The Effect of exchangeable cations

(Mg, Sr, Ca, Na, Cd) on the

hydrogen adsorption values in zeolite LTA

Mahmoud Rahmati
Hamid Modarress
Department of Chemical Engineering, AmirKabir University of Technology, Tehran, Iran

Abstract
The adsorption of molecular hydrogen on zeolite LTA metal-hydride storage systems have all been discussed . However, these storage
containing various exchangeable cations (Mg, Sr, Ca, Na, Cd) methods cannot match the requirement for hydrogen as a fuel in car engines or
have been simulated employing grand canonical monte carlo aircraft turbines because of the low hydrogen uptake and ungovernable
(GCMC) procedure for a temperature 77 K and a pressure hydrogen desorption rate. So the search for new hydrogen-storage methods has
become an important aspect in hydrogen energy applications. Recently,
range of 0–10 bars. Quantum effects were included in the
physisorption has attracted more attention because the adsorption is reversible
simulations through the Feynman-Hibbs effective potential.
and thus the adsorbent can be recycled . Moreover, physisorption offers the
The simulation results were compared with experimentally
possibility of high hydrogen-storage capacity and quick hydrogen desorption.
measured values at 77 K and indicated a good quantitative
As a result, many investigations have focused on encapsulating hydrogen
agreement. The results showed that hydrogen adsorption in molecules in microporous media at low temperature .
zeolites is strongly dependent upon pressure, and also on
Zeolites are a family of highly crystalline aluminosilicate materials. Abounding
cation type in the zeolite framework, and the highest storage with cage and channel structures, and having high thermal stability and large ion
capacity was obtained for CaA. -exchange capacity, they offer enormous potential for the encapsulation of
nonpolar gases. In the past decade, some zeolites and mesoporous silicate have
been investigated as sorbents for hydrogen storage. Experimental data have
shown that many parameters affect hydrogen storage in microporous materials,
including the specific surface area and pore volume, the interaction of molecular
hydrogen with the internal surfaces of the micropores, the stability of the
molecular adducts and the optimal storage temperature (At low temperature),
microporous adsorption is the dominant mechanism. The mechanism of
adsorption in zeolites is that hydrogen molecules are forced into the cavities
under pressure and low temperature. Comparing the hydrogen-storage data of
zeolites and zeolite-like materials revealed that adsorption at extremely high
pressure does not follow the same rule as at low pressure. Zeolites are of interest
values. In all calculations each LTA framework is treated as a rigid structure. Each structure was
because the diameter of the cages and the channels can be controlled by
represented by a 2 * 2 * 2 super cell with periodic boundary conditions containing 8 LTA cages ( A
exploiting their ion-exchange property to modify the valence state and the size
of the exchangeable cations. = Si192O432 and a = b = c = 2.36193 nm) .
The interactions between H2 and the zeolite framework atoms were modelled with Lennard Jones
(LJ) potentials. For the hydrogen molecule, the approximation due to Feynman-Hibbs was
employed for all the involved dispersion-type interactions in order to account for its quantum
Simulation Details nature. The complete set of parameters is given in a previous work.

Studies performed on the adsorption of H2 in other zeolite structures using

GCMC have demonstrated the usefulness and accuracy of the method. The
loading at a given fugacity and temperature was calculated by attempting, with
equal probability, to insert, delete or translate equilibration time, leading to
effectively the same results for all test cases, thus, showing that this number of

With fossil hydrocarbon resources becoming scarce, the concept of steps and the adopted equilibration time were large enough to obtain reliable

using hydrogen as a future energy vector has been under discussion for
at least the past 30 years. The use of hydrogen as a fuel in car engines or
aircraft turbines is a potential area of application owing to its notable
advantages, such as light weight, high burning heat and very low
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132  30   ij 2
U ij  4 ij [( )  ( ) 
ij 12 ij
environmental pollution. The prerequisite for its use is a device for safe
and easy handling, storage and transportation. Several methods have
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( 2 ( )  2 ( )) ] 6
been proposed for this purpose. In the past several years,high-pressure
tanks for gaseous hydrogen, cryogenic vessels for liquid hydrogen and
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Results and discussion

Conclusions
Ion exchange has been shown to have an effect
on the hydrogen adsorption values at 77 K,
however, it is not yet clear whether the observed
differences in adsorption values are due to pore
blocking by cations, or variations in the
interaction of hydrogen with different cations. As
the size of cations increases, the electrostatic field
or basicity of an ionexchanged zeolite increases
due to the electronegativity differences between
Aluminosilicate zeolites are well known for their electrostatic fields due to the electronegativity differences between Al, Si and
O and the contribution of charge-balancing cations. As the size of metal cations increases, the electrostatic field or basicity of an
ionexchanged zeolite increases due to the electronegativity differences between the cations, aluminum, silicon and oxygen. The
effect of type of cation or electrostatic field on hydrogen adsorption, so far has not been established conclusively. The adsorption
isotherms are given in the form of uptake plots, i.e., the uptake as a weight percentage is given as a function of gas pressure. The
adsorption isotherms of hydrogen molecules on model zeolites LTA containing various exchangeable cations (Mg, Sr, Ca, Na,
Cd), have been determined using GCMC simulations. The simulation results and experimental data are given in Figure 2. The
results for CaA and SrA are in reasonable agreement with experimental data 29
.Hydrogen uptake as a function of adsorption
pressure varies slightly depending on the type of cations. The normalized uptakes are shown in Figure 3 for the zeolite with
various cations. The hydrogen storage capacities obtained at 77 K and 10 bar were 2.02 and 1.42 wt.% for zeolites CaA and
MgA, respectively.

the cations, aluminum, silicon and oxygen. The

hydrogen adsorbs readily at relatively low 2.5
Na-A
2.5
Ca-A Sim.
Sr-A Sim.
pressure over zeolite A containing cations (such
Ca-A
Ca-A expt.
Mg-A
SrA expt.
2 Sr-A 2

as Mg, Sr, Ca, Na, Cd ) when the

Hydrogen Adsorption (wt.%)
Hydrogen Adsorption (wt.%)

Cd-A

electronegativity of these is low. Therefore, it is 1.5 1.5

suggested that the ideal zeolite for efficient

1

hydrogen storage, especially at low pressure, is a

1

zeolite having high electrostatic field due to ion- 0.5 0.5

exchanged cations.
0 0
0 2 4 6 8 10 12 0 2 4 6 8 10 12

Pressure (bar) Pressure (bar)