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Journal of Colloid and Interface Science 281 (2005) 6879

www.elsevier.com/locate/jcis

The concept of capacity in zeolite ion-exchange systems


Vassilis J. Inglezakis
National Technical University of Athens, School of Chemical Engineering, General Chemistry Lab.,
Heroon Polytechniou 9 Str., Zografou, 157 73 Athens, Greece
Received 10 June 2004; accepted 10 August 2004
Available online 5 October 2004

Abstract
In the present paper a study is conducted in order to distinguish the several types of capacity used in the literature on zeolite ion-exchange
systems, to verify the use of each capacity type, and to analyze the several experimental methods used for capacity determination. Although
the study is focused on zeolite clinoptilolite as a characteristic paradigm, its theoretical approaches and experimental findings and methods
could also apply to other zeolites.
2004 Elsevier Inc. All rights reserved.

Keywords: Zeolites; Capacity; Ion exchange; Clinoptilolite

1. Introduction changers such as zeolites are studied. These phenomena and


differences in experimental procedures, as well as differ-
Zeolites are widely used in ion-exchange applications, ences in terms used to define a measured quantity, are a
where they exchange cations from their structure with dis- major cause for poor comparability of ion-exchange data ob-
solved ones. Ion exchange is one of the methods used for the tained by different authors for a given system.
removal of several toxic substances, including heavy metals, More specifically, considerable confusion can arise from
from industrial and municipal wastewater [1,2]. Clinoptilo- the fact that in the field of zeolite science various concepts
lite is one of the zeolite species and is found in abundance of zeolite capacity are encountered and various kinds of ca-
in many deposits around the world. It belongs to the heulan- pacities, measured by different experimental methods, are
dite group, with a three-dimensional framework of silicon used. Ion-exchange capacity is often determined simply by
and aluminum tetrahedra, having the typical chemical for- equilibrating batchwise a sample of an ion exchanger with a
mula Na6 [(Al2 O3 )(SiO2 )30 ]24H2O [3]. The most important solution of an ion and calculating the capacity from the up-
property of zeolites is the ion-exchange capacity expressing take value thus obtained. As will be analyzed, this is by no
the ability of the material to take up cations. means an appropriate method to determine the capacity: it
Proper experimentation and unified terminology are im- only gives the amount of the specific ions taken up by a unit
portant tasks in any field of science. To obtain reliable and amount of the ion exchanger in the specific conditions used
comparable results requires careful consideration of many in the experiment.
experimental factors. For example, as will be discussed On the other hand, it is well known that capacity is needed
later, ion-exchange experiments performed using fixed-bed in several determinations, such as the normalization of equi-
columns may result in erroneous results, since columns may librium isotherms and the application of kinetic models in
suffer from flow nonidealities. Many other interfering phe- order to determine ion-exchange diffusion coefficients. The
nomena may be present, especially when inorganic ion ex- differences in the exchange isotherms derived by different
researchers for the same ion-exchange systems are mainly
* Fax: +30-2107723285. due to the assumption of different cation-exchange capaci-
E-mail address: v_inglezakis@yahoo.com. ties for the zeolitic material [4,5].
0021-9797/$ see front matter 2004 Elsevier Inc. All rights reserved.
doi:10.1016/j.jcis.2004.08.082
V.J. Inglezakis / Journal of Colloid and Interface Science 281 (2005) 6879 69

The aim of the present study is to review the already electric field [1]. Thus, the most important property of the
known theoretical considerations and experimental methods solid phase is its active charge, which is straightforwardly
for the subject of capacity, to clarify the meaning and the use related to its ion-exchange capacity.
of zeolite capacity, and to propose a unified capacity termi- In the definition of theoretical capacity the term iono-
nology. genic groups is included. Ionogenic groups can be defined
easily in the case of resins. Resins are typical gels. Their
framework, the so-called matrix, consists of an irregular,
2. Ion exchange and capacity macromolecular, three-dimensional network of hydrocar-
bon chains. The matrix carries ionic groups such as SO 3,
2.1. Capacity definitions COO , and PO2 3 . These radicals are fixed in the frame-
work and are the ionogenic groups of the resins. However,
IUPAC recommendations on ion-exchange nomenclature these ionogenic groups are not always ionized. For example,
define the following capacity types [6,7]: a typical weak acid group is the fixed radical COO . This
is a fixed ionogenic group ionized only at high pH. At low
Theoretical (specific) capacity is the number of iono- pH, the fixed radical is combined with H+ , forming undisso-
genic groups per specified amount of ion exchanger. ciated COOH, and thus no longer acts as a fixed charge [1].
This type of capacity is a constant used for character- In other words, it is inactive in respect to ion exchange. This
izing ion exchangers. For the same capacity type, Helf- is why Helfferich states that only when they are ionized
ferich used the term capacity (maximum capacity, ion- do the ionogenic groups act as fixed charges which must be
exchange capacity) [1]. balanced by counter ions [1]. For that reason, Helfferich
Helfferich used the term apparent capacity (effective introduced the term available capacity in order to cover
capacity) [1]. According to Helfferichs definition, ap- the part of the theoretical capacity which is actually avail-
parent capacity is the number of exchangeable counter able. Strong-acid and strong-base groups are, by definition,
ions per specified amount of the material and depends practically completely ionized under any conditions [1]. The
on the experimental conditions. apparent capacity of resins with such groups thus is essen-
Practical (specific) capacity is the total amount of tially constant and equivalent to the theoretical capacity.
ions taken up per gram of ion exchanger under spe- In zeolites there are no separate ionogenic groups: in fact
cific conditions, which should be always given. Practical there is a lack of definite ionogenic groups [6]. In the case
capacity may be lower than the theoretical exchange ca- of zeolites, the lattice consists of SiO4 and AlO4 tetrahedra,
pacity if the experimental conditions do not allow full which have their oxygen atoms in common. Since aluminum
exchange [6]. is trivalent, the lattice caries a negative electric charge. This
Useful capacity (defined by Helfferich) [1] is the capac- charge is balanced by alkali and alkaline earth cations which
ity utilized when equilibrium is not attained. Depends do not occupy fixed positions, but are free to move in the
on experimental conditions. channels of the lattice framework; these ions act as coun-
Breakthrough capacity (IUPAC and Helfferich) is the terions and can be replaced by other cations [1]. Thus, the
capacity utilized in column operations. Depends on the negative charge of zeolites is not localized but is more or less
experimental conditions. uniformly distributed in the framework [6]. Furthermore, un-
like the charge in resins, the framework charge does not
2.2. Ion exchange depend on external conditions. In the case of zeolites the
term ionogenic groups, which are essentially fixed radi-
In order to clarify the above definitions some basic the- cals, is more conveniently replaced by the term framework
oretical concepts will be analyzed. As is well known, ion charge. In zeolites the framework charge is balanced by free
exchange is the exchange of ions between a liquid and a cations and in that case these cations are the counterions in
solid phase. The solid phase is charged and this charge is Helfferichs terminology. In the case of resins, the ionogenic
balanced by ions of the opposite charge, named counterions. groups may be partially inactive. Then counterions are those
When the ion exchanger, containing ions A, is immersed in cations that associate to the active ionogenic groups (fixed
a liquid phase, containing ions B, then a diffusion process is charges).
established where A ions diffuse out from and ions B diffuse Another difficult term is exchangeable cations or
into the solid structure. This diffusion is a result of the con- exchangeable counterions. By exchangeable, Helfferich
siderable concentration difference between the phases [1]. If meant the part of resin cations that are free to move and
the ions carried no electric charges, these concentration dif- participate in ion exchange. Essentially, these cations are the
ferences would be leveled out by diffusion. However, such counterions balancing the charge of the ionized ionogenic
a process would disturb electroneutrality since, actually, the groups (fixed ionic groups). Similarly, in zeolites, exchange-
ions are charged. Eventually, an equilibrium is established in able cations are the cations that are balancing the framework
which the tendency of the ions to level out the existing con- charge. In both cases, the part of the exchangeable cations
centration differences is balanced by the action of the solids that will eventually be exchanged is dependent on the experi-
70 V.J. Inglezakis / Journal of Colloid and Interface Science 281 (2005) 6879

mental conditions. However, in resins the active fixed charge they are not exchangeable [1,4,13,14]. Obviously, REC is
of the solid phase depends on the experimental conditions: equal to IEC in the case of pure zeolites.
in zeolites the framework charge is constant. In conclusion, IEC is a characteristic property of pure
In conclusion, it can be stated that during the diffusion zeolite species, while TEC and REC are characteristic prop-
process, the framework charge of zeolites is forming a non- erties of a zeolite sample (tuff ) with a specific purity. The
localized electric field which is influencing the exchange values of TEC and REC depend on the amount and the na-
process regardless of a complete or partial exchange of its ture of impurities.
balancing cations. However, the active charge in resins may
be different from case to case and the exchangeable cations
are at the same time equal to the ionized ionogenic groups. 3.1.2. Minerals found in zeolite ores: the case of
Although the IUPAC and Helfferich definitions may impurities
cover many ion-exchange systems (mainly resins), the spe- In this section the minerals that frequently coexist with
cific nature of natural zeolites creates a need for the intro- zeolites in ores will be analyzed. This analysis is important,
duction of new capacity type definitions. In the following because these minerals (or other impurities) could be active
paragraphs the several types of capacities will be separated (or inactive) with respect to ion exchange and thus they could
into three groups. In these groups seven types of capaci- influence the exchange capacity of the zeolite tuff.
ties will be included: ideal exchange capacity, theoretical Clinoptilolite is found along with other minerals of sil-
exchange capacity, real exchange capacity, maximum ex- icate class: feldspars, quartz and other zeolites (members
change level, operating capacity, breakthrough capacity, and of the tectosilicates subclass), clays (members of the phyl-
effective capacity. losilicates subclass), and volcanic glass [4]. From the zeolite
group clinoptilolite can be found along with heulandite and
mordenite, which are materials of high cation capacity.
3. Proposed terminology Feldspars are anhydrous aluminosilicates of potassium,
sodium, and calcium. The silicons and aluminums occupy
the centers of interlinked tetrahedra of SiO4 and AlO4 .
3.1. Ideal, theoretical, and real exchange capacity
These tetrahedra connect at each corner to other tetrahedra,
forming an intricate, three-dimensional, negatively charged
3.1.1. Definitions
framework. The potassium, sodium, and calcium sit within
In the present paper, in the IUPAC definition of theoret-
the voids in this structure. Thus, feldspars can exchange
ical exchange capacity (TEC) the term exchangeable cat-
these cations with others.
ions instead of ionogenic groups will be used. The total
Most clays are chemically and structurally analogous to
charge of these exchangeable cations is equal to the zeolite
other phyllosilicates but contain varying amounts of water
framework charge. A common method for the determina-
and allow more substitution of their cations. These cations
tion of the theoretical exchange capacity of ion exchangers
are exchangeable [15]. The most important clay minerals
(including zeolites) is chemical analysis of the material [1,
related to zeolite ores are kaolinite (Al2 Si2 O5 (OH)4 ), smec-
812].
It is well known that zeolites are rarely found in nature in tites (vermiculite and montmorillonite(Ca, Na, H)(Al,
their pure form. Considering zeolite tuffs, containing sev- Mg, Fe, Zn)2(Si, Al)4 O10 (OH)2 xH2 O)), and illite ((K, H)
eral impurities which can be active or inactive in respect Al2 (Si, Al)4 O10 (OH)2 xH2 O). It is well known that clays
to ion exchange, TEC is expressing the amount of possible exhibit high cation exchange capacities [16]. Several studies
exchangeable cations. However, in the case of pure zeo- have been published on ion exchange of Cs+ , U, NH+ 4,K ,
+

lites, TEC corresponds to the actual amount of exchangeable Na+ , Ca2+ , and Mg2+ on several clays such as montmo-
cations. In order to distinguish the case of pure zeolites TEC rillonite, vermiculite, and illite [15,17,18]. The cation-ex-
the term ideal exchange capacity (IEC) is introduced. change capacity of smectites is 80150 meq/100 g, of illites
Real exchange capacity (REC) refers to the amount of the 1040 meq/100 g, and of kaolinites 315 meq/100 g [19].
actual exchangeable cations of the zeolite, measured by ion- From the quartz group, clinoptilolite is found along with
exchange methods, and is a characteristic constant of the ion quartz and cristobalite [16]. Quartz is a neutrally charged
exchanger independent of the experimental conditions. The inert mineral. Quartz has a three-dimensional rigid frame-
total charge of the exchangeable (removable) cations is equal work but does not have the capacity for cation exchange,
to the active negative charge of the zeolite structure [8]. Es- as there are no aluminum atoms present. Aluminum is im-
sentially, REC is the upper limit of actual zeolite capacity. portant because it is replacing part of the silicon atoms in
In the case of zeolite ores (tuffs), TEC is always higher the framework of silicates (aluminosilicates) and creates a
than REC; this difference is due to the fact that some of the charge imbalance (negatively charged structure). It is char-
zeolite cations cannot be removed from the zeolite structure acteristic that sandy soils, which contain large amounts of
because of strong bonding forces within the structure of the quartz, have cation-exchange capacities lower than 23.5
material, or they are part of the material impurities and thus meq/100 g [19].
V.J. Inglezakis / Journal of Colloid and Interface Science 281 (2005) 6879 71

Finally, several inorganic compounds are present, such ion exchanger (upper limit of equilibrium loading), with a
as the calcium and magnesium carbonates calcite (Ca), specific ion under specified normality and temperature, is
dolomite (Ca, Mg), and magnesite (Mg) [2023]. more important than the other equilibrium points (see Figs. 1
and 2). In the present paper, a specific term is used for that
3.2. Maximum exchange level and operating capacity saturation equilibrium loading: this term is maximum ex-
change level. This type of capacity is equivalent in nature
In the IUPAC definition, it is not clear if the practical to the apparent capacity of resins in Helfferichs terminol-
specific capacity is the capacity utilized under equilibrium ogy.
conditions. On the other hand, available capacity in Helf- Maximum exchange level (MEL) is a characteristic prop-
ferichs terminology refers to equilibrium conditions; for erty of the specific ion-exchange system. An ion-exchange
capacity measurements under nonequilibrium conditions, system is defined here as a system consisting of a mater-
Helfferich uses the term useful capacity. ial and a liquid solution which contains the ion to be ex-
In any case, even if practical (and available) capacity is changed, under a specified temperature and normality. MEL
referring to the loading achieved under equilibrium condi- is straightforwardly related to the equilibrium behavior of
tions, it is not clear which is this equilibrium loading. For a the specific ion-exchange system and like the equilibrium
specified ion-exchange system, practical capacity could be isotherm depends only on the temperature and the normality
equal to one of several equilibrium points of its equilibrium of the solution.
curve. The point which corresponds to the saturation of the The maximum exchange level (MEL) is measured by re-
peated equilibrations or by determinations using equilibrium
data (equilibrium isotherm) and is expressed in terms of
exchangeable ions per unit mass of the exchange material
[20,24]. This type of capacity is frequently used in zeolite
science and is well defined [9,20,24].
Furthermore, MEL can be measured using column exper-
iments [1]. However, in practice, under dynamic conditions,
such as in the case of column experiments, the achieved
capacity is influenced by the operational conditions: liquid
flow rate (or contact time) and flow quality [20,25,26]. Thus
this kind of capacity is frequently found to be different in
value, with respect to MEL, and it is well known as oper-
ation capacity (OC) [1]. OC is equal to MEL in the case of
infinite contact time and ideal flow in column operation [26].
Practically, MEL is always higher than OC.
MEL and REC could be equal for ideal ion-exchange
systems, i.e., systems where complete exchange is achieved.
Fig. 1. Typical equilibrium curve. This is the case for most of the meso- and macro-porous ion-

Fig. 2. Relationship between IUPAC (and Helfferichs) definitions and the definitions introduced in the present paper.
72 V.J. Inglezakis / Journal of Colloid and Interface Science 281 (2005) 6879

exchange materials such as resins. For example, in Lewatit


resin (a sulfonated polystyrene resin), the saturation capac-
ity (MEL according to our terminology) for Ni2+ , Cu2+ , and
Mn2+ is essentially the same in a wide range of solution nor-
mality (0.011 eq/L) [27]. This is why the authors state that
exchanger saturation capacity is a parameter usually con-
sidered as a characteristic constant and independent from
the involved cations [27].
However, generally, MEL is only a fraction of REC and
this is the case of partial exchange. Partial exchange in zeo-
lites is mainly a result of the ion-sieving phenomenon in the
microporous structure and thus the nature (shape, size, and
charge) of the incoming cation is critical [1]. Also, this dif-
ference in capacity is due to the fact that some of the zeolite
cations cannot be removed easily or even at all under the spe- Fig. 3. Typical kinetic curve.
cific experimental conditions, because of low mobility and
strong bonding forces within the structure of the material [1,
13,14]. Thus, MEL also depends on the characteristics of the librium loading which is in turn a point on the equilibrium
outgoing (zeolite) cations. This is why, frequently, the zeo- curve. Thus, several kinetic experiments eventually result
lites are pretreated and converted to the so-called homoionic in a corresponding number of equilibrium points. All equi-
forms, mainly in Na-form: for example, it is well known that librium and nonequilibrium loadings, except the saturation
Na+ ions are the weakest bound ions in clinoptilolite and equilibrium point, can be grouped under the term effective
thus they are most easily exchanged with cations from solu- capacity. In Figs. 1 and 3 the several experimental points
tions [2830]. Finally, temperature is a critical factor, as it are presented.
influences the equilibrium and kinetics of the ion-exchange Effective capacity (EC) can be defined as the amount of
system [1]. For example, in clinoptilolite systems the level the cations of the zeolite contained in a specific amount of
of exchange of zeolite Ca2+ ions by 1 M Cs+ and Na+ so- the material, which are exchangeable under specific exper-
lutions was found to be 59% and 57% at 5 C and 91% and imental conditions. In the present paper this term is used
100% at 90 C, respectively [31]. In those cases, MEL is in- only for batch-type effective capacity, as the breakthrough
creased, but in every case, REC is active and independent of capacity covers the case of column-type effective capacity.
the conditions. EC could be equal to MEL if an infinite contact time and
ratio of solution volume to solid mass is used.
3.3. Effective and breakthrough capacity Concluding, effective (EC) and breakthrough capacities
(BC) depend not only on the specific ion-exchange system
According to Helfferichs and IUPAC definitions, break- but also on the experimental conditions used for its determi-
through capacity is the loading of the ion-exchange mater- nation.
ial in a column (fixed bed) when the incoming ion is first Experimental conditions are the liquid-volume-to-solid-
detected in the effluent or when the concentration in the ef- mass ratio, agitation rate, and contact time for batch systems
fluent reaches some arbitrarily defined value [1,6]. Since the and the volumetric flow rate and breakpoint concentration
level at which the ion is first detected in the effluent mainly for column systems (temperature and normality of the solu-
depends on the sensitivity of the analytical method used to tion are characteristic properties included in the term ion-
measure the breakthrough, this part of the breakthrough ca- exchange system).
pacity definition is rather diffuse. Instead, the use of a spe- In Fig. 2 the relationship between Helfferichs (and the
cific concentration in the effluent for the determination of IUPAC) definitions and the definitions introduced in the
that capacity is more clear. This kind of capacity completely present paper is diagrammatically presented.
depends on the arbitrary selection of breakpoint concentra- Finally, from the analysis it is clear that TEC  REC 
tion: in practical use of ion exchangers it is appropriate to MEL  OC  EC, BC.
use certain breakthrough levels such as 110% [6].
As pointed out previously, the term maximum exchange
level is introduced for the upper limit (saturation) equilib- 4. Experimental methods for capacity measurements
rium loading. The other equilibrium loadings (included in
the term practical specific capacity), as well as the use- 4.1. Theoretical exchange capacity
ful capacity (nonequilibrium loading), can be grouped in one
term expressing the available capacity under specified exper- In the case of a zeolite tuff, TEC is determined after
imental conditions. Typically, a kinetic experiment results in chemical analysis of the material. The exchangeable cations
several loadings for several time intervals and a final equi- of zeolites are Mg, Ca, K, and Na. Thus TEC is the total sum
V.J. Inglezakis / Journal of Colloid and Interface Science 281 (2005) 6879 73

Table 1 solution of the same cation until no further uptake from


Ideal exchange capacity of some natural zeolites: data calculated using the zeolite is observed [20]. Exchange temperature is kept con-
unit cell formula stant during the batch reaction time. A repeated equilibration
Zeolite Cation exchange capacity procedure, using several concentrations or renewals of satu-
(meq/g) ration solutions, is used for several forms of clinoptilolites,
Chabazite 3.84 zeolites and other tuffs, active carbon, bones, and ceramics
Clinoptilolite 2.16 in order to evaluate the maximum exchange level (also called
specific-cation exchange capacity) of NH+
Erionite 3.12 2+ 2+
Ferrierite 2.33 4 , Cu , Zn ,
2+ + + 2+
Cd , Li , Cs , and Pb [5,24,3436]. A similar proce-
Heulandite 2.91
Laumontite 4.25 dure, referred to as exhaustive equilibration, was applied
Mordenite 2.29 in Y zeolites, clinoptilolite, ferrierite, and mordenite for the
Phillipsite 3.31
determination of maximum exchange levels of Cu2+ , NH+ 4,
Faujasite 3.39
and Pb2+ [9,22,37].
An alternative to the repeated equilibration method is the
of the zeolite (free) cations [3,32]: estimation of maximum exchange levels using the equilib-
 rium isotherms [10,3840], a method which is, however,
TEC = (Na, K, Mg, Ca). (1)
time-consuming, since it needs the experimental points from
In the case of a pure zeolite, its chemical formula can be the whole range of the equilibrium curve and is suspect
used for the determination of IEC. Then the amount in equiv- of errors resulting from the fit of the equilibrium equation
alents of the exchangeable cations for each formula unit can to experimental data [38]. The Langmuir isotherm is fre-
easily be calculated. The weight of a formula unit is cal- quently used for ion exchange on clinoptilolite, e.g., for ion
culated by adding up the atomic weights of the constituent exchange of NH+ 2+ 2+
4 , Cd , Pb , and other cations [26,41
atoms and finally the capacity is expressed as meq/g. 44].
In Table 1 the IEC for several zeolites is presented, based The Langmuir equation in its linear form is used to cor-
on the chemical formula of pure species [33]. relate the equilibrium data,
Ideal exchange capacity, estimated for 100% clinoptilo- qmax bC C 1 1
lite-rich rocks (20 samples) from chemical formulae, is re- q= = C+ , (2)
1 + bC q qmax bqmax
ported to be 2.32 0.12 [5].
where q is particle-phase equilibrium concentration in mg/g,
4.2. Effective capacity C is liquid equilibrium concentration in mg/L, qmax is ulti-
mate capacity of the material in mg/g, equivalent to MEL in
Effective capacity (EC) of the samples can be measured our terminology, and b is the Langmuir equilibrium constant
under several arbitrarily chosen conditions: thus there are (L/mg). Then the slope and the intercept of the line are used
no specific experimental conditions for this measurement. for the determination of the isotherm constants.
EC depends on the experimentalist to choose the appropriate
conditions in order to have representative results. Effective 4.4. Real exchange capacity
capacity can be measured easily in batch systems and for a
4.4.1. XRD method
specific ion-exchange system it depends on the solid-mass-
In the case of a zeolite tuff of known composition, REC
to-liquid-volume ratio, agitation rate, and contact time. The
can be calculated using the following equation
solution-volume-to-exchanger-mass ratio used in effective 
capacity measurements has certain practical limits. When REC = Pi IECi , (3)
usual laboratory equipment is used, this ratio cannot be very i
low or high in order to have enough solution or exchanger where Pi is the fraction of each mineral (zeolite or impu-
available for analysis. Ratios between 10 and 100 ml/g are rity) i in the zeolite tuff having an ideal exchange capacity
commonly used, 1000 ml/g often being a practical upper of IECi . The limitation of this equation is that the process to
limit [6]. identify and quantify the minerals that are part of a zeolite
tuff is difficult and time-consuming and even in that case the
4.3. Maximum exchange level IEC of each mineral should be known.
It has been suggested that there should be a linear corre-
Maximum exchange level of ion-exchange materials
lation between zeolite content and real exchange capacity
is commonly measured using the repeated equilibrations
of the bulk sample for ideal cases [45,46]. The basic as-
method [1]. MEL studies are conducted as follows: A mea-
sumption is that several minerals or impurities, contained in
sured quantity of zeolite is added to a vessel containing a
the zeolite tuff, are inactive regarding ion exchange (such as
measured volume of a cation solution of known initial con-
quartz, for example). Thus, Eq. (3) is simplified to
centration. The solution is analyzed periodically with time
for cation concentrations and then it is replaced with a fresh REC = pIEC, (4)
74 V.J. Inglezakis / Journal of Colloid and Interface Science 281 (2005) 6879

where p is the fraction of the zeolite in the tuff (purity), pacity determinations [21,44,51,5659]. According to Sirke-
having an ideal exchange capacity of IEC. This equation is cioglu and Erdem-Senatalar, zeolites should be converted to
linear and the results can be easily presented graphically. near-homoionic form in order to eliminate as much as pos-
While IEC are readily available in the related literature sible the well-known effects of the variation of the cationic
(Table 1), the mineral content of a tuff should be experimen- composition with location on capacity [51]. During the ho-
tally evaluated. Among the traditional methods for quanti- moionic form preparation there are two different ways to
tative phase analysis of natural mineral samples, X-ray dif- determine the REC: by chemical analysis of the solid or liq-
fraction techniques (XRD) are widely used [47,48]. They are uid phase.
based on the fact that the intensities of specific diffraction Obviously, great care should be taken to ensure the attain-
peaks from a given phase are related to the phase abundance ment of full conversion to the desired homoionic form. In
in a mixture. These methods use integrated intensities of se- both cases, whether done in columns or batchwise, the max-
lected reflections and need calibration curves using internal imum uptake may not represent the real exchange capacity
or external standards. Several XRD-based methods are avail- of the material. This is the case, for example, when various
able for quantitative analysis of minerals. The most effective ions have different accessibilities to the exchange sites [6].
is the Rietveld method, which requires a structural model for The most favorable conditions for successful cation loading
each major mineral present in the mixture and is therefore of ion-exchange materials should be the use of cations of
limited to minerals having well-defined structures [49,50]. low valence and large ionic radius (small hydrated radius)
Another method is to use pure mineral species as intensity using increased temperature and rather high pH [60]. By
references [49,51]. increasing the temperature at which exchange is performed
Several limitations of XRD methods exist, as discussed the attainment of full exchange of the zeolite cations is en-
in the related literature [48]. Many crystalline substances abled. For example, it is well known that overall exchange
are strong diffractors of X-rays and can be detected when of cations out of the clinoptilolite is favored at higher tem-
present in concentrations as small as 12%. Other materials peratures [23,31]. However, this is not always the case, as
diffract X-rays less efficiently and yield diffraction patterns for example in Na-homoionic synthetic Y zeolites, since it
of measurable intensity only when they constitute a major is found that the maximum exchange levels of Cu2+ are not
portion of the sample. As a result, certain minor constituents significantly influenced by temperature in the range of 25
cannot be identified by XRD alone. Furthermore, it is known 100 C (differences lower than 8%) [37]. The restriction of
that X-ray line intensities may not always be proportional to neutral pH is a result of the fact that at a high concentration
the zeolite contents [51]. For these reasons, XRD methods of H+ cations (low pH), H+ will be competitive against the
should be used along with other methods for the determina- incoming cation and thus the exchange of the latter will be
tion of zeolite capacity. hindered.
Other factors that should be taken into account are the
4.4.2. Ion-exchange methods solid/liquid ratio, which should be low, and the treatment
Real exchange capacity is representing the (negative) time, which must be long and combined with renewals of
framework charge of the zeolite structure; thus, the goal of the solutions (step-by-step ion exchange). In fact, the above
a REC determination method is to estimate all the cations statements are strictly true mostly for the alkali and alka-
of the zeolite that could be exchanged from the solid phase. line earth element cations, which are practically stable in
This means that the zeolite cations should be exhaustively aqueous solutions with respect with further hydrolysis re-
(totally, fully) exchanged: in other words, the zeolite nega- actions [60]. Na+ is preferred against the other alkali and
tive charge should be balanced by an equivalent amount of alkaline earth cations, as its homoionic forms are produced
incoming cations. This total (exhaustive) exchange could be much more easily. Also, Na+ is the most weakly bound ion
achieved by in clinoptilolite and thus it is most easily exchanged with
cations from the solution [2830].
(a) repeated equilibrations in batch systems with periodical Consequently, Na forms of clinoptilolite are expected to
renewal of the solution phase [5,5154]; remove other cations easily in ion-exchange applications.
(b) one simple equilibration in a batch system using a high For that reason, Na-homoionic forms are the forms most fre-
solution-volume/zeolite-mass ratio [32,55]; quently prepared for research in clinoptilolite literature [23,
(c) under dynamic conditions (in columns): the term cross- 31]. Na-homoionic forms are also used for other zeolites,
exchange method is used in order to present this proce- such as, for example, synthetic Y and A-type zeolites, as
dure [5]. well as for other materials such as bentonite [37,58,61].
It should be noted that in the related literature, exper-
These exchanges are essentially a procedure of satura- iments are performed in order to study the ion-exchange
tion of the zeolite with an incoming cation from a solu- behavior of the system and they are not ad hoc studies for
tion and the result is to convert the zeolite to its homoionic the determination of REC. The latter is measured mainly in
form. Conversion of all exchangeable ions to one species order to analyze the ion-exchange equilibrium results: REC
(homoionic form) is a common step for cation-exchange ca- is compared with MEL to find out if the exchange is par-
V.J. Inglezakis / Journal of Colloid and Interface Science 281 (2005) 6879 75

tial (REC > MEL) or complete (REC = MEL). It is clear pacity measurements for natural clinoptilolite using NH+ 4
that if the aim is to study methods for REC measurement, ions and repeated equilibrations, in the normality region of
other cations, such as Cs+ and NH+ 4 , can also be used, since 0.53 eq/L small differences (<9%) were found without
clinoptilolite exhibits higher selectivity for these cations a specific trend [5]. These results can be explained by as-
than alkali and alkaline earth cations [5]. However, these suming that higher concentrations of the replacement cation
cations are not found always to result in higher capacity val- result in depressing its activity coefficient and in increasing
ues with respect to methods using Na+ solutions [5,62]. the difficulty of exchange due to the ionic drift [5].
The Na-homoionic form of clinoptilolite can be prepared NH+ 2+
4 can be used instead of Pb , as it has been observed
in batch reactors using concentrated sodium chloride so- that in some clinoptilolite samples its uptake is higher than
lution (0.52 M), low solid-to-liquid ratio (0.0250.1 g of that of Pb2+ [24,39]. An example of NH+ 4 use is the work of
clinoptilolite per ml of solution), under high temperature Barrer et al. for clinoptilolite, where the Na+ content of the
(6090 C) for a long time period (710 days) and with Na-homoionic clinoptilolite, measured by chemical analy-
periodic (24 h) renewal of the solution. Several batch and sis of the material, is considered to be equal to the capacity
column methods using Na+ treatment for the preparation of of the material since it was found, using ion-exchange tech-
homoionic forms are presented in the literature [8,12,21,29, niques with NH+ +
4 ions, that all the Na ions (98%) were
38,51,5456,58,59,6366]. Finally, for capacity measure- exchangeable [21]. However, for Na-rich clinoptilolite it is
ments, the NH+ 4 -form of clinoptilolite has been also used
found that the maximum exchange levels for NH+ 4 and Pb
2+

[52,57,67]. are practically equal (differences of 49%) [35,39]. In an-


In the case of Na-homoionic clinoptilolite, REC is con- other study for Na-rich clinoptilolite, the cation-exchange
sidered to be equal to the Na+ content of the material capacity measured with NH+ 4 was lower than about 30%
[8,21,59]. However, the main assumption is that all Na+ is of the maximum exchange level of Pb2+ in the same sam-
exchangeable, or in other words, it is not part of zeolite im- ples [10]. It is characteristic that the exchange of Pb2+ with
purities [8]. Also, chemical analysis cannot distinguish the NH+ 4 initially present in clinoptilolite is irreversible and the
ingoing Na+ amount and the Na+ initially present in the ze- latter is fully replaced by Pb2+ [22]. Concluding, at least
olite which could be non-exchangeable. Despite the fact that in the case of clinoptilolite, the preference of Pb2+ against
extensive washings with water can remove the soluble salts, NH+ 4 is well established [4,29,39,59,63,69,71,72].
it is possible that some of these are related to insoluble im- The basic assumption for REC measurement following
purities. the double-exchange method is that cations other than Na+ ,
For that reasons the following procedure is proposed: af- which are present in the homoionic form of the zeolite, are in
ter the preparation of homoionic forms (referred to from now inaccessible exchange sites (or related to impurities) and do
on as single exchange), the method could be followed us- not participate in the ion-exchange process [8,54]. This as-
ing a second cation (from now on this two-step exchange sumption seems reasonable considering that the homoionic
will be referred to as double exchange). Considering batch forms of zeolites are prepared using concentrated solution
methods, which are most frequently used, the above steps under high temperatures and for long periods of time. Gen-
are performed using repeated equilibrations. The goal of this erally, it is expected that at high temperatures (in the range
procedure is to re-exchange the cations of the homoionic of 6090 C) cations located in sites that are difficult to
zeolite and determine the amount of these cations that is ac- be accessible at low temperatures can be fully displaced in
tually exchangeable. equilibrium (capacity) measurements [11,29,57,73]. As de-
For the second exchange step, Pb2+ is proposed due scribed earlier, some of the Na+ in the raw material are
to its superior selectivity, in clinoptilolite, against ions possibly related to inactive impurities and thus the REC de-
such as copper, iron, cadmium, chromium, cobalt, nickel, termination by repeated equilibrations could be lower than
ammonium, sodium [4,20,6870], barium, strontium, and the one derived from chemical analysis. Thus, the REC value
cesium [10]. Due to the high selectivity of clinoptilolite for determined by chemical analysis can be considered as an
Pb+ it is found that all the exchangeable cations (96100%) upper limit of the real capacity of the material, under the
are exchanged from Na-homoionic clinoptilolites at low assumption that the exchangeable cations are fully displaced
temperatures and low solution concentrations (25 C and by Na+ during pretreatment.
0.010.1 eq/L, respectively) [10,32,59]. Also, Pb2+ was
used for the determination of cation-exchange capacity of 4.4.3. Analysis of REC determination methods
NH+ 4 -clinoptilolite [69]. Despite the fact that high Pb
2+
Experimental studies found that clinoptilolite content
concentrations could be used to force the system to com- (% purity of raw zeolite) and exchange capacity exhibit only
plete exchange of Na+ , it has been observed that the maxi- a weak linear relationship (R 2 = 0.62) [51]. In Fig. 4
mum exchange level is not a function of solution concen- capacity values derived from the related literature are pre-
tration in Pb+ Naclinoptilolite systems in the range of sented.
0.10.5 eq/L [22]. The same was observed in clinoptilo-
lite cation-exchange capacity using ammonium acetate in The REC values that are above the ideal line can be
the concentration range of 12 eq/L [67]. Finally, in ca- explained in the case where the zeolite tuff contains im-
76 V.J. Inglezakis / Journal of Colloid and Interface Science 281 (2005) 6879

Fig. 4. Capacity vs purity of clinoptilolite samples (60 capacity values). For ideal line Eq. (4) is used with IEC = 2.16 meq/g (Table 1).

purities that are active. Thus the resulting REC is higher REC values that are below the ideal line are suspect of
than the one determined using Eq. (4). Furthermore, experimental errors: REC is expected to be equal (in-
when the REC is calculated only by chemical analysis active impurities) or higher (active impurities) than the
of the Na-forms, some Na that are inactive are also in- ideal line values. For example, capacities measured us-
cluded in its value. For that reason chemical analysis of ing the cross-exchange method were found to be lower
Na-homoionic forms is expected to result in higher val- than the predicted ones using the ideal line values [5].
ues of REC. The deviation in REC values for the same According to that study, the cross-exchange method
purity is the result of the different quality of the impuri- does not adequately predict the capacity of clinoptilo-
ties that coexist with the zeolite content. For example, lite, although it works well in the case of phillipsite
mordenite exhibits higher capacity than clay impuri- and chabazite tuffs. The possible reason is that under
ties. dynamic conditions the exchange is not complete [5].

Table 2
Methods used in the related literature for the determination of REC and purity of the zeolite tuff
Method Cation Double exchange Method for purity Reference
used cation determinationa
Double exchange Na+ NH+4 XRD [51]
Single exchange Na+ XRD [54]
Cross exchange Na+ , K+ XRD [5]
Single exchange Na+ , K+ , NH+
4 XRD [5]
Cross exchange Cs+ , Na+ n.m. [62]
Single exchange Na+ n.m. [8]
Cross exchange (DE)b Na+ NH+4 XRD [72]
Cross exchange Na+ , K+ XRD [24]
Double exchange NH+4 Pb , Na+
2+ n.m. [69]
Double exchange Na+ Pb2+ XRD [74]
Single exchange Na+ XRD [59]
Single exchange NH+4 n.m. [18]
Cross exchange Na+ , K+ n.m. [39]
Double exchange Na+ NH+4 n.m. [21]
Single exchange Na+ XRD [53]
Single exchange Na+ XRD [73]
Cross exchangec NH+4 n.m. [75]
Cross exchange (DE) Na+ NH+4 XRD [76]
Single exchange NH+4 XRD [52]
Double exchange Na+ H+ n.m. [56]
Double exchange Na+ NH+4 n.m. [44]
Double exchange Na+ Pb2+ n.m. [32]
a n.m.: not mentioned.
b DE refers to double exchange, a cross-exchange method followed by a second exchange step, again under dynamic conditions.
c A column method used, referred to as reflux, with saturated ammonium chloride solutions.
V.J. Inglezakis / Journal of Colloid and Interface Science 281 (2005) 6879 77

Obviously, according to Fig. 4, batch methods (single 38]. The dependence of OC on contact time has been studied
and double exchange) are giving the best results. In Ta- and modeled in the case of zinc and acid dye adsorption by
ble 2 the methods used in the related literature for the bone char and activated carbon, respectively [80]. The fol-
determination of the REC and purity of the zeolite tuff lowing equations were successfully applied,
are presented.  
OC = MEL 1 exp(tres ) , (7)
4.5. Operating and breakthrough capacities   
OC = MEL 1 exp tres
0.5
, (8)
Operating and breakthrough capacities can be determined
where t res is the contact (residence) time and is a system-
simultaneously using fixed bed reactors. Fixed bed exper-
specific constant. It is obvious that if residence time is in-
iments are conducted using vertical columns packed with
finite the operation capacity is equal to the maximum ex-
zeolite material. The feed is introduced using peristaltic
change level. These observations seem to be a result of the
pumps, at low volumetric flow rates (expressed in bed vol-
limiting (low) contact time in fixed beds and of the different
umes per hour, BV/h), in upflow mode. Low flow rates in
concentration gradients in fixed beds and batch reactors [26].
the range of 510 BV/h were found to be adequate for ion-
It must be recognized that batch reactors do not approx-
exchange applications in columns packed with zeolites [20,
imate the hydrodynamic and mass-transfer patterns of fixed
26]. Samples are withdrawn at the exit of the bed at desired
bed (column) reactors and probably a partial equilibrium
time intervals, depending on the flow rate, and analyzed for
state in fixed beds is taking place. In addition to that, in
cations. Operating and breakthrough capacities can be eval-
column methods flow may suffer from nonidealities such
uated by integration using the experimental breakthrough
curves obtained in the column studies [1,20,38,7779]. In as channeling or insufficient wetting of the material. Such
problems may reduce the process efficiency and lead to er-
Fig. 5 a typical breakthrough curve is presented.
The operating and breakthrough capacities can be evalu- roneous results in capacity determinations. For this reason
ated using the equations the column should be long enough (typically longer than 20
  Veff,T  30 cm) and operated under up-flow conditions [74,81,82].
Veff,T Veff,O X(Veff ) dVeff C0
OC = , (5)
b V0
5. Uses of the several capacity types
  Veff,B 
Veff,B Veff,O X(Veff ) dVeff C0
BC = , (6) Real exchange capacity, as defined in the present paper,
b V0 is the amount of all removable cations (counterions) and is
where V eff,O is the effluent volume until the first appearance equal (as charge) to the active negative charge of the zeolite
of the solute in the exit stream, V eff,B is the effluent volume framework [8]. Helfferich uses the total solid concentra-
until the breakpoint (breakthrough), and V eff,T is the effluent tion of counterions in the isotopic exchange kinetic models
volume until the exit solute concentration is equal to its in- in order to evaluate the solid diffusion coefficients. Total
let concentration. Breakthrough point is defined as the point solid (and liquid) concentration of counterions (in equiva-
where the exit concentration reaches an upper limit, which lents) is constant, irrespective of ionic composition, since ion
is a portion of the inlet concentration (for example 10%). exchange is a stoichiometric process [1]. Thus, since real ex-
The operating capacity is theoretically independent of change capacity is essentially equal to the concentration of
the flow rate [1]. However, operating capacity is found to counterions (exchangeable cations) of the solid phase, it is
be flow-rate-dependent and different from that measured in used in batch kinetic models for the determination of ion-
batch systems [20,25,26]. Thus this kind of capacity is es- exchange diffusion coefficients [20,21,26,55,83,84].
sentially different from and lower in value than MEL [20,26, MEL is a characteristic constant of the specified cation-
exchanger system and it is used in equilibrium studies. For
the construction of isotherms and the processing of equilib-
rium data, the dimensionless solid (Y ) and liquid (X) con-
centrations of the incoming cations are used,
q
Y= , (9)
qref

c
X= , (10)
cref
where c and q are the liquid and solid concentrations of
the incoming cation and cref and q ref are the corresponding
reference values: cref is taken equal to the initial liquid con-
Fig. 5. Breakthrough curve. centration and q ref to the capacity of the ion exchanger [77].
78 V.J. Inglezakis / Journal of Colloid and Interface Science 281 (2005) 6879

This capacity is the REC in the case of complete exchange task since several impurities are usually present in natural
of the cations initially present in the solid phase. However, zeolites and experimental errors can mask its accurate deter-
most ion-exchange processes in zeolites are characterized mination. Another problem is that in some cases metals are
by partial exchange and thus the exchange level is differ- not only exchanged but also adsorbed or precipitated onto
ent for different incoming cations and is expressed by the the solid surface. In this case the zeolite capacity is the sum
MEL. Again, REC could be used (the same reference value) of the active ion exchange and adsorption sites.
for the construction of isotherms if the aim is to compare the
selectivity of the ion exchanger for different cations. On the
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