Industrial Zeolite Molecular Sieves

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OPEN ACCESS PEER-REVIEWED CHAPTER
Industrial Zeolite Molecular Sieves

Submitted: October 26th, 2015 , Reviewed: April 4th, 2016 , Published: August 24th, 2016
DOI: 10.5772/63442
W R I T T E N BY
Kristin Gleichmann, Baldur Unger and Alfons Brandt
R E G I ST E R TO D O W N LOA D F O R F R E E
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Zeolites
Useful Minerals
Zeolites
Edited by Claudia Belviso Edited by Claudia Belviso
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Abstract
Zeolite molecular sieves are used in industrial applications since more than 60 years, mainly as highly
efficient adsorbents for separation processes in gas or liquid phase. Zeolite molecular sieves may be
applied in powder form, preferably in static applications, but to a much larger extent as shaped
material in both static and dynamic (flowing media) applications. Many shaping technologies for
molecular sieves have been developed over the last decades, reflecting the different requirements for
molecular sieves in different applications. This review deals with the influence of the applied zeolite
synthesis and shaping methods for hydrophilic zeolite molecular sieves (procedures, materials,
recipes) on the potential industrial applications; thereby considering powders, binder-containing
shapes as well as binderless shapes (including compact structures such as honeycombs, multi-channel,
and foam-like structures). Due to new challenges from the market, more specialized, tailor-made
types of zeolite molecular sieves are required. Such a higher specialization can be achieved by applying
new types of zeolites or zeolite-like materials, modified synthesis and/or post synthesis treatments,
and by modified, to the needs of the application adjusted shaping processes.
Keywords
zeolite molecular sieve adsorption fixed bed compact zeolite bodies
Author Information Show +
1. Introduction
Zeolite molecular sieves are used in industrial applications since more than 60 years, mainly as highly
efficient adsorbents for separation processes in gas or liquid phase. The current market volume for
molecular sieves (especially for zeolites for adsorption applications) is 150.000–200.000 t with a sales
volume of 450–550 Mio. USD with an annual growth forecast up to 2020 of 3–5% [1–3]. Growth drivers
are environmental protection and conservation of resources (deeper processing of crude oil, using of
coal and natural gas (especially from off-shore and shale gas deposits coming [4–6]) as raw material
for petrochemical products in the so-called coal-to-liquid (CTL) or gas-to-liquid (GTL) processes) [7–
9].
Zeolite molecular sieves can be applied in powder form, preferably in static applications. During the
polyurethane production, zeolite 3A powder is mixed with the polyol component to enable exclusion
of moisture and prevent the chemical reaction of water with the isocyanate component [10]. To
support the material handling, and to avoid, for example, dust formation molecular sieve beads are
used in non-regenerative applications, too. Dry sealing plug or small dry bags filled with zeolite A (or
silica) [11, 12] to guaranty a dry transport or storage of humidity sensitive goods such as electronical
products, leather ware, or pharmaceuticals are common [11, 12]. The application of zeolite 3A in
insulating glass panes is well-known, too. By putting the adsorbent material as desiccant in the
perforated spacer between the two or three window panes moisture condensation between the panes
(fogging) is prevented [13]. Refrigerant drying [14, 15] is also a static adsorption process, where in the
coolant circuit formed, water and acidic components are removed [14, 15].
Besides the mentioned application examples, shaped zeolite molecular sieve material in flowing media
is used to a much larger extent. For instance, the purification of technical hydrogen (removal of
nitrogen and carbon monoxide) on zeolite 5A [16], the pre-purification of raw air on zeolite NaX [17]
for the cryogenic air separation or the adsorptive oxygen enrichment, for example, on zeolite type 5A
[18] or LiX [19, 20] should be mentioned in this place. Applied technologies for purification and
drying of natural gas are operating with zeolite molecular sieves [21] of zeolite 5A and/or NaX type
[22]. In petro chemistry applications especially in steam cracking plants, light hydrocarbons are
separated by low temperature rectification. To avoid ice crystal and gas hydrate formation, cracked
gases have to be dried to a residual water content <1 ppm [23]. Zeolite molecular sieves of type 3A
meet the requirements for that complex process [22]. For the sake of completeness, the principle of
the simulating moving bed (SMB) should also be mentioned. This practically continuous liquid phase
adsorption process is based on the countercurrent extraction principle [24]. The so-called Molex
process, where paraffin mixtures (zeolite molecular sieve of type 5A [25, 26]) are separated, and the
so-called Parex processes, where p-xylen is separated from C8 aromatic mixture (zeolite molecular
sieve of type KY or BaX [27]) are known SMB processes. Furthermore, the dehydration of preferably
bio-ethanol above the azeotropic point to more than 99.5% on zeolite 3A is common practice [28, 29].
Besides the mentioned examples, the use of zeolite molecular sieves in automotive applications such as
drying of brake air in rail vehicles, trucks, or busses is also a well-known application. To avoid
corrosion or freezing caused by humidity, such pneumatically working breaking systems are equipped
with zeolite 4A molecular sieve or silica gel-containing desiccant cartridges [22].
Another field for the application of zeolite molecular sieves is the utilization of the adsorption heat
during the adsorption process. Different applications such as building heating [30–32] or enhanced
household devices such as dish washers [33, 34] based on the thermo-chemical energy properties of
zeolites are introduced into the market.
The above-mentioned examples clearly demonstrate the demand for zeolite molecular sieves with
special properties depending on the different requirements in the application.
Many synthesis and shaping technologies for molecular sieves were developed over the last decades.
Within the following descriptions, the influence of the applied synthesis and shaping methods for
hydrophilic zeolite molecular sieves of zeolite A, X, and NaY on their properties, and thus, on their
potential applicability in industrial adsorption processes is discussed. The procedures, materials, and
recipes for the manufacturing of zeolite powders, binder-containing shapes as well as binderless
shapes are described. Also compact structures such as honeycombs and multi-channel tubes are
considered.
Figure 1 summarizes different manufacturing procedures and materials dealt with in this review.
Figure 1.
Overview of the manufacturing of different zeolite molecular sieves (figure compact zeolite bodies [35]).
A dv e rt i s e m e n t
2. Zeolite powder with different particle sizes

Within the manufacturing of synthetic zeolite molecular sieves, the synthesis of the related zeolite
powder is first step. There are two different principles for the synthesis of aluminum-rich zeolites in
industrial processes:
Manufacturing of highly pure crystalline zeolite powders from a synthesis gel and
Conversion of natural minerals into zeolite matter.
Usually, in the industrial production of zeolite A, X, and NaY, the sodium form is manufactured
(except the zeolite LSX synthesis [36]). Therefore, different raw materials as silicon source such as
silicic acid, colloidal silica, sodium silicate, or silica gel [37] are used. Possible alumina sources are
alumina trihydrate, sodium aluminate, activated alumina, gamma alumina. Sodium may be obtained
from sodium hydroxide which controls simultaneously the pH value [37]. A convenient way to
prepare such a reactant mixture is to pour under more or less intensive stirring an aqueous solution
containing the aluminum source and sodium hydroxide into an aqueous solution containing the silica
source. After gel formation and generating a homogeneous mixture, the mixture is heated up to
maximal 120°C at atmospheric pressure or moderate overpressure [37]. After crystallization, the
zeolite suspension is filtered at temperatures between room temperature and reaction temperature
[37], for example, in a filter press [38] or a centrifuge [39, 40] or a vacuum belt filter [40]. The zeolite
crystals are washed directly on the filter device till a pH value between 9 and 12 [37] is achieved. If
desired, the zeolite powder in its (virgin) sodium form can be ion exchanged or otherwise modified.
For example, the filter cake can be suspended in a suitable salt solution and stirred at a suitable
temperature. Alternatively, the exchange step is done in a column [41] or directly on the filter press
[42] with a suitable salt solution at a suitable temperature. After the ion-exchange procedure is
completed, the zeolite is washed as described above. Afterwards, the filter cake is dried in a direct or
indirect heated thermal treatment process, as, for example, spray drying, spin flash drying, or long
gap mill drying [40, 43]. The dried zeolite powder is processed in the following steps. The mother
liquor from the filtration step can usually (at least to a certain extent) be reused in the following
zeolite synthesis batch [37, 44].
The manufacturing of zeolites by conversion of minerals is not really a commonly used process. In
several papers which deal with the synthesis of zeolite A, X, and NaY from minerals, kaolin or
metakaolin is used as aluminum source [45–47]. A disadvantage of such procedures is the presence of
impurities in the applied minerals [45], but some advantages (simple treatment of the mother liquor
and a nearly waste-free production) support the application of that synthesis method especially in the
case of zeolite NaY [46].
The properties of zeolite molecular sieves can be influenced by the properties of the starting zeolite
powder. For instance, the hydrothermal stability or desorption characteristics of FAU vary with the
chemical composition, especially the aluminum content [48]. The particle size, particle size
distribution, and the surface characteristics of single zeolite crystals affect the adsorption properties
as well as the mechanical stability of zeolite molecular sieves. By varying the synthesis gel
composition, time, or temperature or by adding additives to the synthesis gel, the mentioned
properties of the zeolite powder can be changed [49, 50]. Depending on the intended applications, the
particle size distribution is adjusted. Besides the described classical gel synthesis [51] resulting in
particles of about 5 µm, microparticles (particle size of approx. 1 µm) and nanoparticles (particle sizes
between 50 and 100 nm) can be achieved via new synthesis routes [52].
3. Binder-containing zeolite molecular sieves

In dynamic adsorption processes, where the adsorbent has to be regenerated frequently, the fluid
dynamics (e.g., the pressure drop over the fixed bed of molecular sieves) has to be taken into account.
Therefore, the zeolite has to be applied in a suitable particle size (usually in the form of shaped
mechanically stable macroscopic particles such as beads/spheres or extrudates/cylinders).
Because pure zeolite powder does not exhibit binding properties, an appropriate binder needs to be
applied to form the above-mentioned macroscopic particles. Figure 2 shows the main principles for
the manufacturing of conventional binder-containing zeolite molecular sieves (bulk material).
The zeolite component is the main component of the pre-mixture and can be applied as dried zeolite
powder (occasionally as filtercake). Usually, the zeolite component is modified (as described above,
e.g., ion exchanged or dealuminated) prior to the shaping step. Besides the zeolite component a binder
material is put into the pre-mixture. Mineral binders such as bentonite, attapulgite, or kaolin are
common [53, 54] as well as synthetic binders such as alumina, silica [54, 55], or a mixture thereof [56].
The type of binder material to be applied depends on the shaping procedure and on the final
application of the zeolite molecular sieve. Bentonite (montmorillonite) for example is commonly used
for extrusion [57, 58], attapulgite for beading [59]. It should be noted that (natural) mineral binders
may contain impurities (e.g., catalytically active heavy metals), which could cause undesired side
reactions in the final application. If necessary, additives such as shaping aids (e.g., mineral oil, PVA,
starch derivate solutions [60]) are put into the pre-mixture to make the shaping process most
effective. Such mainly organic compounds are burnt out in subsequent thermal treatment steps. In
order to create a defined secondary pore system (see below) thermally or chemically, removable
spacers (e.g., cellulose fibers or soluble salts) are added to the pre-mixture. In most of the bulk zeolite
molecular sieves, a binder content of around 20% (anhydrous basis) is used. But also lower (down to
around 5%) and higher (above 30%) binder amounts are described [59].
Figure 2.
Scheme of the principle manufacturing procedures for binder-containing zeolite molecular sieve shapes (bulk
material).
After the (mainly dry) mixing of all aforementioned materials in the pre-mixture usually a certain
amount of water is added in order to adjust the viscosity and plasticity of the mixture for the related
shaping process that can be agglomeration granulation [59], spray granulation [61], or extrusion [62].
After the shaping process, the molecular sieve has to be dried and activated in a thermal step, for
example, in a rotary kiln [63] or belt calciner [64] to remove the water and other adsorbed
compounds. The applied temperature is often higher than required for the zeolite activation, since the
binder system needs such higher temperatures for setting. The zeolite component in zeolite NaX beads
with attapulgite as binder materials, for example, needs not more than 350–400°C for a complete
activation (residual water content <1 wt% measured by Karl-Fischer titration) [65]. But the
attapulgite binder needs approximately 500 °C for getting converted into a mechanically stable
structure [53, 59]—a temperature which can already be critical for the structural stability of the zeolite
[66, 95]. Due to the limited hydrothermal stability [67–69, 95] of hydrophilic zeolites, the activation
step has to be carried out carefully. To avoid (partial) zeolite destruction during the activation step,
the released water needs to be removed from the shape as fast as possible in order to avoid the
appearance of hydrothermal conditions. The higher the temperature and higher the moisture
concentration directly at the zeolite centers the higher the probability for (partial) zeolite destruction
[70]. By applying a controlled temperature increase, a low height of the granules bed and/or a dry
purge gas can be met these conditions. Depending on the particular conditions, a residual water
content of less than one percent can be reached. During the cooling step as well as during the storage
of the activated material, the presence of humidity or other adsorptive components should be avoided
to prevent undesired adsorption on the material. Therefore, activated zeolite molecular sieves are
usually packed in hermetically sealed packaging units, as, for example, sealed steel drums or big bags
equipped with sealed inliners.
The mentioned use of a binder system opens a large variety of zeolite molecular sieves with different
properties. Depending on the final application, the properties of the single shapes or the bulk material
have to be optimized. For instance, with regard to the particle size, two limits should be considered:
The bigger the single shape, the higher the probability for a possible limitation of the mass transfer
within the shape. That means the diffusion within the single shape might be so slow that the active
adsorptive matter is not completely used if the full adsorption/desorption cycle is very fast (e.g., in
(vacuum) pressure swing processes [71]) [72]. But the smaller the single shapes, the larger the
pressure drop over the fixed bed and the higher the risk of fluidization. Therefore, the adjustment of
the size of the shapes is a critical parameter in the design of an adsorption process. Besides the size
also other characteristics of the bulk material are to be adjusted such as mechanical properties such as
dust formation caused by attrition/abrasion between shapes or the shapes and the wall of the adsorber
vessel. Because dust may cause problems in a running adsorption process (e.g., blocking of valves), the
dust formation has to be avoided by applying an optimal type and amount of binder as well as by
generating single shapes with as smooth as possible surfaces. To receive smooth surfaces on single
shapes of bulk material, the shaping process has to be run accurately. So, for example, in the case of
extruded material an optimal plasticity of the extrusion mixture (pre-mixture), and in the case of
agglomeration granulation, a post-granulation surface polishing step may help avoid/lower
attrition/dust formation. Besides dusting, the mechanical stability (crush resistance) of the shapes has
to be considered. The higher the bulk bed in the adsorber the bigger the weight and force that affects
the lowest single shapes in the bed, which could finally result in a destruction of the shapes, and
hence, generation of fines and an increased pressure drop. The binding mechanism of activated
binder-containing zeolite molecular sieves is based on the generation of a network of binder material,
wherein the zeolite crystals are embedded. Figure 2 shows SEM pictures of the raw materials. The
zeolite crystal agglomerates (top left) and the binder (top right) form a physically strong bound
shape, which is demonstrated in Figure 2 downright. As mentioned earlier, the use of (adsorption
inert) binder material reduces the adsorption capacity zeolite molecular sieves by approximately the
percentage of binder in the shape (see Table 1).
Zeolite NaX
Binder-containing
powder zeolite NaX beads
Zeolite NaX
Binder-containing
powder zeolite NaX beads
Water adsorption capacity at 55% relative
31.5 26.5
humidity, 25°C/wt%
N2 adsorption capacity at 1000 mbar, 25°C/cc(STP)/g 10.7 8.0
CO2 adsorption capacity at 333 mbar, 25°C/cc(STP)/g 120.7 95.4
Table 1.
Adsorption capacities for zeolite NaX (pure zeolite NaX powder and binder-containing bulk material with 82.5
wt% zeolite NaX and 17.5 wt% attapulgite).
Chapter sections
Figure 3.
Hg intrusion curves of binder-containing zeolite NaX bulk material with 17.5 and 10.0 wt% of attapulgite binder.
In addition to the mechanical properties, the type and amount of binder (and the shaping process
applied) have an essential influence on the structure of the secondary pore system of the shape—the
part of the shape through which the transport of the molecules to and from the zeolites crystals within
the shape is realized [66, 73]. Said secondary (or transport) pore system strongly influences the
kinetics of the adsorbent, and hence, the adsorption process. So the zeolite NaX beads mentioned in
Table 1
show an attrition of <0.1 wt% (determined using Chemiewerk Bad Köstritz GmbH method)
but relatively tight transport pores, which can lead to a slower diffusion within the zeolite beads.
Using a lower amount of binder material, the adsorption capacity increases and the transport pores
become slightly wider; see Figure 3. A faster diffusion is possible. But using a lower amount of binder
material leads to an increased attrition value (0.2 wt%, determined using Chemiewerk Bad Köstritz
GmbH method); for some applications that might be a high risk for an operating plant.
4. Binderless zeolite molecular sieves

To avoid the above-mentioned disadvantages of binder-containing zeolite molecular sieve bulk
materials such as adsorption capacity reduction by adsorption inert binders or influence of the
secondary pore structure by the binder material, the so-called binderless zeolite molecular sieves were
developed. There are different manufacturing procedures for binderless molecular sieves described in
the open or patent literature. In most of those processes, the same shaping principles as mentioned
earlier for the manufacturing of binder-containing zeolite molecular sieve are applied. They differ in
the raw materials, respectively, the composition—especially the type and amount of the so-called
temporary binder—of the starting pre-mixture, or the conditions for the conversion of the temporary
binder into zeolite matter. Important for the generation of binderless zeolite molecular sieve is that the
temporary binder contains only those elements, which are present in the target zeolite matter; that
means in most of the cases silicon, aluminum, and sodium, for example, for binderless molecular
sieves of A, NaX, and NaY type (or mixtures thereof). Only for the preparation of binderless zeolite
LSX-type molecular sieves, potassium-containing systems are used [74].
Thus, it is possible to generate binderless zeolite shapes using temporary binder material such as
kaolin as starting material [75]. A mixture of temporary binder material such as kaolin, metakaolin or
silica, and zeolite powder or zeolite filter cake is also mentioned [76–83]. The conversion step can be a
wet chemical [75, 79] or an at least partially autogenic thermal reaction [84].
Figure 4.
Scheme of the principle manufacturing procedure of binderless zeolite molecular sieve shapes (bulk material).
Figure 4 shows the principle manufacturing procedure starting with shaping a pre-mixture using the
above-mentioned technologies agglomeration granulation, spray granulation, or extrusion. Taggart
[75] reported about shaping a mixture of kaolin and sodium hydroxide followed by drying of the
shapes. It should be considered that kaolin has good binding properties but nearly no chemical
reactivity. Due to that fact, the kaolin needs to be converted thermally (about 600 °C) into the
chemically more reactive metakaolin. Depending on the target zeolite type, a suitable reaction
solution comprising of sodium, aluminum, and/or silicon components is prepared. Usually, the shapes
are aged and further processed in that reaction solution to convert the temporary binder into the
desired zeolite matter. Finally, the shapes are washed, dried, and activated. Taggart mentioned that,
due to the limited accessibility of the interior of the shapes by the mentioned reaction solution
(blocked or too tight secondary pore system), the degree of the conversion of the temporary binder
into zeolite matter, and hence, the adsorption capacity of the resulting material is limited, and can be
enhanced if zeolite powder is used in the starting mixture. However, the mechanical stability of the
resulting shapes is lower. Therefore, Howell et al. [85] propose the utilization of pore-forming agents
(spacers), which are burned out in the following thermal treatment, thereby leaving space for the
better accessibility of the interior of the shapes. Goytisolo et al. [76], Barrer et al. [77], Nozemack et al.
[78], Brandt et al. [79], and Schumann et al. [80] described the manufacturing of binderless zeolite
molecular sieves using a mixture of metakaolin, zeolite powder of such zeolite type, in which the
metakaolin should be converted into, and additional sodium and silicon compounds such as sodium
hydroxide, silicic acid or sodium silicate as feed for the shaping process. The zeolite powder in the
mixture has obviously crystallization triggering properties and supports the generation of an open,
for the reaction solution accessible pore system. It has to be considered that metakaolin has practically
no binding properties. Thus, one has to make sure, that the process is carried out in a way, that the
shapes, which are coming out of the shaping process, are mechanically stable enough until the
conversion of the non-zeolitic compounds into zeolite matter in the reaction solution is completed.
Said conversion is the basis for the mechanical stability of binderless molecular sieve shapes (see
below). If it is possible to put all necessary compounds into the starting mixture for the shaping the
reaction solution can be water [77, 78], otherwise all missing components for the desired zeolite
formation have to be present in the reaction solution [75, 79, 80]. Another way to manufacture
binderless zeolite molecular sieves is the use of silica as synthetic temporary binder. The shapes
obtained are aged to achieve a certain water stability [81] followed by the conversion of the temporary
binder in a solution consisting of aluminum and sodium components [82, 83].
The wet chemical reaction for the conversion of the temporary binder is preferably carried out by
recirculating the reaction solution over the bulk material at suitable temperatures without moving the
single shapes in order to avoid attrition between the still relatively soft shapes.
In the course of the chemical conversion of the non-zeolitic components into zeolite matter, the
binding mechanism changes. In the case of kaolin/metakaolin-based systems, the mechanical stability
of the shapes is now based on intergrowths between zeolite crystals in the single shape (see Figure 4
bottom). Said intergrowths are formed during the conversion of the metakaolin into a polycrystalline
zeolite matter [86]. Such unusual crystallization behavior can be explained by considering the
available space for crystallization in a shape. On the outer surface of a single shape, there is enough
space for a conventional and epitaxial crystal growth (see Figure 4 down left for zeolite NaX), whereas
in the interior, the space is obviously limited in a way that typical zeolite crystals such as octahedrons
or cubes with rounded corners cannot be formed, but polycrystalline structures consisting of zeolite
in untypical shape only (see Figure 4 bottom right for zeolite NaX) [86]. After the chemical
conversion, the bulk material is separated from the mother liquor (which can reused for further
reactions) and washed until a desired pH or conductivity of the effluent is achieved. Optionally, an ion
exchange (applying a suitable ion exchange solution) can be affiliated. Finally, the material is dried
and thermally activated in a suitable device (e.g., rotary kiln or belt calciner). As the mechanical
stability of binderless molecular sieve shapes is already achieved during the temporary binder
conversion step said thermal treatment is just needed to activate the zeolite, and not anymore to set a
binder component. Thus, usually lower temperatures can be applied, which saves costs and is more
gentle to the thermally sensitive zeolite structure. Despite the different manufacturing procedures of
binder-containing and binderless zeolite bulk material, the mechanical stability of the resulting shapes
is similar. In the case products produced according to [79] and [80], a higher mechanical strength for
bigger binderless zeolite spheres in comparison with binder-containing zeolite spheres of the same
size and zeolite type is observed. Using comparable analytical methods for both kinds of zeolite bulk
material, the attrition/dust formation is also similar.
As can be shown exemplary in Table 2, the static adsorption capacity of binderless zeolite NaX bulk
material is similar to that of pure zeolite NaX powder. That indicates that the binderless zeolite bulk
material consists of nearly 100% of zeolite matter.
Zeolite NaX Binder-containing zeolite NaX Binderless zeolite NaX
powder beads beads
Water adsorption capacity at 55% relative humidity,

31.5 26.5 31.2
25°C/wt%
N2 adsorption capacity at 1000 mbar, 25°C/cc(STP)/g 10.7 8.0 10.5
CO2 adsorption capacity at 333 mbar, 25°C/cc(STP)/g 120.7 95.4 119.4
Table 2.
Adsorption capacities for zeolite NaX (pure zeolite NaX powder, binder-containing bulk material with
82.5 wt% zeolite NaX and 17.5 wt% attapulgite and binderless zeolite NaX bulk material).
A further interesting observance is, that in the above-described special manufacturing process for
binderless molecular sieves, a very open secondary pore system is generated, which allows faster
kinetics as compared to conventional binder-containing zeolite molecular sieves with the (usual)
binder content of around 20% [86], Figure 5 proves the presence of a larger amount of macro pores.
While the ratio of meso-pore to the sum of meso- and macro-pores is 30% for conventional binder-
containing zeolite molecular sieves (pre-mixture consisting only of zeolite and attapulgite) the same
ratio is only 5% for binder-less zeolite molecular sieves (produced according to [80]) [66].
Figure 5.
Hg intrusion curves of binder-containing and binderless zeolite NaY bulk material.
Due to the mentioned open secondary pore system, the above-mentioned problems concerning the
inner shape transport limitations in binder-containing shapes depending on the size are eased in the
case of binderless shapes.
It should, however, besides all obvious advantages of binderless over binder-containing molecular
sieves mentioned earlier, noted, that, at least in the case of the kaolin/metakaolin-based systems, the
structure of the binderless shapes is more rigid (less flexible) than the one of related binder-
containing shapes. This can easily be explained by the different binding mechanisms: intergrowths in
the case of the binderless structures, embedment in the case of binder-containing structures. This is a
fact which must not be underestimated and needs to be taken into consideration especially in
applications, which are connected with structural compressions/expansions (e.g., as a result of fast
heat release and/or lattice changes by adsorption/desorption).
5. Compact zeolite bodies

In order to improve the overall effectivity of a given adsorption process, the increase of the volume-
related adsorption capacity of the adsorbent used is often desirable. Said volume-related adsorption
capacity is depending on the (bulk) density of the bulk material and on the amount of adsorption
active matter within the shape (binder-containing or binderless zeolite bulk material). The bulk
density itself depends on the density of the single shape(s) and on the void space between the shapes.
It is known, that, for example, the packing density of a close-packing of spheres of equal diameter is
ca. 74%; thus, the void space is about 26%. Theoretically, an increase of the packing density (and thus,
of the bulk density) can be achieved by mixing spheres of optimal adjusted sizes, but it is certainly
very difficult and expensive to produce and arrange such bed consisting of spheres of optimal sizes,
the more, as the influence of the packing density on the pressure drop has always to be considered. An
alternative to dense packed bulk beds can be compact zeolite bodies such as multi-channel tubes or
honeycombs. By choosing appropriate geometries of such compact zeolite bodies with optimal
channel dimensions a space filling (packing density) of much more, the mentioned 74% (theoretically
up to 100% in the case of a void free compact body) is possible. In addition, such compact bodies can
be modified in many ways to meet the requirements of the related adsorption process. Thus, a gas flow
can be guided straight through the parallel arranged channels of a honeycomb-like structure, but
through alternately blocking of the channels, a compulsorily perfusion is also possible [35].
Most of the manufacturing procedures of such compact zeolite bodies described in the literature are
based on the use of (adsorption inert) binder material. As in the above-mentioned cases of binder-
containing zeolite bulk material, synthetic binder [87] and mineral binder materials [88] are applied
in the case of compact shapes as well. Consequently, the same disadvantageously impacts on the
properties of the related adsorbents need to be considered: The introduction of the mentioned binder
material causes a dilution of the adsorptive active matter and consequentially a reduction of
adsorption capacities, and the binder material could affect the desired adsorption and desorption
processes by forming a disadvantageous secondary pore system [66], an effect which at least partly
can be cured by applying thermally removable pore-forming substances [89], and the fact, that
impurities present in mineral binders may support undesired chemical side reactions.
At that point, it seems to be worth to remember, what was discussed above in this regard—to
overcome the disadvantages of binder-containing molecular sieves bulk material. The solution (at
least to a certain extent) was the application of binderless systems. And recently it could clearly be
demonstrated that the same principle concept works in the case of zeolite-containing compact bodies
as well: A high volume-related adsorption capacity can be reached [35]. The related honeycombs,
multi-channel tubes, cylinder, etc. exhibit a remarkable adjustable high space filling (up to 100%), but
at the same time a similar open secondary pore system such as mentioned earlier for binderless zeolite
bulk material [90, 35].
For both types of compact zeolite bodies (binder-containing and binderless structures), the
production process starts with mixing the ingredients zeolite powder, (temporary) binder, water and
if needed shaping aids (such as e.g., glycerol or cellulose derivates) or in case of binder-containing
compact bodies pore-forming substances if necessary (see Figure 1). Shaping technologies can be
extrusion, pressing, or molding—depending on the desired geometry of the compact zeolite body. It
should be noted that in the case of the binderless systems, the application of kaolin instead of
metakaolin as main non-zeolitic component has been shown as being advantageous. In case of the
binder-containing compact zeolite bodies, the following and final manufacturing step is the thermal
treatment for drying and activation, where the organic compounds are burned out as well as the all
water and other adsorbed compounds present in the system is removed and the binder is set. In case of
binderless compact zeolite bodies, a first thermal treatment is needed for removing the organic
shaping aids and converting kaolin into metakaolin [35, 91]. The generated metakaolin is converted
into zeolite during a following wet chemical reaction. The related reaction solution consists of all
ingredients necessary for the conversion of the metakaolin into the desired zeolite type (A, X or NaY)
similar to the manufacturing of binderless zeolite bulk material. The conversion can be followed by
further modification processes, for example, ion exchange. The completeness of the conversion of the
non-zeolitic into zeolite matter can be demonstrated, for example, by adsorption measurements (in
combination with XRD [35]). The static water adsorption capacity for zeolite 4A honeycombs in
comparison with the fully crystalline zeolite 4A powder is shown in Table 3
proving that the
honeycomb consists of nearly 100% zeolite 4A matter.
Zeolite 4A
Binderless
powder zeolite 4A honeycomb
Water adsorption capacity at 55% relative
24.8 24.7
humidity, 25°C/wt%
Table 3.
Adsorption capacities for zeolite 4A (pure zeolite 4A powder and binderless zeolite 4A honeycomb).
Just for completion it should be noted that compact zeolite-containing bodies can also be
manufactured by washcoating [92, 93], where mainly for catalytic applications, the catalytically active
zeolite component is deposited onto monolithic support structures, as, for example, ceramic (in most
cases cordierite) honeycombs by washcoating. The result is a compact body with a thin zeolite layer.
Furthermore, the crystallization of zeolite matter directly on aluminum foams is published [94]. Such
structures exhibit interesting flow characteristics, but due to the rather large void fraction and a
relatively thin zeolite layer onto the aluminum support, a low volume-related zeolite amount, and
hence, a low volume-related adsorption capacity is observed.
6. Conclusion
Zeolite molecular sieves play an important role as highly effective adsorbents in major industrial
adsorption processes. The properties of such molecular sieves can be tailored according to the
requirements of the related applications. Besides the common binder-containing molecular sieves,
binderless grades are applied. Due to the particular binding mechanism and the related special
secondary pore system, binderless molecular sieves are mainly applied where fast kinetics is required,
thus, especially in (vacuum) pressure swing adsorption processes. Furthermore, the principle concept
for the manufacturing of binderless zeolite bulk material can be applied to the manufacturing of
compact zeolite bodies, too. This opens ways for a further improvement of the related adsorption
processes.
Acknowledgments
The authors gratefully acknowledge Gundula Fischer, Hannes Richter, and Andreas Häusler from
Fraunhofer IKTS Hermsdorf, Germany for the contribution to this work.
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Industrial Zeolite Molecular Sieves

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zeolite molecular sieve adsorption fixed bed compact zeolite bodies

Author Information Show +

2. Zeolite powder with different particle sizes

Conversion of natural minerals into zeolite matter.

3. Binder-containing zeolite molecular sieves

powder zeolite NaX beads

powder zeolite NaX beads

Water adsorption capacity at 55% relative

N2 adsorption capacity at 1000 mbar, 25°C/cc(STP)/g 10.7 8.0

CO2 adsorption capacity at 333 mbar, 25°C/cc(STP)/g 120.7 95.4

4. Binderless zeolite molecular sieves

Zeolite NaX Binder-containing zeolite NaX Binderless zeolite NaX

powder beads beads

Water adsorption capacity at 55% relative humidity,

N2 adsorption capacity at 1000 mbar, 25°C/cc(STP)/g 10.7 8.0 10.5

CO2 adsorption capacity at 333 mbar, 25°C/cc(STP)/g 120.7 95.4 119.4

5. Compact zeolite bodies

powder zeolite 4A honeycomb

Water adsorption capacity at 55% relative

3. The Catalyst Group: The Industrial Adsorbents Business, 2013

10. S. Nicolas, P.-G. Schmitt, US Patent 2002 / 0 141 940, 2002

12. DIN 55417, Packhilfsmittel – Trockenmittelbeutel – Anwendung, 1997

15. T. Tsuchiya, S. Ide, T. Shibanuma, EP Patent 0 974 633, 2000

16. H. Meyer, R. Doclo, J. Seynaeve, DE Patent 2 823 211, 1979

18. K. Haruna, K. Ueda, M. Inoue, H. Someda, EP Patent 0 334 495, 1989

19. D. A. Lagree, F. W. Leavitt, US Patent 4 810 265, 1989

24. D. Broughton, C. Gerhold, US Patent 2 985 589, 1961

25. S. Sohn, S. Kulprathipanja, J. Rekoske, US Patent 6 407 305, 2002

27. T. Mori, T. Tsuchiya, Y. Noguchi, T. Yamamoto, I. Takeuchi, K. Matsumura, S. Akita, K. Sando, M.

30. W. Schulz, Wärmespeicher für die Energieeffizienz, Energiespeichersymposium, Stuttgart,

31. P. Feddeck, F. Meyer, Heizen mit Zeolith-Heizgerät. BINE-Informationsdienst,

32. T. Nonnen, S. Beckert, K. Gleichmann, A. Brandt, B. Unger, H. Kerskes, B. Mette, S. Bonk, T.

34. A. Jakway, H. Disch, W. Neumaier, EP Patent 2 617 343, 2013

36. F. Wolf, H. Fürtig, E. Lemnitz, GDR Patent 43 221, 1965

37. R. M. Milton, US Patent 2 882 244, 1953

39. J. G. Moscoso, US Patent 9 133 037, 2015

40. D. Täschner, A. Pritzl, DE Patent 10 2009 012 532, 2010

41. R. M. Milton, US Patent 2 996 358, 1961

42. R. J. Ross, J. D. Sherman, US Patent 4 666 693, 1987

47. M. L. Pavlov, O. S. Travkina, R. A. Basimova, I. N. Pavlova, B. I. Kutepov, Petroleum Chemistry,

49. V. H. Grassian, S. C. Larsen, Dekker Encyclopedia of Nanoscience and Nanotechnology. In: J. A.

52. D. R. Corbin, A. J. Sacco, S. L. Suib, Q. Zhang, US Patent 7 014 837, 2006

55. K. C. Weston, P. Purcell, US Patent 8 680 344, 2014

56. A. K. Ghosh, C. Mihut, M. Simmons, US Patent 9 180 441, 2015

57. J. G. Heinrich, C. M. Gomes, Einführung in die Technologie der Keramik – Vorlesungsmanuskript

58. W. J. Mitchell, W. F. Moore, US Patent 2 973 327, 1961

59. D. Jaussaud, K. Weston, A. Pfenninger, B. Kleeb, US Patent 6 743 745, 2004

61. Y. Chang, S. N. Waughn, P. R. Stafford, E. Nebesh, B. Slawski, WO Patent 2005/056184, 2005

64. L. R. M. Martens, M. J. Janssen, N. Coute, J. R. Lattner, US Patent 7 754 933, 2010

66. K. Schumann, A. Brandt, B. Unger, F. Scheffler, talk: Adsorptionseigenschaften bindemittelfreier

71. C. Benkmann, US Patent, 4 326 858, 1982

72. F. Bretschneider, C. Van Lookeren, M. Nebelung, H. Klemm, WO Patent 03/040259, 2003