Special Collection: 15thUkrainian-Polish Symposium

Adsorption Science & Technology

Adsorption of methanol and 0(0) 1–9
! The Author(s) 2018
water vapor on modified DOI: 10.1177/0263617417733585
journals.sagepub.com/home/adt

forms of mordenite–
clinoptilolite rock
Antonina D Kustovska
National Aviation University, Ukraine

Abstract
The influence of thermal activation, decationation, and dealumination on adsorption properties of
rock from Transcarpathian deposit (Lypcha village, Ukraine) containing mordenite and clinoptilolite
at the ratio 1:1 was studied in this research. Taking into account the need of preliminary thermal
activation of adsorbent, the research of thermal stability of zeolite component of rock was
conducted. Parameters of microporous structure of decationated and dealuminated samples
were calculated. Obtained results show that decationation of mordenite–clinoptilolite rock
leads to insignificant increase and dealumination leads to significant decrease of adsorption
capacity for water. Maximal adsorption ability for methanol is about 50% dealumination degree
of the sample.

Keywords
Natural zeolites, mordenite, clinoptilolite, chemical modification, adsorption

Submission date: 30 December 2016; Acceptance date: 29 August 2017

Introduction
Today the role of synthetic zeolites applied as adsorbents and catalytic agents can hardly be
overestimated. Natural zeolites often do not rank in technological properties below the
synthetic analogs. However, the cost of natural zeolites preparation is much lower than
the cost of production of synthetic zeolites.
Although the deposits of zeolites have the broad geography and possess its large volumes,
the scope of its application is now limited mainly with the fields of agriculture and
construction. However, researches of these materials for increasing of their scope of

Corresponding author:
Antonina D Kustovska, Institute of Ecological Safety, National Aviation University, 1 Kosmonavta Komarova Avenue, Kyiv
03058, Ukraine.
Email: akust@bigmir.net

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2 Adsorption Science & Technology 0(0)

application are permanently carried out. Due to their high cation-exchange ability natural
zeolites can be used as adsorbents in water treatment (Wang and Peng, 2010) including
drinking water (Li et al., 2011), effluents from industrial enterprises (Yousefa et al., 2011),
agricultural productions (Montegut et al., 2016; Smedt et al., 2015), and landfills (Tuncan
et al., 2003). The molecular sieve properties allow application of initial and modified forms
of natural zeolites for separation and purification of gas mixtures (Ackley et al., 2003;
Aguilar-Armenta and Romero-Perez, 2009; Cakicioglu-Ozkan and Ulku, 2003; Shafie
et al., 2012). Also the works for application of these materials in pharmacy are carried
out (Cerria et al., 2016; Gennaro et al., 2016).
Possibilities of natural zeolites application in energy recovery technologies are now
expanding (Nizamia et al., 2016). In the process of biofuels production these materials
can be used as recyclable adsorbents/catalysts for biogas upgrading (Cabrera-Codony
et al., 2017) and bioethanol absolutization (Karimi et al., 2016). As a result of
chemical and structural modification of natural raw materials, catalysts and catalyst
supports for such processes as conversion of methanol to dimethyl ether (Kustovska and
Kosenko, 2014; Royaee et al., 2008) and dimethyl ether to olefins (Nassera et al., 2016) can
be obtained. These processes allow obtaining synthetic fuels with improved ecological
characteristics.
The main reasons of narrow use of mineral raw materials are highly variable mineral
content and nonhomogeneity of phase composition of zeolite rocks. That is why most of
processes mentioned above require preliminary modification of minerals. Chemical
modification allows the regulation of phemical and phase compositions of natural
materials, and therefore, adsorption properties that determine main exploitation
characteristics of adsorbents and catalysts. Since in the deposits different zeolite structures
often crystalize jointly, research of regularities of modification of rocks containing the
mixture of zeolites, namely mordenite–clinoptilolite, is the subject of special interest. The
relevant rocks can be found in Transcarpathian deposits, which are unique in terms of
amount and quality of raw materials (Survey of natural zeolites market in the CIS, 2010).
Therefore, the aim of the work was to study the adsorption of methanol and water vapor
on modified rocks containing a genetic mixture of zeolites for the purpose of their further use
as adsorbents and catalysts for the methanol conversion toward dimethyl ether or
hydrocarbons.

Materials and methods

As the main object of research sample of zeolite rock from Transcarpathian deposit (Lypcha
village, Ukraine) containing mordenite and clinoptilolite at the ratio 1:1 with little amount of
feldspar was applied. Total content of zeolites in rock was more than 90% mass. Chemical
content of rock (mas%): SiO2—–64.95; TiO2—0.20; A12O3—12.23; Fe2O3—1.06;
FeO—0.22; MgO—1.21; CaO—3.22; Na2O—0.70; K2O—2.35; S—0.03; P2O5—0.11;
CO2—1.03; H2O—12.33.
Thermal activation of samples was conducted in the temperature of 300–1000 C during
6 h. Powder X-ray diffraction spectra were measured in an X-ray diffractometer DRON-3M
using Cu Ka radiation. The crystallinity of mordenite and clinoptilolite components of the
thermally processed rock was estimated by relative intensity of nonintersecting analytical
diffraction maxima of mordenite and clinoptilolite (d ¼ 0.453 nm and d ¼ 0.298 nm,
respectively). As a reference object a sample of the original rock was used (Figure 1).
Kustovska 3

Figure 1. X-ray diffraction pattern of the mordenite–clinoptilolite rock. M: mordenite component; C:

clinoptilolite component. Analytical diffraction maxima are marked with asterisks.

Chemical treatment of samples was carried out in aqua solutions of NH4Cl and HCl at
the ratio of liquid and solid phases 1:10. After processing, the samples were washed with
distilled water until no Cl ions were present in the filtrate (qualitative reaction to AgNO3)
and dried in air at room temperature. Decationated (hydrogen) forms were obtained by
processing of the sample with a solution of NH4Cl with further calcination in air for 2 h
at 600 C. Dealumination was conducted with HCl solution. Depth of decationation and
dealumination was regulated through the concentration of solutions and the duration of
modification. Control of modification processes was performed through chemical analysis of
the spent solutions. Degree of decationation and dealumination of zeolites were determined
as the number of cations and aluminum removed from the sample during processing, as
percentage of their content in zeolite phase of starting sample.
An adsorption study was carried out at room temperature using a laboratory setup based
on the McBain–Bakr quartz spiral balance. The sensitivity of quartz springs was about
2.5 mg/mm. The Dubinin–Radushkevich equation for volume filling of micropores was
used for a theoretical analysis of adsorption isotherms
"   #
RTlnðPs =PÞ 2
W ¼ W0 exp 
E0
4 Adsorption Science & Technology 0(0)

Figure 2. Dependence of crystallinity degree on temperature of preliminary processing for zeolites

investigated. Curve 1: clinoptilolite component of natural sample; Curve 2: mordenite component of natural
sample; Curve 3: synthetic mordenite.

where W is the volume of the pores that has been filled at P/Ps (m3/g), W0 is the total volume
of the micropore system (m3/g), E0 is the characteristic energy of adsorption (J/mol), T is the
temperature at which the isotherm has been taken (K), R is the gas constant R ¼ 8.314 (J/
(K mol)), P is the pressure (Pa), Ps is the saturation vapor pressure (Pa).

Results and discussion

Taking into account the need of preliminary thermal activation of adsorbents and catalysts,
the research of thermal stability of zeolite component of sample (Figure 2) was conducted.
With increasing calcination temperature, the crystal structure of zeolites is gradually
destroyed. Moreover, resistance to temperature for mordenite is substantially higher than
for clinoptilolite. After heat treatment at 400 C destruction of mordenite is less than 10%,
whereas clinoptilolite is destroyed for more than 50%. In 500 C more than 80% of
mordenite structure is retained, while reflexes of clinoptilolite on the diagram cannot be
found. Even during calcination at 800 C mordenite undergoes less than 50% degradation.
In the same time the higher thermal stability of natural mordenite comparing to synthetic
can be observed. It can be explained by the stabilization of the structure of the natural
mordenite with alkaline earth metal cations.
Adsorption isotherms of initial rock as well as thermally processed samples are typical for
microporous sorbents. Figure 3 shows the dependence of adsorption capacity of mordenite–
clinoptilolite rock on temperature of preliminary processing and reveals that above-
mentioned destruction of the crystal structure of zeolite components is accompanied by a
decrease in the adsorption capacity of the sample. For initial sample (T ¼ 50 C), full sorption
volumes (P/Ps ¼ 1) for water and methanol are the same, although the nature of the isotherms
is different. In the case of adsorption of water about 75% of volume accounts for micropores
(P/Ps ¼ 0.4), whereas only 60% of methanol is adsorbed in micropores and the rest accounts
Kustovska 5

Figure 3. Dependence of adsorption capacity of mordenite–clinoptilolite rock on temperature of

preliminary processing. Curve 1: for water as adsorbent at P/Ps¼1; Curve 2: for methanol as adsorbent at
P/Ps ¼ 1; Curve 3: for water as adsorbent at P/Ps ¼ 0.4; Curve 4: for methanol as adsorbent at P/Ps ¼ 0.4.

for macropores that may be explained by the inaccessibility of polycationic form of

clinoptilolite for methanol molecules. For samples heated at 500 and 600 C adsorbed
volume of water and methanol are significantly different, and at 700 C they become close
again. This is the result of sintering (seal) of the amorphous phase, created during the
destruction of clinoptilolite. After calcination at 500 and 600 C, this phase is partially
accessible for water molecules, and after heating to 700 C it is sealed so much that the
adsorption of water is minimized. According to X-ray analysis (Figure 2), heat treatment of
the sample at 700 C leads to the complete destruction of clinoptilolite, while mordenite is
destroyed for only 23%, and remains the only active sorbent component. So, the total content
of mordenite in the sample is 38%. The total volume of micropores of such sample should
theoretically be 3.0  0.3 mmol of H2O/g, which coincides with the experimentally determined
at P/Ps ¼ 0.4 adsorption magnitude 3.1 mmol of H2O/g. This shows that results are quite
correct. So, for maximum preservation of the microporous structure of such zeolite rocks
the preliminary thermal activation at temperatures above 400–450 C is undesirable.
Structural changes that take place during the process of chemical modification of natural
samples also reflect on these samples’ adsorption ability to different substances. Isotherms of
both initial and decationized samples are typical for microporous sorbents. Through the
calculation of parameters of microporous structure of decationized samples applying
equations of volume filling of micropores theory, it was demonstrated (Table 1) that
characteristic energy of water adsorption (E0) is almost constant with the increasing of
extent of decationization. It means that during zeolites transition from cation to
hydrogenous form the strength of hydrophilic adsorption centers stays constant and some
increasing of volume of micropores (W0) is caused by clearing of zeolites channels from
cations and occluded salts that takes place while decationization process.
Correspondence of adsorption capacity (for water and methanol) and degree of
decationation is provided in Figure 4. Comparison of adsorption amount of different
6 Adsorption Science & Technology 0(0)

Table 1. Adsorption of water vapor on initial and decationated forms at 25 C.

Decationation degree (%)

Parameters of microporous
structure – 45 62 78 88 93

E0 (kJ/mol) 18.3 19.2 19.2 18.5 19.2 18.5

W0 (cm3/g) 0.14 0.14 0.14 0.14 0.15 0.16

Figure 4. Dependence of adsorption capacity of mordenite–clinoptilolite rock on decationation degree.

Curve 1: for water as adsorbent at P/Ps ¼ 1; Curve 2: for methanol as adsorbent at P/Ps ¼ 1; Curve 3: for
water as adsorbent at P/Ps ¼ 0.4; Curve 4: for methanol as adsorbent at P/Ps ¼ 0.4.

adsorbates with decationated samples has shown that almost full replacement of cations
leads to relatively low increasing of sorption capacity for water, whereas methanol
adsorption significantly increases and becomes similar to water adsorption. Along with
this, the most significant changes of adsorption capacity take place after removal of
nearly half of exchange cations from sample. It may be related to the fact that the size of
entries to intracrystalline cavities of zeolites in initial sample doesn’t limit water adsorption,
so the influence of deactivation is low. Adsorption of bigger molecules of CH3OH in initial
sample is complicated, but even 45% decationation ensures its free diffusion. Thus, in order
to increase the efficiency of methanol adsorption it is necessary to conduct decationization of
rocks at a minimum of 45%.
Adsorption curves of water and methanol vapors depending on the degree of sample’s
dealumination are presented in Figure 5. With the extent of dealumination the form of
isotherms is gradually changing. While the increasing of dealumination depth, adsorption
amount of water is decreasing in case of low values of P/Ps, and increasing in case of high
values of this ratio. It demonstrates the change in the character of porosity—microporous
structure of clinoptilolite breaks and wide-pore amorphous phase appears. It should be
Kustovska 7

Figure 5. Dependence of adsorption capacity of mordenite–clinoptilolite rock on dealumination degree.

Curve 1: for water as adsorbent at P/Ps ¼ 1; Curve 2: for methanol as adsorbent at P/Ps ¼ 1; Curve 3: for
water as adsorbent at P/Ps ¼ 0.4; Curve 4: for methanol as adsorbent at P/Ps ¼ 0.4.

noted that acid modification affects on changes of adsorption capacity of water and
methanol samples not equally. At almost the same total amount of adsorbed water and
methanol (P/Ps ¼ 1) micropore capacity for various adsorbates is significantly different.
With increasing of dealumination activity degree, adsorption for water vapor decreases,
whereas for methanol extremum dependence is observed. This is probably a result of
change in both pore structure and chemical nature of zeolite surface in the process of acid
treatment. Thus, adsorption of methanol occurs mainly in large channels of mordenite,
because the pores of clinoptilolite are not available for this adsorbate. Dealumination,
which is accompanied by widening of zeolite channels until their destruction, leads first to
increase of adsorption of relatively large methanol molecules (at dealumination degree up to
50%), and then to its reduce as a result of dealumination, the concentration of hydrophilic
adsorption centers is decreased and the crystalline structure is destroyed. Furthermore, in the
process of dealumination the formation of X-ray amorphous microporous phase that is able
to sorb large molecules is possible. However, the contribution of this phase in the sorption
capacity of the sample is obviously insignificant. The adsorption capacity of micropores by
water at dealumination monotonically decreases as small water molecules do not experience
steric constraints upon adsorption on initial form, whereas during removing of aluminum
from framework, concentration of active adsorption centers is reduced. It leads to reduction
of micropores capacity of this adsorbate.
Theoretical analysis of isotherms of water adsorption shows (Table 2) that dealumination
leads to decreasing of W0 that comes with decreasing of E0. It is caused by decreasing of
concentration of cation and proton hydrophilic centers while removal of cations and
alumina, and, therefore, the decreasing of adsorption amount of polar water molecules. It
also can be explained due to the fact that there is the most efficient dealumination degree of
the sample (from 20 to 50%), when maximal adsorption ability for methanol can be noted
8 Adsorption Science & Technology 0(0)

Table 2. Adsorption of water vapor on initial and dealuminated forms at 25 C.

Dealumination degree (%)

Parameters of microporous
structure – 8 17 49 69 74

E0 (kJ/mol) 18.1 17.0 17.0 13.0 11.7 9.6

W0 (cm3/g) 0.141 0.145 0.140 0.140 0.129 0.123

(Figure 5). For effective methanol adsorption dealumination should not be less than 20%,
for the adsorption of water dealumination is not required.

Conclusions
Obtained results show that decationation of mordenite–clinoptilolite rock leads to
insignificant increase and dealumination leads to significant decrease of adsorption
capacity for water. Therefore, for preparation of adsorbents for dehydration of gases and
organic liquids on the basis of zeolite-containing rocks, it is possible to carry out only
fractionation and washing of raw materials. It will lead to significant cheapening of
process. In case of adsorption of larger molecules, like methanol, widening of zeolite
channels is necessary. It can be achieved through acid treatment, which is necessary for
preparation of catalysts or catalyst carriers for methanol conversion processes.

Acknowledgment
First presented at the 15th Ukrainian–Polish Symposium on Theoretical and Experimental Studies of
Interfacial Phenomena and their Technological Applications, Lviv, Ukraine, 12–15 September 2016.

Declaration of Conflicting Interests

The author(s) declared no potential conflicts of interest with respect to the research, authorship, and/or
publication of this article.

Funding
The author(s) received no financial support for the research, authorship, and/or publication of this
article.

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