ± 3e-4 0
bi [bar−1 ] b0,i [bar−1 ] 1.129e-4 ± 1e-7 5.8470e-5 ± 7e-9

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13X
Qb,i [kJ/mol] 28.389 ± 2e-3 18.4740 ± 3e-4
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ci [–] cref,i [–] 0.42456 ± 8e-5 0.98624 ± 5e-5
α [–] 0.72378 ± 7e-5 0

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Table 3: Henry’s constants reported as ln Hi . Note that the correct units of Hi are
[mol/kg/bar].
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25 ◦ C 45 ◦ C 65 ◦ C 100 ◦ C 140 ◦ C
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CO2 2.03 1.18 0.47 -0.54 -1.34
ZSM-5
N2 -1.60 -2.04 -2.46 -3.08 -3.61
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CO2 8.81 7.30 5.83 3.91 2.25
13X
N2 -0.78 -1.27 -1.70 -2.33 -2.89
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Table 4: RAST parameter estimates for the two models for the activity coefficients.
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model λ1 λ2 ω Φb
[kJ/mol] [kJ/mol] [kg/mol] [–]
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6.2 ± O 1010

3-parameter Wilson 6.1 ± 8.8 -5.5 ± 0.9 -16.683
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1-parameter Wilson 5.4 ± 0.1 -λ1 ∞ -16.667
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Table 5: Overview of the uncertainties in the experimental variables.
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variable value source
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sinker volume 0.05 % of sinker volume Rubotherm
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measuring points 0.05 mg Rubotherm
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sinker mass 0.01 mg Rubotherm
sorbent mass
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standard deviation
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sample/metal volume maximal error of repetitions Di Giovanni et al. 24
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feed concentration specific Pangas

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composition standard deviation

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947 Appendix A. Error propagation
In this work the errors were approximated through the first order variance ap-
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948
949 proximation also known as the error propagation law for uncorrelated measurables.
950 Mathematically, this method is simple but yields considerably big expressions. More
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951 details can be found in Di Giovanni et al. 24 and Ottiger et al. 27 . We omit the com-
952 plete derivation for the sake of readability. The relevant uncertainties that were
used are reported in Table 5.
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953
954 Appendix B. Parameter uncertainty
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955 To determine the confidence intervals of the estimated parameters, i.e. the
956
957
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entries of the vector θ∗ , the parameter covariance matrix Vθ is required. A similar
methodology as in Rawlings et al. 75 and Ochsenbein et al. 51 was employed. Here,
958 it is briefly explained how Vθ is obtained and the confidence intervals of θ∗ may
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959 be determined.
960 For non-linear problems such as the minimization of equations (25) and (27),
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961 the confidence region in the vicinity of θ∗ is approximated by linearization:

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n (θ) ≈ n (θ∗ ) + W (θ − θ∗ ) (B.1)
962 where n is the Sips isotherm model in the case of pure component adsorption
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963 (equation (6)) and the RAST model with the associated activity coefficient model
964 in the case of the binary adsorption (equations (15), (16), (18), (19) and (22)
965 to (24)). W is the output sensitivity, i.e. the gradient vector of the adsorption
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966 model n:
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W = ∇n (θ) (B.2)
967 It can be shown that Vθ is well approximated by 49 :
−1
Vθ ≈ WT V−1 W (B.3)
53
ACCEPTED MANUSCRIPT
968 where V is the measurement covariance matrix. In this work, under the assumptions
969 imposed on the measurement errors as stated in 3.3 Parameter estimation, V is
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970 diagonal 50 . The elements of V are approximated by error propagation calculations
971 yielding the measurement error covariances as summarized in the Appendix A.
Given Vθ the (symmetric) confidence intervals are approximated by
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972
1/2
θ ± (Vθ ) tα/2 (Ntot − Nθ ) (B.4)
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973 where tα/2 is obtained from the Student’s T-distribution with (Ntot −Nθ ) degrees of
974 freedom. For a more detailed discussion how to obtain (B.4) the reader is referred
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975 to Bard 49 and Rawlings et al. 75 .
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Highlights
 Pure component adsorption data of CO2 and N2 on ZSM-5 and 13X

 Binary adsorption equilibria of the CO2 and N2 mixture
 Non-ideal behavior of the CO2/N2 mixture in the adsorbed phase of 13X
 Proper description by ideal and real adsorbed solution theory
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Supporting Information to:

Adsorption Equilibrium of Binary Mixtures of Carbon Dioxide and Nitrogen on
Zeolites ZSM-5 and 13X
Max Hefti, Dorian Marx, Lisa Joss, Marco Mazzotti
ETH Zurich, Institute of Process Engineering, Sonneggstrasse 3, CH-8092 Zurich, Switzerland
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1 Pure component adsorption data
1.1 CO2 on ZSM-5
25 ◦ C 45 ◦ C 65 ◦ C 100 ◦ C 140 ◦ C
P [bar] nex [mol/kg] P [bar] nex [mol/kg] P [bar] nex [mol/kg] P [bar] nex [mol/kg] P [bar] nex [mol/kg]
PT
0.041 0.216 0.051 0.150 0.050 0.106 0.050 0.045 0.051 0.021
0.043 0.230 0.102 0.229 0.101 0.162 0.100 0.076 0.101 0.037
0.092 0.344 0.200 0.352 0.201 0.245 0.250 0.145 0.247 0.082
0.092 0.352 0.300 0.457 0.291 0.316 0.500 0.235 0.250 0.077
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0.188 0.532 0.496 0.632 0.300 0.316 0.749 0.312 0.500 0.128
0.189 0.531 0.745 0.810 0.498 0.439 0.992 0.389 0.772 0.176
0.200 0.564 0.994 0.955 0.747 0.570 0.999 0.382 1.001 0.213
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0.204 0.566 1.000 0.967 0.993 0.687 1.496 0.501 1.498 0.286
0.490 0.947 1.293 1.097 0.997 0.683 1.994 0.606 1.999 0.350
0.787 1.207 1.596 1.212 1.492 0.866 2.785 0.745 2.798 0.441
0.991 1.341 1.996 1.333 1.994 1.013 2.811 0.754 2.821 0.446
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1.004 1.355 2.028 1.349 2.000 1.031 3.8 0.894 3.8 0.543
1.010 1.348 2.8 1.512 2.791 1.190 5.0 1.025 5.0 0.647
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1.010 1.349 3.8 1.669 3.8 1.356 6.5 1.158 6.5 0.753
1.489 1.562 5.0 1.797 5.0 1.495 8.0 1.265 8.0 0.846
1.987 1.708 6.5 1.904 6.5 1.627 10.0 1.378 10.0 0.951
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2.012 1.713 8.0 1.990 8.0 1.719

2.682 1.847 10.0 2.073 10.0 1.817
2.696 1.855
3.6 1.972
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4.3 2.050
5.0 2.103
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5.1 2.111
6.0 2.171
8.0 2.265
10.0 2.338
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1.2 N2 on ZSM-5
25 ◦ C 45 ◦ C 65 ◦ C 100 ◦ C 140 ◦ C
0.100 0.024 0.246 0.035 0.248 0.021 0.250 0.015 0.251 0.007
0.249 0.052 0.491 0.064 0.498 0.041 0.502 0.026 0.501 0.014
0.252 0.050 0.747 0.091 0.748 0.060 0.739 0.037 0.749 0.020
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0.498 0.096 0.998 0.117 0.997 0.079 1.000 0.048 1.000 0.027
0.745 0.134 1.498 0.166 1.500 0.115 1.501 0.069 1.494 0.039
0.999 0.171 1.985 0.210 1.978 0.147 2.001 0.090 1.999 0.052
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1.001 0.169 2.715 0.270 2.799 0.198 2.773 0.120 2.807 0.071
1.500 0.238 3.8 0.352 3.8 0.259 3.8 0.160 3.8 0.095
1.993 0.297 5.0 0.430 5.0 0.322 5.0 0.201 5.0 0.123
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2.794 0.383 7.0 0.542 7.0 0.413 7.3 0.274 7.0 0.165
2.798 0.384 9.9 0.669 10.0 0.529 9.9 0.372 10.0 0.225
3.8 0.481
5.0 0.577
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7.0 0.709
10.0 0.859
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1.3 CO2 on 13X
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25 ◦ C 45 ◦ C 65 ◦ C 100 ◦ C 140 ◦ C
D
0.027 2.725 0.030 2.110 0.037 1.623 0.028 0.603 0.056 0.356
0.034 2.912 0.058 2.640 0.064 2.050 0.064 1.096 0.105 0.581
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0.056 3.327 0.105 3.144 0.108 2.461 0.126 1.571 0.211 0.970
0.088 3.691 0.218 3.746 0.236 3.123 0.233 2.046 0.410 1.427
0.100 3.834 0.332 4.088 0.412 3.586 0.403 2.495 0.627 1.768
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0.199 4.320 0.618 4.547 0.637 3.945 0.653 2.914 1.051 2.216
0.288 4.585 1.021 4.883 1.034 4.324 1.048 3.359 1.593 2.597
0.311 4.678 1.518 5.125 1.549 4.619 1.571 3.713 2.632 3.069
0.485 4.922 2.002 5.283 2.512 4.940 2.551 4.143 4.1 3.503
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0.738 5.172 2.823 5.445 4.0 5.219 4.0 4.505 6.0 3.860
0.999 5.346 3.8 5.600 6.0 5.429 6.1 4.806 9.9 4.281
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1.003 5.382 5.0 5.724 10.0 5.654 9.9 5.115

1.505 5.562 7.0 5.862
2.003 5.705 10.0 5.994
2.801 5.865
2.821 5.898
3.8 6.019
5.0 6.134
7.0 6.265
10.0 6.386
3
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1.4 N2 on 13X
25 ◦ C 45 ◦ C 65 ◦ C 100 ◦ C 140 ◦ C
0.048 0.020 0.093 0.026 0.094 0.017 0.092 0.009 0.093 0.006
0.096 0.040 0.289 0.077 0.289 0.051 0.294 0.029 0.294 0.017
0.194 0.081 0.565 0.146 0.592 0.102 0.593 0.057 0.590 0.032
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0.392 0.160 0.994 0.248 0.993 0.168 0.994 0.093 0.992 0.054
0.595 0.237 1.464 0.354 1.485 0.245 1.490 0.138 1.487 0.080
1.000 0.381 2.501 0.564 2.497 0.392 2.476 0.222 2.512 0.132
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1.511 0.547 4.0 0.827 4.0 0.593 4.0 0.347 4.0 0.206
2.448 0.811 6.0 1.112 6.0 0.820 6.0 0.492 6.0 0.299
4.0 1.176 10.0 1.545 10.0 1.178 9.9 0.743 10.0 0.467
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6.1 1.527
10.0 2.008
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1.5 High pressure data
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1.5.1 CO2 on 13X at 45 ◦ C
P [bar] ρb [mol/L] nex [mol/kg]

M
171.0 17.65 2.427

155.6 17.11 2.579
D
119.8 14.94 3.106

103.5 12.39 3.807
95.7 9.76 4.536
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87.7 7.08 5.300

80.7 5.63 5.660
69.6 4.13 6.047
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1.5.2 CO2 on ZSM-5 at 45 ◦ C

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P [bar] ρb [mol/L] nex [mol/kg]

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142.5 16.54 0.803

123.9 15.41 1.012
103.5 12.65 1.389
90.9 8.29 2.102
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8 3.5
T=45°C 3 T=45°C
6
2.5
[mol/kg]
nex [mol/kg]
2
4
1.5
ex
n
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2
0.5
0 0
0 10 20 30 0 10 20 30
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ρb [mol/L] ρb [mol/L]
(a) 13X (b) ZSM-5
Figure S1: Excess adsorption data of CO2 and linear regression to determine the adsorbed phase density of CO2 . The value
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obtained on is 26.58 mol/L on zeolite 13X and 21.76 mol/L on ZSM-5.
2 Binary adsorption data
2.1 CO2 /N2 on ZSM-5

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T [ ◦ C] f
yCO2
[–] P [bar] yCO2 [–] nex
CO2 [mol/kg] nex
N2 [mol/kg]
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0.25 1.200 0.134 0.455 0.126

3.0 0.162 0.851 0.202
9.9 0.202 1.504 0.227
D
0.5 1.220 0.360 0.848 0.091

25 ◦ C 3.2 0.409 1.395 0.126
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9.9 0.458 1.977 0.086

0.75 1.206 0.644 1.189 0.025
3.1 0.691 1.716 0.031
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9.9 0.727 2.206 0.039

10.0 0.727 2.215 0.027
0.25 1.226 0.157 0.345 0.085

1.254 0.159 0.350 0.092
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3.1 0.181 0.638 0.158

3.1 0.182 0.645 0.163
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10.0 0.209 1.207 0.212

0.5 1.216 0.391 0.608 0.058
45 ◦ C
3.2 0.426 1.077 0.095
9.9 0.463 1.654 0.125
0.75 1.205 0.672 0.859 0.023
3.1 0.701 1.374 0.029
3.1 0.701 1.361 0.032
10.1 0.729 1.946 0.026
10.1 0.730 1.925 0.050
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2.2 CO2 /N2 on 13X
T [ ◦ C] f
yCO2
[–] P [bar] yCO2 [–] nex
CO2 [mol/kg] nex
N2 [mol/kg]
0.25 1.260 0.002 1.304 0.275

3.1 0.013 2.913 0.284
10.1 0.127 5.020 0.426
0.5 1.229 0.053 3.305 0.166
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3.3 0.236 5.063 0.063
25 ◦ C
3.2 0.233 5.001 0.091
10.1 0.403 5.874 0.063
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10.2 0.404 5.868 0.070
0.75 1.202 0.415 4.809 0.022
3.2 0.606 5.516 0.016
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9.9 0.702 6.019 0.013
0.25 1.192 0.005 1.129 0.232

3.1 0.024 2.638 0.290
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10.2 0.127 4.678 0.202
10.1 0.127 4.653 0.224
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45 ◦ C 0.5 1.150 0.074 2.773 0.117
3.3 0.251 4.549 0.028
10.2 0.406 5.428 0.063
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0.75 1.208 0.439 4.252 0.044

3.2 0.614 5.050 0.056
10.1 0.701 5.740 0.015
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3 Thermodynamic Consistency
1.0 1.0 1.0

yN [−]
yN [−]
yN [−]
0.5 0.5 0.5
2
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(a) ZSM−5 (b) ZSM−5 (c) ZSM−5
25°C | 1.2bar 25°C | 3bar 25°C | 10bar
0 0 0
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0 0.5 1 0 0.5 1 0 0.5 1
x [−] xN [−] xN [−]
N
2 2 2
1.0 1.0 1.0
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yN [−]
yN [−]
yN [−]
0.5 0.5 0.5
2
2
(d) ZSM−5
U (e) ZSM−5 (f) ZSM−5

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45°C | 1.2bar 45°C | 3bar 45°C | 10bar
0 0 0
0 0.5 1 0 0.5 1 0 0.5 1
xN [−] xN [−] xN [−]
2 2 2
M
Figure S2: Binary adsorption equilibria of the CO2 and N2 mixture on ZSM-5 shown in the x,y-plane. The symbols are the
experimental values; also shown are the predictions according to IAST (dashed lines) and the extended Sips isotherm (dotted
lines). The diagonal is shown to guide the eye.
D
TE
C EP
AC
7
ACCEPTED MANUSCRIPT
0 0 0
10 10 10
−2 −2 −2
10 10 10
yCO [−]
yCO [−]
yCO [−]
−4 −4 −4
10
2
10 10
2
−6 −6 −6
10 10 10
(a) 13X (b) 13X (c) 13X
25°C | 1.2bar 25°C | 3bar 25°C | 10bar
PT
0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 1
xCO [−] xCO [−] xCO [−]
2 2 2
RI
0 0 0
10 10 10
−2 −2 −2
10 10 10
SC
yCO [−]
yCO [−]
yCO [−]
−4 −4 −4
10 10 10
2
2
−6 −6 −6
10 10 10
(d) 13X (e) 13X (f) 13X
45°C | 1.2bar 45°C | 3bar 45°C | 10bar
U
0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 1
xCO [−] xCO [−] xCO [−]
AN
2 2 2
Figure S3: x,y-diagrams for zeolite 13X. The solid lines represent the RAST simulations, while the predictions by IAST are
shown as dashed lines. Note that the y-axis is shown in logarithmic scale.
M
1.0 1.0 1.0

D
yN [−]
yN [−]
yN [−]
TE
0.5 0.5 0.5

2
(a) 13X (b) 13X (c) 13X

25°C | 1.2bar 25°C | 3bar 25°C | 10bar
EP
0 0 0
0 0.5 1 0 0.5 1 0 0.5 1
xN [−] xN [−] xN [−]
2 2 2
1.0 1.0 1.0

C
AC
yN [−]
yN [−]
yN [−]
0.5 0.5 0.5

2
(d) 13X (e) 13X (f) 13X

45°C | 1.2bar 45°C | 3bar 45°C | 10bar
0 0 0
0 0.5 1 0 0.5 1 0 0.5 1
xN [−] xN [−] xN [−]
2 2 2
Figure S4: Binary adsorption equilibria of the CO2 and N2 mixture on zeolite 13X shown in the x,y-plane. The symbols are the
experimental values; also shown are the predictions according to IAST (dashed lines) and the extended Sips isotherm (dotted
lines); the RAST complemented with the 1-parameter Wilson model fits are shown as solid lines. The diagonal is shown to
guide the eye.

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Adsorption Equilibrium of Binary Mixtures of Carbon Dioxide and Nitrogen on Zeolites

Max Hefti, Dorian Marx, Lisa Joss, Marco Mazzotti

To appear in: Microporous and Mesoporous Materials

Received Date: 18 November 2014

Zeolite 13X at 45°C

1 Adsorption Equilibrium of Binary Mixtures of Carbon

application of ideal adsorbed solution theory (IAST). In the context of the

solution theory (RAST) to accurately describe the binary adsorption data.

Preprint submitted to Microporous and Mesoporous Materials February 24, 2015

23 A key component of the evaluation of a cyclic adsorption process is the

25 sorption equilibrium data is required. Frequently, only pure component equi-

27 in measuring multi-component adsorption. Ideally, the sorbent features a

30 While experimental efforts to develop novel materials are underway in many

31 groups, in this work we would like to focus on the characterization of two

35 perature from 25 ◦C to 140 ◦C, and described with an appropriate isotherm.

48 description and interpretation of the adsorption behavior only. A detailed

50 systems will be the subject of a follow-up work.

51 2. Experimental setup and methods

55 pellets of diameters ranging from 1.2–2mm and 1.6–2mm, respectively; both

56 manufactured by ZeoChem (Uetikon, Switzerland). According to the man-

73 produced by Pangas with a relative error of ± 1 %.

74 2.2. Interpretation of adsorption data

75 In practice and for rigorous thermodynamic calculations, it is often de-

78 directly accessible. Adsorption is determined as an incremental quantity

80 A set of assumptions is required to convert the raw data to an absolute

98 as defined by Gumma and Talu 16 .

mnet = mex − ρb V s (3)

2.3. Single component adsorption equilibrium

113 All equilibrium adsorption measurements were done with a gravimetric

142 To determine ρa of CO2 on each sample, the CO2 isotherm at a tem-

147 is common when it is not experimentally accessible, the adsorbed phase

152 2.4. Binary adsorption equilibrium

178 adsorption experiments in this work. A maximum number of three subse-

188 wifeed . ∆msample

195 3.1. Single component

199 the surface sites towards the sorbate molecules as follows:

200 where i indicates component i (i.e. CO2 or N2 ), P the pressure, n∞

204 Note that for ci = 1 the Langmuir isotherm is obtained.

temperature Tref and χi is a dimensionless fitting parameter.

210 The temperature dependence of the affinity parameter bi is commonly

213 Qb,i the characteristic energy for the affinity constant bi (T ) 35 .

214 The temperature dependence of the heterogeneity parameter ci is essen-

where cref,i is the heterogeneity parameter at the reference temperature Tref

217 and α is a dimensionless fitting parameter.

218 3.1.2. Henry’s constant

3.2. Binary system

235 To convert the individual excess adsorbed amount nex

236 to the absolute quantity nabs

248 3.2.1. Extended Sips isotherm

257 3.2.2. Adsorbed Solution Theory

259 a thermodynamically consistent framework to predict multicomponent ad-

260 sorption equilibria based on pure component parameters.

262 T and spreading pressure Π is given by 38 :

274 can be expressed in closed form as:

276 definition of the molar area of mixing is used 38;39 :

285 coefficients two thermodynamic constraints must be fulfilled 41;35 :

286 (i) γi approaches unity when the composition of i approaches unity:

287 (ii) At infinite dilution the ideal solution behavior is approached:

302 coefficients. Therefore, in line with Suwanayuen and Danner 48 we propose

304 the temperature dependence:

Λ0ij = exp − = exp − (24)

307 denoted here by λi .