Article

pubs.acs.org/jced

Adsorption of Propylene and Propane onto Mn+X (Mn+ = Cr3+ and/or

Ni2+) Zeolites and Comparison between Binary and Ternary
Exchanges
Hanaa Merad−Dib,† Souhila Bendenia,*,† Djilali Reda Merouani,† Chahrazed Bendenia,†
Isabelle Batonneau−Gener,‡ and Amine Khelifa†
†
Laboratoire de Structure, Elaboration et Applications des Matériaux Moléculaires (S.E.A.2M.), Département de Chimie, Université
de Mostaganem, B.P. 981, R.P., Mostaganem 27000, Algeria
‡
Institut de Chimie des Milieux et Matériaux de Poitiers IC2MP − UMR 7285 CNRS-Université de Poitiers, 4 rue Michel Brunet,
86022 Poitiers, France

ABSTRACT: Mn+X zeolites (Mn+ = Ni2+ and/or Cr3+) were

prepared and characterized by various techniques. The adsorption
of propylene and propane onto these zeolites was investigated, and
thermodynamic properties were discussed. The objective is to
establish a comparison between the binary (introduction of Ni2+ or
Cr3+ instead of Na+) and ternary (introduction of Ni2+ and Cr3+
instead of Na+) exchanges. To our knowledge, there is no work in
this field, in spite of a growing interest in bimetallic zeolites.
Isotherms of C3H6 and C3H8 were successfully modeled using the
Toth equation. A change in KH, Henry’s law slope, confirms the
strong and weak characters of the interactions with propylene and propane, respectively. CrNi(39)X has an intermediary
behavior between Cr(39)X and Ni(40)X. It manifests specific interaction with C3H6 molecules through the deep implication of
Cr3+ cations, at low coverage. With increasing adsorbate concentration, the contribution of Ni2+ occurs.

1. INTRODUCTION thermodynamic data permits the prediction of how these gases

Various nanomaterials have been considered by the scientific
community for water treatment, encapsulation of radionuclide
elements, adsorption and/or separation of olefin/paraffin
mixtures.1−18 For the latter, faujasite zeolites are very efficient
for this purpose because it is well-established that the presence
of a great number of exchangeable cations, which balance the
negative charge of the lattice, plays a predominant role. In
previous studies, CaX and CaY zeolites were used for propane
adsorption;19 other work has used Cd-exchanged 13X for the
separation of isobutene from n-butane,20 or C3H6 from C3H8
by NaX.21 All these investigations were devoted to binary
exchange (i.e., substitution of one cation by another). To our
knowledge, no study has examined the effects of binary and
ternary (substitution of one cation by two others) exchanges
onto propylene and propane adsorption by X zeolites, in spite
of a growing interest in bimetallic zeolites.
This paper investigates the adsorption characteristics of
propylene and propane on Ni(x)-, Cr(x)-, and CrNi(x)-
exchanged X zeolites; x being percentage of ion-exchange. The
experimental isotherms were compared with those of Toth.
The parameters of the current model were examined, and the
interaction nature was discussed via thermodynamic data, such
as isosteric heat and differential entropy. A comparison between
the binary and ternary exchanges was also reported. The
adsorption of pure olefin and paraffin represents a preliminary
and essential stage because the assessment of equilibrium and
behave in any given multicomponent system. Prior to
adsorption, the samples were characterized by XRD, DTA/
TG, SEM, and nitrogen adsorption at 77 K.
The choice of the zeolite can be explained as follows:
synthetic faujasites such as X zeolites have good selectivity and
cation exchange capacity, due to an open framework and
negative charge. Furthermore, the low Si/Al ratio leads to
numerous exchangeable cations, located in various sites easily
accessible22 to propylene and propane. The insertion of Ni2+
and/or Cr3+ into NaX results in attractive adsorptive and/or
catalytic features. For example, the output of fuel and lubricants
was achieved by oligomerization of olefins in zeolites modified
by nickel and chromium.23,24 On the other hand, Cr3+ and/or
Ni2+ would interact differently with propene and propane,
namely, a π-complexation with the double bond of C3H6 and
weak van der Waals interactions with C3H8.10
2. MATERIALS AND METHODS
2.1. Materials. The NaX zeolite (Si/Al = 1.21, with unit cell
formula Na87(AlO2)87 (SiO2)105 nH2O) was purchased from
CECA company. Ion-exchange was performed at ambient
temperature, for 24 h, by stirring 2 g of NaX in 100 mL of an
Received: May 24, 2016
Accepted: August 24, 2016
Published: August 31, 2016

© 2016 American Chemical Society 3510 DOI: 10.1021/acs.jced.6b00420

J. Chem. Eng. Data 2016, 61, 3510−3518