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Investigation of the Adsorption of Hydrogen Sulfide on Faujasite

Zeolites Focusing on the Influence of Cations
Annika Starke,* Christoph Pasel, Christian Bläker, Tobias Eckardt, Jens Zimmermann, and Dieter Bathen
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ABSTRACT: During the conversion of natural gas to liquified natural gas, sulfur components are separated by adsorption on
zeolites. New zeolite materials may improve this adsorption process. In this paper, the adsorption of hydrogen sulfide is studied on
seven faujasite (FAU) zeolites, which differ only in the number of sodium and calcium cations. From a pure NaX zeolite (13X),
which contains only sodium cations, the calcium cation content was gradually increased by ion exchange. In a fixed-bed adsorber,
cumulative equilibrium loadings of H2S on these zeolites were determined at concentrations between 50 and 2000 ppm at 25 and 85
°C and 1.3 bar (abs). Adsorption isotherms were analyzed considering the influence of cation positioning in the FAU zeolites. The
experimental data indicate a superposition of a chemisorptive and a physisorptive mechanism. At a small number of chemisorptive
sites, we conclude a dissociation of hydrogen sulfide and covalent bonding of the proton and the hydrogen sulfide ion to the zeolite
lattice. The contribution of chemisorption exhibits a very low temperature dependence, which is typical for nearly irreversible
reactions with an equilibrium strongly shifted to one side. With an increase in the proportion of Ca2+ cations, only physisorptive
adsorption by electrostatic interaction with the cations in the lattice was observed. A large number of physisorptive sites have a lower
energetic value. The share of physisorption strongly depends on temperature, which is characteristic of reversible equilibrium
reactions.

1. INTRODUCTION swing adsorption (TSA) processes are used with polar

Natural gas covered 24.7% of primary energy consumption adsorbents such as zeolites, silica gels, or silica alumina
worldwide in 2020.1 Forecasts predict an increase in demand gels.5,6 Separation of sulfur components in particular is
over the next few years.2 The main components of natural gas preferably carried out with zeolites with a faujasite (FAU) or
are methane and other short-chain hydrocarbons. Depending a Linde type A (LTA) structure. 7 As zeolites are
on the production region, it may also contain higher aluminosilicates and consist of an anionic framework with
hydrocarbons, carbon dioxide, and sulfur-containing compo- exchangeable cations, the type and number of cations strongly
nents. Natural gas can be transported from the production sites influence adsorption properties.8−10 LTA zeolites are primarily
to the consumer by pipelines or in a cryogenic liquefied state used to dry the natural gas, but they also come into contact
[liquefied natural gas (LNG)]. Global demand for LNG is with H2S molecules and can separate them from the gas.7,11,12
forecast to double by 2035.3 Transport as LNG is subject to
strict purity requirements with respect to toxic and corrosive
components, so purification of the raw gas is necessary.4 Sulfur Received: July 21, 2022
components such as hydrogen sulfide (H2S), mercaptans Accepted: October 25, 2022
(CxHx+2SH), and carbonyl sulfide (COS) are present in trace Published: November 18, 2022
concentrations in the raw gas. The process of adsorption is
particularly suitable for separating substances in trace
concentrations. In natural gas cleaning, cyclic-temperature
© 2022 The Authors. Published by
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We have already investigated the adsorption properties of LTA temperatures of 350 °C, a chemisorptive mechanism is
zeolites in the adsorption of H2S depending on the Na+ and suspected. In this, a dissociation of H2S in pore water of the
Ca2+ cations they contain in a previous study.13 The present zeolite is supposed to occur in the first step followed by an
work deals with the adsorption properties of FAU zeolites and oxidation reaction.24
can be considered as a continuation of the first study. The field Fellmuth et al. investigated the catalytic activity in the
of application of FAU zeolites in natural gas processing is in reaction during the adsorption of H2S and CO2 on LTA and
the separation of higher hydrocarbons and mercaptans.5,14 In FAU zeolites. A decrease in catalytic activity with an increase
this process, the FAU zeolites also come into contact with in the proportion of divalent cations was observed for both
residual concentrations of H2S, which are also to be separated. FAU and LTA zeolites. Furthermore, the catalytic activity of
1.1. Literature Overview. Due to its importance for the zeolites is correlated with the number of weakly bound
industrial applications, the adsorption of H2S on zeolites has cations.25 Investigating the adsorption of H2S on a fully
been studied several times. Cruz et al. examined H2S exchanged CaX zeolite by X-ray diffraction, Jang et al. were
adsorption in various zeolites, including FAU zeolites (NaX able to locate 16 Ca2+ cations at position I and 30 Ca2+ cations
and NaY) and LTA zeolites (NaA). The FAU zeolites showed at position II. The authors propose that three H2S molecules
a higher capacity than the LTA zeolites. However, for a more were attached to each of the cations at position II, and the
detailed description of the mechanistic processes during other 59 H2S molecules formed hydrogen bonds to 2 oxygen
adsorption, further investigation is recommended.15 Tomada- atoms of each of the 12-membered rings per supercage.
kis et al. investigated the adsorption of H2S and CO2 during Dissociative adsorption of H2S was not observed.26
pressure swing adsorption on NaA, CaNaA, and NaX zeolites. Many studies deal with highly exchanged calcium FAU
The three zeolites adsorbed H2S more strongly than CO2, and zeolites. Data from zeolites with lower calcium content are
the highest H2S capacities were found on fresh CaNaA and lacking. These are important, however, to better describe the
NaX zeolites.16 Especially, for FAU zeolites, the influences of influence of cation type and positioning as well as to allow a
occupying different cation positions in the zeolite structure discussion of different adsorption mechanisms. In previous
with different cation species are difficult to determine because work, we investigated the influence of sodium and calcium
there is no consensus in the literature on the distribution of cations on the adsorption of H2S on binder-free LTA zeolites.
cations among the sites. Evidence for dissociative adsorption of H2S on weakly bound
Mauer et al. examined the influence of the type and number Na+ cations was found at site III. With an increase of Ca2+
of cations on the adsorption of methane on FAU zeolites. The cations, only physisorptive adsorption was observed.13 Based
measured adsorption isotherms and enthalpies indicate a on this publication, we commissioned PXRD measurements of
significant influence of the occupied cation positions and the LTA zeolites, which confirmed the assumptions made in
cation type on the strength of interactions.17 Frising and ref 13 about the cation positions.27
Leflaive studied the occupation of cation positions in detail and Following this publication, we started to study the FAU
prepared a comprehensive review paper on the cation zeolites since LTA and FAU are the technically relevant
distribution in X- and Y-FAU zeolites. The authors compiled zeolites for natural gas processing. We investigated the
studies on FAU zeolites including the cations Na+, Li+, K+, influence of cations in FAU zeolites on the adsorption of
Rb+, Cs+, Mg2+, Ca2+, Sr2+, and Ba2+ as well as other cations. H2S in cooperation with BASF Catalysts Germany GmbH and
Differences in the occupation of cation positions were found, Chemiewerk Bad Köstritz GmbH. From the binder-free base
depending on the type of cation and the degree of exchange. material NaX, which contains only sodium cations, the calcium
Mostly cation positions I and II are preferred, and positions III content was gradually increased by ion exchange. Cumulative
and III′, on the other hand, are occupied less frequently and breakthrough curves were measured at 25 and at 85 °C in a
are judged to be unstable.18 In addition, a shift of the cations fixed-bed adsorber, and adsorption isotherms were determined.
during the adsorption process could be shown for the Subsequently, the data were discussed with respect to
adsorption of certain adsorptives based on molecular dynamics temperature dependence, and mechanistic suggestions were
simulations. For example, Plant et al. considered the developed.
adsorption of CO2 on NaX and NaY zeolites. Especially at
low loadings, the cations located at position III′ moved to a 2. EXPERIMENTS
position close to III′.19 The same could be observed during the 2.1. Methods and Experimental Setup. Cumulative
adsorption of methanol and butane.20,21 During the adsorption breakthrough curve measurements are performed in a fixed-
of water, on the other hand, a migration of the cations can only bed adsorber (Figure 1). The feed gas mixture is generated by
be shown for the FAU zeolite with a low cation content thermal mass-flow controllers (MFCs). The adsorber has a
(NaY); this does not occur for FAU zeolites with a large cation diameter of 3.8 cm and a height of 17.5 cm. With a height/
content (NaX).22 diameter ratio of 4:1 and a ratio of 19 between the particle
The adsorption of H2S on NaX and NaY zeolites was diameter of the adsorbent (2 mm) and the adsorber diameter
studied by Karge et al. in 1987 by UV/vis and IR spectroscopy. (3.8 cm), the dimensions of the adsorber comply with the
A larger capacity was observed on NaX than on the NaY general technical design rules. The adsorber wall is designed as
zeolite. Therefore, it is assumed that different adsorption a double jacket and thus enables the temperature control of the
mechanisms take place. From the experiments, dissociative adsorber interior with a temperature-controlled fluid. In
adsorption of H2S on the NaX zeolite is concluded at low addition, electrically heatable pipes are installed to adjust
coverage levels at so-called “strong centers”. With an increase temperatures between 25 and 300 °C. The process is
in the degree of coverage, physisorption of undissociated H2S monitored by five type-T thermocouples along the adsorber
molecules dominates.23 Sigot et al. studied the desorption of and two thermocouples at the inlet and outlet of the adsorber.
H2S on NaX zeolites and came to similar conclusions. Since All thermocouples have a measuring accuracy of ±0.5 K. The
complete regeneration of the zeolites was not achieved at operating pressure of 1.3 bar (abs.) is set by an electronic
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bypass directly to the μ-GC. As soon as the concentration of

the adsorptive is constant for 30 min, the experiment is started
by switching the feed gas flow to the fixed-bed adsorber.
If the adsorptive concentration at the outlet of the adsorber
corresponds to the adsorptive concentration at the inlet of the
adsorber and the outlet concentration is within the statistical
deviation of the μ-GC for a period of 45 min, the system has
reached equilibrium. By increasing the volumetric flow rate of
H2S, the concentration of the adsorbent can then be increased
and the next equilibrium step approached. Isotherms with 11
equilibrium points each were measured using this cumulative
measurement method.
To determine the equilibrium loading , a mass balance
around the adsorber is done by integrating the area above the
breakthrough curve (eq 1). describes the total flow,
consisting of the nitrogen flow and the adsorptive flow, is
the mass of the adsorbent, is the inlet concentration of the
adsorptive, and is the measured outlet concentration.
The integration of the area above the measured break-
through curves can be expressed as the sum of the
concentration differences over a time interval. Due to the
cumulative measurement method, the determined loading of
the previous equilibrium point is added.
Figure 1. Process scheme of the experimental plant.

pressure control. Pressure monitoring is ensured by two

pressure gauges from BD Sensors. The gas mixture is analyzed (1)
by a μ-GC (micro-gas chromatograph Varian CP-4900).
For conditioning, the adsorbent is heated in a nitrogen- To fit the experimental data, a dual-site Langmuir isotherm
purged oven at 350 °C for 4 h before the experiments. The hot is used (eq 2). In the dual-site Langmuir isotherm, two
adsorbent is then filled into the adsorber. Dry nitrogen is flown Langmuir terms are added. This allows the consideration of
through the adsorbent until the experimental temperature is
two energetically very different adsorption sites. The
reached. For mixing the raw gas, the sample gas is added to the
matrix gas stream by an MFC. To adjust the concentration on parameters and give the monomolecular loading and
the wanted level, the entire gas flow is passed first through the the affinity parameter of the respective adsorption site .28

Figure 2. Schematic view of (a) a sodalite cage and (b) a super cage with the distribution of cation positions in the FAU zeolite (according to refs 9
and 20. Position I: This position is centered inside the double six-membered ring that connects the sodalite cages. Per super cage, this position is
present 16 times. Position I’: Position I′ is located on the double six-membered ring surfaces of the sodalite cages. In total, this position is present
32 times per supercage. Position II: Cation site II is located on the six-membered ring surfaces of the sodalite cages, which are oriented toward the
supercage. These are present 32 times per supercage and are accessible to adsorptive molecules. Position II’: This cation position corresponds to
position II and is also present 32 times per supercage, but cation position II′ has shifted into the sodalite cage. Thus, this position is not accessible
from the supercage and therefore is inaccessible to many adsorptive molecules. Moreover, positions II and II′ cannot be occupied simultaneously.
Position III: This position is located inside the supercage near the four-membered rings. From this, a total of 48 sites are available per supercage.
Adsorptive molecules can easily reach cations at this position. Position III’: While position III is centrally located on the surface of the four-
membered ring, position III′ is located offset from the four-membered ring. Similarly, this position is described as lying in the 12-member ring,
which forms the entrance to the supercage. Cation position III′ occurs up to 96 times per supercage.

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of 1.17. According to the structural formula of the FAU

zeolites (eq 3), a unit cell with this Si/Al ratio consists of 88
aluminum atoms and 104 silicon atoms. Accordingly, 88
charges must be introduced via the cations for charge balance.
(2) M represents the cation type, and y is the valence of the
cations.
Fitting was performed by nonlinear regression using the
Levenberg−Marquardt algorithm to minimize the squared (3)
errors.
2.2. Error Analysis. For the systematic error, instrumental To reduce the Gibbs energy, cations initially occupy
errors must be considered. This includes the error of adsorbent positions with strong interactions. These positions are as
mass determination (Acculab 3100.2 balance), measurement of close as possible to the zeolite lattice. There are different views
gas concentration (Varian Micro GC CP4900 gas chromato- in the literature on the occupation and order of energetic value
graph), and setting of gas flows (Bronkhorst EL-FLOW mass- of the positions.
flow controller). This results in a systematic error of 3.5%. In this paper, we follow the proposal of Frising and Leflaive
Gaussian error propagation is used to calculate the statistical as it is very comprehensive and includes many sources.18
error. Variables subject to error in the calculation of the Decisive factors influencing the distribution of cations at the
equilibrium loading are mass flow rate, adsorbent mass, time, corresponding positions are the activation process, the cation
and inlet, as well as outlet concentration of the adsorptive. The type, and impurities in the zeolite. In addition, it must be taken
statistical error of time is neglected due to the precise time into account that even with identical zeolites, a slightly
measurement. Moreover, the inlet concentration is obtained different cation distribution cannot be ruled out as a result of
from the arithmetic mean of the outlet concentration with a small differences in the manufacturing process. There is
large number of measured values, so the error on this value is agreement on the assumption that cation positions I, I′, and II
also negligible. Thus, the total error varies between approx. 3.7 provide sites of higher energetic quality than positions III and
and 10%. III′. According to Takaishi et al., the order of energetic valence
is I, I′, II, and III′, with position I having the highest value.30
3. MATERIALS On the contrary, Abrioux et al. consider position II to be the
most stable position in the FAU zeolite lattice since they
In this paper, we studied seven FAU zeolites, which differ in estimate that the electrostatic repulsive forces are lowest
the number of sodium and calcium cations. Zeolites consist of there.31 This is in agreement with some results of Frising and
SiO4 and AlO4 tetrahedra, which are linked via oxygen atoms. Leflaive, who also identify position II as the favored position
The Si/Al ratio can range from 1 to 3 for FAU zeolites. In the for certain cation species.18 In addition, the adjacent cation
range of 1−1.5, FAU zeolites are called type X zeolites, with positions I and I′ cannot be occupied simultaneously.30,32,33
Si/Al ratios of 1.5 to 3 type Y zeolites.8 In this work, zeolites Thus, a maximum of 32 cations can be placed at these two
with a Si/Al ratio of 1.17 belonging to type X were positions. This can be explained by repulsive forces among the
investigated. The tetrahedra assemble into secondary building cations resulting from the geometry (Figure 3).9,31,32,34,35
units (SBUs). These form the polyhedral tertiary structure of
the zeolites. Figure 2 shows one of these tertiary structures, the
sodalite cage, consisting of 24 tetrahedra. In the FAU structure,
the sodalite cages are linked by double six-membered rings.
Eight sodalite cages form a supercage (Figure 2) with a free
diameter of 1.37 nm. It can be accessed via four apertures
consisting of 12-membered rings with an effective diameter of
0.74−0.8 nm, depending on the number and type of cations.
The symmetry of the FAU zeolite is described in the literature
by the space group Fd 3m.9
Since a negative charge is introduced into the zeolite lattice Figure 3. Position of the cation sites I and I′ in the double six-
by the aluminum atoms, cations must be present to balance the membered ring.
charge. These cations are located in different positions in the
cage structure. In the scientific literature, there is no consensus
on the number and distribution as well as the occupation of Occupation of the positions is only possible by one cation
cation positions, but various approaches and models have been on position I or by two cations on the two positions I’.
published. The most common is the assumption that there are Depending on the exchange rate, the total number of cations
six cation positions (Figure 2).8,29 changes if monovalent Na+ is exchanged by divalent Ca2+. The
The cation positions II, III, and III′ are important for relationships with the energetic valence of cation sites and their
adsorption processes since they are accessible to adsorptive occupancy then lead to the following distribution scheme for a
molecules via the supercage. In contrast, cation positions I, I′, supercage unit:
and II′ are only accessible via the six-membered rings of the <32 cations per unit: depending on the type of cations,
sodalite cages. The free diameter of these rings is 0.28 nm, so position I or II is preferred; for example, Ca2+ cations
only adsorptive molecules with a smaller critical diameter can prefer position I18
enter the sodalite cages and reach the cation positions I, I′, and <64 cations per unit: depending on the type of cations,
II′. The number of charges required to balance the total charge position I or II is preferred, if position I cannot be
is determined by the number of aluminum atoms and thus by occupied due to too many cations, the cations settle on
the Si/Al ratio. All the zeolites studied here have a Si/Al ratio positions I′ and II
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Figure 4. Changes in the unit cell during the exchange of Na+ cations for Ca2+ cations (according to ref 18).

>64 cations per unit: positions I′ and II are completely are gradually removed. From an exchange rate of 56%, no more
occupied; all other cations are placed in positions III and cations are present in this position. Below a total number of 64
III′.18 cations (degree of exchange of 54.5%), a statement on the
occupancy of cation positions I, I′ and II becomes difficult.
The base material NaX was synthesized by Chemiewerk Bad Since it cannot be clearly determined which and how many
Köstritz GmbH from sodium silicate, sodium aluminate, and cations are in positions I and I′ in each case, which has a direct
sodium hydroxide in the liquid phase by a well-known effect on the number and type of cations relevant for
industrial synthesis route.36 The primary crystals have a size adsorption in position II, no figure is given here for the
of 2.0−5.0 μm. During ion exchange in the liquid phase, occupation of the respective positions. Accordingly, the
sodium ions were exchanged for calcium ions. For this interpretation of the experimental results is limited to those
purpose, the granulated sodium form (NaX) was continuously effects that can be clearly explained with knowledge of the
flown through by a solution consisting of water and calcium cation distribution. For a more detailed discussion, it would be
chloride with a molarity between 0.1 and 0.5 mol·l−1 in an ion
necessary to determine the exact occupation of the cation
exchange column at 298.15 K. This was followed by activation
positions, for example, by XRPD measurement. However, this
of the zeolites at temperatures ranging from 573.15−673.15 K.
is not the subject of this work.
The exchange rate indicates the amount of sodium cations
Nitrogen isotherms were measured volumetrically at 77 K
removed from the base material NaX and exchanged by
using a Bel-Sorb Mini measuring device (Bel Japan). Before
calcium cations. The materials in this work have exchange rates
measurement, the zeolites were conditioned under vacuum for
of 0, 19, 36, 50, 56, 71, and 90%. All zeolites examined are
6 h. The specific BET surface area (DIN ISO 9277) and pore
binder-free.
volume according to Gurvich (DIN 66134) are shown in Table
Figure 4 lists the data on cations in the zeolite with
1. The pore size distributions of the FAU zeolites are shown in
increasing degree of cation exchange. Following the consid-
the Supporting Information (figure S1).
erations described above, we assume a complete occupation of
the cation positions I′ and II with 32 cations each for the
sodium form NaX (exchange rate 0%; 88 Na+ cations). The Table 1. BET Specific Surface Area and Pore Volume of the
remaining 24 cations occupy places at positions III and III’. FAU Zeolites
Since only cations at positions II, III, and III′ are accessible to adsorbent BET surface (m2 g−1) pore volume (cm3 g−1)
H2S molecules, this results in a 56 accessible cations. In the Na88X 847 0.32
cation exchange process, two monovalent sodium cations are Ca8Na72X(19%) 831 0.32
exchanged for one divalent calcium cation. With increasing Ca16Na56X(36%) 831 0.32
exchange rate, the total number of cations decreases. Thus, Ca22Na44X(50%) 830 0.32
with an exchange rate of 19%, the total number of cations is 80, Ca29Na30X(56%) 833 0.32
divided into 72 Na+ and 8 Ca2+ cations. It is assumed that the Ca36Na16X(71%) 842 0.33
cations weakly bound at positions III and III′ are the first to be Ca38Na12X(90%) 837 0.33
removed during ion exchange. Since the total number of
cations is still greater than 64, the two cation positions I′ and II
continue to be fully occupied. The remaining 16 cations
occupy positions III and III’. The number of accessible cations The values for BET surface area and pore volume are each of
becomes 48. The introduced calcium cations presumably the same order of magnitude and within the error range of 2%.
accumulate at the higher value positions I′ and II and not at Moreover, no trend can be observed (average BET surface area
positions III or III’. Hence, when the degree of exchange is 835.8 m2 g−1 and average pore volume 0.3215 cm3 g−1).
gradually increased to 50%, the cations on positions III and III′ Therefore, it is assumed that the BET surface area and pore
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Figure 5. H2S isotherms on calcium-exchanged FAU X zeolites at 25 °C.

Figure 6. H2S isotherms on FAU X zeolites at 25 °C: (a) exchange rates 0−50% and (b) exchange rates 56−90%.

volume of the zeolites studied are independent of the degree of determined equilibrium loadings are shown as symbols, and
cation exchange. the lines indicate calculated isotherm equations. The
Nitrogen from the university’s own infrastructure with a corresponding isotherm parameters are given in Tables S1
purity of 99.999% and a dew point lower than −80 °C is used and S2, and the measured data points are given in Tables S3
as the carrier gas. Hydrogen sulfide (H2S) with a purity of and S4 in the Supporting Information For the sake of clarity,
>99.5% from Air Liquide was used as an adsorptive. H2S the isotherms at 85 °C are not shown with error bars.
molecules have a critical diameter of 0.36 nm and a molar mass 4.1. Adsorption of H2S on FAU Zeolites at 25 °C.
of 34.08 g·mol−1. Additionally, H2S is considered polar with a
Figure 5 shows the measured adsorption isotherms at 25 °C.
dipole moment of 0.98 D. Thus, the adsorption on the zeolites
is expected to be mainly caused by attractive electrostatic For clarity, the isotherm field is split. Figure 6a shows the
cation−dipole interactions with the cations and anion−dipole isotherms on the FAU zeolites with exchange rates of 0−50%.
interactions with oxygen atoms of the zeolite lattice, which These four isotherms have a very steep increase in the low
carry delocalized negative charges.37 This paper focuses on the concentration range and a marked decrease in the isotherm
influence of the cation−dipole interactions, which can be slope from about 50 ppm. The three zeolites NaX,
better analyzed due to the localized character of the cations in CaNaX(19%), and CaNaX(36%) show a comparable loading
the zeolite structure. of approximately 0.75 mol·kg−1 at 50 ppm. Consequently,
these materials have a similar slope in the initial range. The
4. RESULTS AND DISCUSSION material CaNaX(50%) reaches a loading of only 0.56 mol·kg−1
The H2S isotherms were measured at a temperature of 25 and at 50 ppm. From concentrations of approximately 200 ppm,
85 °C in the concentration range of 50 to 2000 ppm. In the the loadings of the CaNaX(19%) and the CaNaX(36%) zeolite
following, the isotherms are shown in the diagram as loading in are above the loading of the NaX zeolite. The CaNaX(50%)
mol·kg−1 versus concentration in ppm. The experimentally zeolite has a lower loading than the other three materials at the
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Figure 7. H2S isotherms on calcium-exchanged FAU zeolites at 85 °C.

beginning of the concentration range. From about 530 ppm, flattens out. When changing from a 50% exchange rate to a
however, this isotherm intersects the NaX isotherm. 56% exchange rate, a strong reduction in capacity can be
With an increase in the degree of exchange from 0 to 19%, observed. At this point, the smallest exchange rate difference
the introduction of calcium cations provides a clear increase in among these two zeolites is noticeable, but the largest loading
capacity. At 2000 ppm, CaNaX(19%) shows a H2S loading of difference occurs. Therefore, the increase in the degree of
2.68 mol·kg−1, whereas the loading of NaX at 2000 ppm is 2.28 exchange from 50 to 56% appears to represent a point of
mol·kg−1. The loading in molecules per unit cell, which can be change in the zeolite material that is relevant to adsorption.
calculated using eq 1 and the molar masses of the respective Clearly, there would be an elimination of relevant adsorption
atomic species, corresponds to 30−36 H2S molecules per unit sites or limited access to important cations. From this point in
cell. With a further increase in the degree of exchange to 36 the exchange series, the cation positions III are no longer
and 50%, a decrease in the loading can be observed. occupied. A correlation between the unoccupied cation
Figure 6b represents the H2S isotherms on the FAU zeolites position III and the decrease in capacity is assumed. When
with the exchange rates of 56, 71, and 90%. The zeolite the degree of exchange is further increased to 71 and 90%, an
CaNaX(56%) exhibits the lowest loading throughout the increase in capacity can be observed compared to
concentration range. Furthermore, the slope in the low CaNaX(56%).
concentration range and the subsequent decrease in slope When comparing the H2S isotherms at 25 °C on the seven
are not as pronounced in this material as in the other materials FAU zeolites investigated, no clear trend can be identified.
investigated. Instead, this material shows a uniform decrease in This suggests overlapping of capacity-increasing and capacity-
slope with no characteristic regions. The materials decreasing effects. Since the materials differ only in their
CaNaX(71%) and CaNaX(90%) show loadings of the same proportion of calcium and sodium cations, the type and
order of magnitude with approx. 0.7 and 0.8 mol·kg−1 at 50 number of cations seem to be decisive for adsorption
ppm, with correspondingly strong slopes in the low properties.
concentration range. When the concentration is increased, a Four effects may be superimposed in an exchange series:
flattening of the slope can be observed again. Over the further 1 Stronger binding cations by ion exchange: In an
concentration range, both isotherms run very similarly. At each exchange series, the substitution of monovalent Na+
exchange rate, both calcium and sodium cations are present at ions with divalent Ca2+ ions will lead to stronger
accessible cation positions (with the exception of 0 and 100%) interactions and thus to an increase in capacity.
(Figure 4). Calcium cations provide adsorption sites of higher 2 Change of cation number: At the same time, however,
energetic value due to their divalent charge. Therefore, calcium the number of cations is reduced, so fewer binding sites
cations form stronger ion−dipole interactions with H2S are available. This leads to a decrease in capacity.
molecules than monovalent sodium cations. The number of 3 Limited accessibility of cation sites: In the FAU zeolite,
H2S molecules per unit cell ranges from 26 to 36 at a not all cations are accessible to the adsorptive molecules.
concentration of 2000 ppm (Table S5 in the Supporting Since it cannot be clearly clarified which and how many
Information). Thus, assuming the distribution according to cations are accessible for adsorptive molecules at
Figure 4, the number of molecules per unit cell is below the different exchange rates, an influence on adsorption
number of accessible cations per supercage. As a result, each properties cannot be quantified in more detail at this
H2S molecule can interact with its own cation. Consequently, point.
the more calcium the cations contained, the more the H2S 4 Change of cation positions: A reduction in the total
molecules that can interact with them, resulting in a steep number of cations as part of a cation exchange of
isotherm at low concentrations. If a large part of the calcium monovalent sodium cations for divalent calcium cations
sites is occupied at higher concentrations, H2S molecules leads to a change in the occupation of the cation
increasingly adsorb at sodium cations. This implies that positions (Section 1.2). In addition, cation migration
energetically less valuable sites are occupied and the isotherm may possibly occur due to the adsorption of the H2S
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Figure 8. H2S isotherms on FAU zeolites at 85 °C: (a) exchange rates of 0−50% and (b) exchange rates of 56−90%.

molecules, as has already been shown, for example, for final capacity could be reached (0.42 mol·kg−1). The isotherm
the adsorption of CO2, methanol, and alkanes.19−21 If of the material CaNaX(36%) is initially below the isotherm of
there are cation sites with strongly differing energetic the material CaNaX(19%). At about 1300 ppm, the isotherms
values, such as chemisorption and physisorption sites, cross and from then on the loading of the CaNaX(36%) is just
these could be varied in number by cation exchange. above the loading of the CaNaX(19%). At this exchange rate,
about 59% of the final loading is reached at 50 ppm. For the
The cation distribution in FAU zeolites is much more zeolite with an exchange rate of 50%, this trend continues, and
complex than, for example, in LTA zeolites because of the the loading in low concentration ranges is below the loadings
different tertiary structures. Due to the structure complexity, of the other three zeolites. At 1600 ppm, the isotherm crosses
commissioned XRPD measurements to determine the cation the isotherm of CaNaX(36%). At the end of the studied
positions in FAU zeolites could not be meaningfully evaluated. concentration range at 2000 ppm, the loading of the material
For this reason, we refrained from a detailed interpretation of CaNaX(50%) is at the same level as the loading of the material
the results based on hypothetical cation positions and limited
CaNaX(19%). The zeolite CaNaX(50%) reaches about 43% of
ourselves to a mechanistic discussion. In the following, we
the final loading at 50 ppm.
would like to discuss the influence of the cations in the
For the second group of zeolites with the exchange rates of
exchange series on the chemisorption and physisorption of
56, 71, and 90%, the initial increase up to the first measuring
H2S. Chemisorption in the form of dissociative adsorption of
point at 50 ppm is less steep. Here, initial loadings are between
H2S on weakly bound cations in the FAU-X zeolite was
suspected in previous work.25,38 To find conclusive evidence 0.07 mol·kg − 1 (CaNaX(56%)) and 0.17 mol·kg − 1
for dissociative adsorption of H2S, we measured isotherms at (CaNaX(90%)). Between CaNaX(50%) and CaNaX(56%),
85 °C to compare them with the data at 25 °C. the smallest exchange rate difference is present. Nevertheless,
4.2. Adsorption of H2S on FAU Zeolites at 85 °C. the highest capacity loss takes place. This was also observed at
Figure 7 shows the measured adsorption isotherms at 85 °C. 25 °C. The zeolite CaNaX(56%) exhibits the lowest capacity
For better clarity, the isotherm field in Figure 8 has been in the test series at 85 °C over the entire concentration range.
divided into two diagrams. Figure 8a shows the isotherms of Increasing the degree of exchange to 71 and 90% leads to an
the zeolites NaX, CaNaX(19%), CaNaX(36%), and increase in capacity in each case. This reverses the previous
CaNaX(50%). Figure 8b presents the isotherms of the zeolites trend of decreasing concentration when the degree of exchange
CaNaX(56%), CaNaX(71%), and CaNaX(90%). increases. The decrease in the slope from 50 ppm and thus the
The H2S isotherms at 85 °C can be divided into two groups flattening of the isotherms in the concentration range between
according to their different shapes. The first group includes 50 and 2000 ppm takes place to a lesser extent in this zeolite
materials with exchange rates between 0 and 50%. These group than in the zeolites from the first group. The majority of
isotherms show a very steep loading increase in the low adsorption in this zeolite group takes place only at
concentration range. Already at an adsorptive concentration of concentrations between 50 and 2000 ppm. For example, for
50 ppm, loading values between 0.27 mol·kg−1 (CaNaX(50%)) CaNaX 71%, the loading increases from 0.14 mol/kg (50 ppm)
and 0.52 mol·kg−1 (NaX) are reached. The NaX material has to 0.5 mol/kg (2000 ppm). In addition, the isotherms of this
the highest capacity. The loadings of the materials group show a concave course without characteristic regions.
CaNaX(19%), CaNaX(36%), and CaNaX(50%) follow a For H2S isotherms at 25 °C, no clear trends can be
descending order. At concentrations above 50 ppm, a sharp identified. When comparing the capacities at 85 °C, at the end
decrease in the isothermal slope occurs. For the base material of the measuring range, one observes a decrease with an
NaX, a final loading of 0.69 mol·kg−1 was measured at 2000 increase in the degree of exchange up to 56% and then an
ppm. Accordingly, at concentrations of 50 ppm, about 75% of increase with a further increase in the degree of exchange. This
the final capacity was already reached. With the first increase in trend reversal again indicates the superposition of capacity-
the exchange rate to 19% (CaNaX(19%)), the loading at 2000 increasing or -decreasing effects.
ppm is reduced to 0.59 mol·kg−1. Also with this zeolite, at However, one result is striking: if we compare the data at 25
concentrations of 50 ppm, already approximately 71% of the and 85 °C, we find that the arrangement of the isotherms
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Figure 9. H2S isotherms at 25 and 85 °C on (a) NaX and (b) CaNaX 56%.

Figure 10. H2S isotherms normalized to the input concentration at 25 and 85 °C on (a) NaX and (b) CaNaX 56%.

within the exchange series at 25 and 85 °C does not match. adsorption of H2S at 25 °C (Table S6 in the Supporting
This suggests a different temperature dependence of relevant Information).
mechanisms. Based on this evidence, we develop a mechanistic In contrast, materials with exchange rates from 56 to 90%
proposal. exhibit a constant decrease in loading over the entire
4.3. Mechanistic Proposal for the Adsorption of H2S concentration range. For example, in case of CaNaX(56%), a
on FAU Zeolites. We will now discuss the existence of 74% reduction in loading can be observed in the low
temperature-independent chemisorptive and temperature- concentration range and a reduction of 80% in the high
dependent physisorptive sites, the number of which depends concentration range is found. For these zeolites, we propose
on the proportion of calcium cations. To investigate these that only physisorptive adsorption with a stronger temperature
effects in more detail, the change in H2S adsorption on some dependence takes place. The energetically high-quality and less
materials when the temperature is increased from 25 to 85 °C temperature-dependent chemisorptive sites observed in the
is analyzed. For further analysis of the results, the adsorption FAU zeolites with exchange efficiencies up to 50% could be
isotherms of selected FAU zeolites at 25 and 85 °C are shown provided by sodium cations at cation positions III and III’. At
exchange rates above 54.5%, the cation positions III and III’
in Figure 9. The base material NaX shows a moderate
remain completely unoccupied (Figure 4). From an exchange
reduction in loading at low concentrations (50 ppm) due to
rate of 56%, the isotherms no longer show any evidence of
the temperature increase by 31%. In the high concentration
energetically high-quality adsorption sites, so a correlation
range (2000 ppm), the reduction increases to 68%. This between energetically high-quality adsorption sites and the
indicates a lower temperature dependence in the low occupation of cation positions III and III′ can be assumed.
concentration range and a stronger temperature dependence Figure 10 shows the isotherms of NaX and CaNaX(56%) at
in the higher concentration range. Similar results are found for 25 and 85 °C normalized to their final concentration. As a
the materials up to an exchange rate of 50%. For these result of the temperature increase, it can be seen that the shape
materials, we suggest the existence of adsorption sites with of the isotherms on the NaX zeolite changes the most. At 85
energetically different values. In the low concentration range, °C, a kink in the isotherm becomes visible. This is not the case
there is a significant contribution of adsorption on sites of high at 25 °C. A similar kink at 85 °C can be observed for the
energetic value, which is less temperature-dependent. Low zeolites with exchange rates of 19, 36, and 50%. On the
temperature dependence is typical for nearly irreversible contrary, the isotherms of the zeolite CaNaX(56%) each
processes with the equilibrium strongly shifted to one side. exhibit a similar shape at both temperatures without a
In adsorption, this applies to chemisorptive sites. In addition, pronounced kink. A similar behavior was found for the
the NaX zeolite could not be completely desorbed after the materials with exchange rates of 71 and 90%.
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Figure 11. Mechanistic proposal of the interaction of an adsorbed H2S molecule on Na+ cations on position III.

The abrupt change in the isothermal gradient at the point of cations, due to their dual charge, stronger electrostatic
the kink suggests that there is a change in the dominant interactions between the cation and the dipole of H2S are
adsorption mechanism. In the region of a large slope, expected between calcium cations and H2S molecules than
predominantly energetically high-quality chemisorptive sites between monovalent sodium cations and H2S molecules.
will be occupied, while in the region of a small slope, However, a clear correlation between the degree of exchange
adsorption occurs predominantly at energetically lower-quality and loading, which should increase as a result of the stronger
physisorptive sites. At 85 °C, physisorption decreases sharply, interactions, cannot be observed. Presumably, the calcium ions
while chemisorption is only slightly temperature-dependent. position themselves at cation position I, where the cation can
Therefore, the transition from the region of predominant interact with a particularly large number of oxygen atoms.
chemisorption to the region of predominant physisorption is However, cations at this position are not accessible for
particularly clear at 85 °C, and a kink in the isotherm is adsorptive molecules because of their position in the sodalite
formed. Because the kink disappears when the exchange rate is cage and in the double six-membered ring.
increased to more than 50%, the chemisorptive adsorption 4.4. Comparison Between the Results of the NaA and
sites at cation positions III and III′ may have disappeared. NaX Zeolite. In a previous study, we have already investigated
Cations in this position are only weakly bound to the lattice the influence of cations on the adsorption of H2S in LTA
and are first removed from the zeolite lattice during cation zeolites.13 The two zeolites are similar in that both are
exchange. Thus, as the degree of exchange is increased to composed of the same SBUs. However, the tertiary building
>50%, the cations at positions III and III’ have been removed. structure differs, resulting in a much more complicated cation
A similar behavior of the isotherm shape with increasing distribution in the FAU zeolite. Due to the same SBUs, the
temperature could already be observed in a work with LTA same adsorption mechanisms can be suspected based on the
zeolites with sodium cations and low calcium exchange rates.13 experimental results in both zeolites. Based on the adsorption
There, too, the existence of adsorption sites with different isotherms of H2S on the NaX zeolite and the NaA zeolite
energetic valence was suspected, as well as the occurrence of (isotherm data from13), the influence of the zeolite structure
dissociative adsorption of H2S. Since the cation positions on adsorption can be discussed. Both zeolites have only
LTA(III) and FAU(III) are geometrically very similar, we also sodium cations. Figure 12 shows the isotherms of both zeolites
assume dissociative adsorption of H2S as on the LTA zeolites at 25 °C (a) and 85 °C (b).
(Figure 11).
In this process, a H2S molecule first physisorbs on a Na+-
cation at position III or III′ in the supercage. The adsorption
enthalpy released leads to the dissociation of the H2S molecule
into SH− and H+, which are subsequently chemisorptively
bound. The SH− anion attaches to the sodium cation, while
the proton interacts with an oxygen atom in the lattice.38−40
The same mechanism is considered to be the first step of the
catalytic activity in the formation of COS during the
simultaneous adsorption of H2S and CO2 on LTA and FAU
zeolites.25,25,40 At other cation positions, the adsorption
enthalpy does not seem to be sufficient for the dissociation
of H2S molecules. This is probably caused at cation position II
by stronger shielding by the oxygen atoms, while positions I, I′,
and II′ are not accessible for the H2S molecules (Figure 4). All
Ca2+-cations are presumably located at cation positions I, I′, II, Figure 12. Isotherms of H2S on zeolites NaX and NaA at (a) 25 °C
and (b) 85 °C.
and II′, so dissociative adsorption to Ca2+-cations is not
assumed. Since this mechanistic discussion of H2S chem-
isorption is theoretical, Figure 11 is only symbolic. At both 25 and 85 °C, the NaX zeolite exhibits a greater
At the adsorption sites present in large numbers at cations capacity for H2S. This is an unexpected finding. The zeolites
on site II and at the negatively charged oxygen atoms, a have different Si/Al ratios. The NaA zeolite has a Si/Al ratio of
temperature-dependent physisorption of the H2S molecules is 1, while the NaX zeolite has a Si/Al ratio of 1.17. Accordingly,
to be expected. Electrostatic ion−dipole interactions act there are more Al atoms in the NaA zeolite than in the NaX
between ions at site II and H2S molecules. In case of the zeolite, relative to mass. Since negative charges are introduced
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Table 2. Parameters for Calculating the Number of Chemisorptively Active Cations per Gram of Adsorbent
NaX NaA

sum formula unit cell

Si/Al ratio 1,17 1
number of Na + cations per unit cell 88 12
residual water content (Karl Fischer titration) 0,96 Ma % 1,16 Ma %
number of unit cells per g adsorbent 4,43025 × 1019 3,49165 E + 20
number of chemisorptively active cations per unit cell 24 1
number of chemisorptively active cations per g adsorbent 1,06326 × 1021 3,49165 E + 20

into the zeolite lattice with the aluminum atoms, more cations positioning, type, number, and accessibility of the cations
must be present in the NaA zeolite than in the NaX zeolite, dominate the adsorption mechanisms and capacity.
relative to the mass, to establish neutrality. The number of
cations present exerts a significant influence on the capacity for 5. SUMMARY
H2S since more cations generally provide more binding sites.
Thus, there must be another influencing factor of the zeolite The adsorption of hydrogen sulfide was studied on FAU
structure on the capacity to explain the loadings on the NaX zeolites in which sodium was exchanged for calcium with
and NaA zeolite. Evidence of dissociative adsorption exchange rates of 0, 19, 36, 50, 56, 71, and 90%. For this
(chemisorption) was found for both zeolites when H2S was purpose, cumulative breakthrough curves were measured at
adsorbed. This takes place at the cation position III in the LTA temperatures of 25 and 85 °C in a fixed-bed adsorber. Using a
zeolite and positions III and III′ in the FAU zeolite. mass balance, the loading could be determined and isotherm
Adsorption sites that cause dissociative adsorption of H2S parameters fitted to the experimental data. No clear trends can
have a high energetic value. As a result, adsorption at these be found with an increasing degree of exchange in the
sites leads to a particularly strong increase in capacity. arrangement of the isotherms. Instead, a trend reversal of the
Therefore, comparing the available number of these sites in capacities with an increasing degree of exchange is found at
the two zeolites is useful. Since the unit cells of the NaX
both temperatures at the end of the measurement range. This
(supercage) and NaA (α-cage) zeolites differ greatly, the
number of dissociative adsorption sites per gram of adsorbent is attributed to the superposition of multiple opposing effects.
is determined. This can be calculated using the knowledge of For example, the type and number of cations have an influence
the cation positions, the sum formula of the unit cell, the Si/Al on the loading due to the different strengths of interactions
ratio, and the residual water content in the zeolite. Table 2 with H2S molecules. In the exchange series, as the proportion
gives an overview of the data used for the calculation and the of calcium ions increases, the total number of cations
results. decreases. At the same time, more divalent cations are present.
This calculation shows that the number of potentially Furthermore, different cation positions exist in FAU zeolites,
chemisorptively active cations in the NaX zeolite is 3 times which are differently attractive for cations. However, some of
higher than in the NaA zeolite. Accordingly, a greater these positions are not accessible to the H2S molecules due to
proportion of dissociative adsorption of H2S can be assumed their location in the zeolite lattice. Finally, to work out a
in the NaX zeolite. mechanistic proposal, the temperature dependence of the
This assumption can be confirmed by observing the
adsorption of H2S on the seven zeolites was considered.
isotherms at 85 °C. Due to the strong temperature dependence
Differentially strong temperature dependences of the isotherms
of the physisorption of H2S on the cations, a strong decrease in
capacity can be expected due to the temperature increase. at exchange rates up to 50% indicate two energetically different
Accordingly, the contribution of physisorption to the total kinds of adsorption sites. The temperature-independent
loading is assumed to be very small. The majority of the total adsorption sites are attributed to a chemisorptive mechanism
loading is caused by chemisorption. Since the loading of the in which the dissociation of H2S molecules occurs. The
NaX zeolite at 85 °C with 0.52 mol kg−1 at an adsorptive resulting proton and hydrogen sulfide ion are covalently
concentration of about 50 ppm is larger than the loading of the bonded to the zeolite lattice. Since evidence for this
NaA zeolite with 0.19 mol kg−1, a larger share of dissociative mechanism cannot be observed at exchange rates above 50%,
adsorption can be assumed. This is consistent with the dissociative adsorption of H2S molecules is associated with
calculations. sodium cations at positions III and III’. When the exchange
Thus, although there are more cations per gram of adsorbent rate is increased, the occupation of these positions disappears
in the NaA zeolite than in the NaX zeolite, a lower loading is and thus chemisorption. Physisorption of H2S molecules on
found on the NaA zeolite because the different structure leads
accessible cations and anions by the formation of electrostatic
to strong differences in cation positioning. Thereby, more
cations are available for the H2S molecules in the NaX zeolite, interactions then dominates.
which allow dissociative adsorption of H2S due to their The comparison of the influence of the structure of the NaA
positioning. This dissociative adsorption makes a large and NaX zeolites on the adsorption of hydrogen sulfite shows
contribution to the total capacity due to its high energetic that consistently higher capacities are achieved on the NaX
valence so that the NaX zeolite has a larger capacity for H2S zeolite. This can be explained by the larger proportion of
than the NaA zeolite over the entire concentration range and at catalytically active sites in the NaX zeolite compared to the
both 25 and 85 °C. This example emphasizes that the NaA zeolite, relative to the adsorbent mass..
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■
*
ASSOCIATED CONTENT
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■ AUTHOR INFORMATION
Corresponding Author
862.
(13) Starke, A.; Pasel, C.; Bläker, C.; Eckardt, T.; Zimmermann, J.;
Bathen, D. Impact of Na+ and Ca2+ Cations on the Adsorption of
Annika Starke − Chair of Thermal Process Engineering, H2S on Binder-Free LTA Zeolites. Adsorpt. Sci. Technol. 2021, 2021,
University of Duisburg-Essen, D-47057 Duisburg, Germany; 1−12.
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uni-due Sorptionsmittel. Chem. Ing. Tech. 2010, 82, 929−940.
(15) Cruz, A. J.; Pires, J.; Carvalho, A. P.; De Carvalho, M. B. de.
Authors Physical Adsorption of H2S Related to the Conservation of Works of
Christoph Pasel − Chair of Thermal Process Engineering, Art: The Role of the Pore Structure at Low Relative Pressure.
University of Duisburg-Essen, D-47057 Duisburg, Germany Adsorption 2005, 11, 569−576.
(16) Tomadakis, M. M.; Heck, H. H.; Jubran, M. E.; Al-Harthi, K.
Christian Bläker − Chair of Thermal Process Engineering, Pressure-Swing Adsorption Separation of H 2 S from CO 2 with
University of Duisburg-Essen, D-47057 Duisburg, Germany Molecular Sieves 4A, 5A, and 13X. Sep. Sci. Technol. 2011, 46, 428−
Tobias Eckardt − BASF Catalysts Germany GmbH, D-31582 433.
Nienburg, Germany (17) Mauer, V.; Bläker, C.; Pasel, C.; Bathen, D. Energetic
Jens Zimmermann − Chemiewerk Bad Köstritz GmbH, D- Characterization of Faujasite Zeolites Using a Sensor Gas
07586 Bad Köstritz, Germany Calorimeter. Catalysts 2021, 11, 98.
Dieter Bathen − Chair of Thermal Process Engineering, (18) Frising, T.; Leflaive, P. Extraframework cation distributions in X
University of Duisburg-Essen, D-47057 Duisburg, Germany; and Y faujasite zeolites: A review. Microporous Mesoporous Mater.
Institute of Energy and Environmental Technology, IUTA e. 2008, 114, 27−63.
V., D-47229 Duisburg, Germany (19) Plant, D. F.; Maurin, G.; Jobic, H.; Llewellyn, P. L. Molecular
dynamics simulation of the cation motion upon adsorption of CO2 in
Complete contact information is available at: Faujasite zeolite systems. J. Phys. Chem. B 2006, 110, 14372−14378.
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Notes H.; Denayer, J. F. M.; Martens, J. A.; Maesen, T. L. M. Understanding
The authors declare no competing financial interest. the role of sodium during adsorption: a force field for alkanes in

■ ACKNOWLEDGMENTS
The authors wish to express their thanks to BASF Catalysts
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