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H. van Bekkum, E.M. Flanigen, P.A. Jacobs and J.C. Jansen (Editors)
9 2001 Elsevier Science B.V. All rights reserved. 11
Chapter 2
The history of zeolites and molecular sieves is reviewed from the discovery of the first
zeolite mineral in 1756 through the explosion in new molecular sieve structures and compositions
in the 1980's and 1990's.
R. M. Barrer's early pioneering work in adsorption and synthesis began the era of
synthetic zeolites. The discovery of the commercially significant synthetic zeolites A, X and Y
by R. M. Milton and D. W. Breck in the late 1940's to early 1950's led to their introduction by
Union Carbide Corporation as a new class of industrial adsorbents in 1954, and in 1959 as
hydrocarbon conversion catalysts. Today synthetic zeolites are used widely throughout the
petroleum refining and chemical process industries as selective adsorbents, catalysts and ion
exchangers, and represent an estimated nearly two billion dollar industry.
The last five decades have seen a chronological progression in molecular sieve materials
from the aluminosilicate zeolites to the microporous silica polymorphs, the microporous
aluminophosphate-based polymorphs, the metallosilicate and metallophosphate compositions,
and to the octahedral-tetrahedral frameworks and mesoporous molecular sieves.
Before detailing the history, a brief review of the fundamentals of zeolites and molecular
sieves will be given, especially for those readers who are new to the field.
1.2. Zeolites
Zeolites are crystalline aluminosilicates of group IA and group IIA elements such as
12
sodium, potassium, magnesium, and calcium (ref. 1). Chemically, they are represented by the
empirical formula:
M2/nO " A1203 9 ySiO2 9 wH20
where y is 2 to 10, n is the cation valence, and w represents the water contained in the voids of
the zeolite. Structurally, zeolites are complex, crystalline inorganic polymers based on an
infinitely extending three-dimensional, four-connected framework of A104 and SiO4 tetrahedra
linked to each other by the sharing of oxygen ions. Each A104 tetrahedron in the framework bears
B D
13
>
"0
I I I I I
10 100
Pore Diameter (A)
a net negative charge which is balanced by an extra-framework cation. The framework structure
contains channels or interconnected voids that are occupied by the cations and water molecules.
The cations are mobile and ordinarily undergo ion exchange. The water may be removed
reversibly, generally by the application of heat, which leaves intact a crystalline host structure
permeated by the micropores and voids which may amount to 50% of the crystals by volume.
The structural formula of a zeolite is based on the crystallographic unit cell, the smallest
unit of structure, represented by:
Mx/n [(A102)x(SiO2)y] 9 wH20
where n is the valence of cation M, w is the number of water molecules per unit cell, x and y are
the total number of tetrahedra per unit cell, and y/x usually has values of 1-5. In the case of the
high silica zeolites y/x is 10 to 100. There are two types of structures: one provides an internal
pore system comprised of interconnected cage-like voids; the second provides a system of
uniform channels which, in some instances, are one-dimensional channel systems. The preferred
type has two- or three-dimensional channels to provide rapid intracrystalline diffusion in
13
Figure 2. Typical zeolite pore sizes illustrated with oxygen packing models
Figure 3. Illustration of the molecular sieve effect. The straight chain molecule normal octane
(left) passes through the eight-ring aperture of 5A (CaA) zeolite; the branched molecule iso-
octane (right) cannot.
of the framework and pore responding to changes in temperature and guest species. For example,
ZSM-5 with sorbed neopentane has a 0.62 nm near-circular pore, but with substituted aromatics
as the guest species the pore assumes an elliptical shape, 0.45 to 0.70 nm in diameter.
Some of the more important zeolite types, most of which have been used in commercial
applications, include the zeolite minerals mordenite, chabazite, erionite and clinoptilolite, and the
synthetic zeolites type A, X, Y, L, "Zeolon" mordenite, ZSM-5, beta, MCM-22, and zeolites F
and W.
1.3 Nomenclature
There is no systematic nomenclature developed for molecular sieve materials. The
discoverer of the synthetic species based on a characteristic x-ray powder diffraction pattern and
chemical composition assigns trivial symbols. The early synthetic materials discovered by Milton,
Breck and coworkers at Union Carbide used the Arabic alphabet, e.g., zeolites A, B, X, Y, L. The
use of the Greek alphabet was initiated by Mobil and Union Carbide with the zeolites alpha, beta,
and omega. Many of the synthetic zeolites which have the structural topology of mineral zeolite
species were assigned the name of the mineral, for example, synthetic mordenite, chabazite,
erionite and offretite. The molecular sieve literature is replete with acronyms: ZSM-5, -11, ZK-4
(Mobil); EU-1, FU-1, NU-1 (ICI); LZ-210 and A1PO, SAPO, MeAPO, etc. (Union Carbide,
UOP); and ECR-1 (Exxon). The one publication on nomenclature by IUPAC in 1979 (ref. 2) is
limited to the then known zeolite-type materials.
The IZA Atlas of Zeolite Structure Types (lst Ed. 1978; 2nd Ed. 1987; 3rd Ed. 1992; 4th
Ed. 1996) published by the IZA Structure Commission assigns a three letter code to be used for
a known framework topology irrespective of composition. Illustrative codes are LTA for Linde
zeolite A, FAU for molecular sieves with a faujasite topology, e.g., zeolites X and Y, MOR for
the mordenite topology, MFI for the ZSM-5 and silicalite topologies, and AFI for the
aluminophosphate A1PO4-5 topology. The acceptance of a newly determined structure of a zeolite
or molecular sieve for inclusion in the official Atlas is reviewed and must be approved by the IZA
Structure Commission. The IZA Structure Commission was given the authority in 1986 at the 7th
15
Intemational Zeolite Conference in Tokyo, to approve and/or assign the three-letter structure code
for new framework topologies.
The definition and usage of the term "zeolite" has evolved and changed especially over
the last decade, to include non-aluminosilicate compositions and structures. The 4 th Edition of the
Atlas uses the term "zeolite and zeolite-like materials" and defines the structures included in the
Atlas as tetrahedral oxide structures with a framework density less than about 20 T-atoms per
1000 A 3 irrespective of framework composition. Similarly the term zeolite has been broadened
in the mineralogy literature to include tetrahedral framework compositions with T-elements other
than A1 and Si but where classical zeolite properties are exhibited, e.g., structures containing open
cavities in the form of channels and cages, and reversible hydration-dehydration characteristics
(ref. 3).
2. EARLY HISTORY
The history of zeolites began in 1756 when the Swedish mineralogist Cronstedt
discovered the first zeolite mineral, stilbite (ref. 4). He recognized zeolites as a new class of
minerals consisting of hydrated aluminosilicates of the alkali and alkaline earths. Because the
crystals exhibited intumescence when heated in a blowpipe flame, Cronstedt called the mineral
a "zeolite" derived from two Greek words, "zeo" and "lithos" meaning "to boil" and "a stone". In
1777 Fontana described the phenomenon of adsorption on charcoal (ref. 5). In 1840 Damour
observed that crystals of zeolites could be reversibly dehydrated with no apparent change in their
transparency or morphology (ref. 6). Schafhautle reported the hydrothermal synthesis of quartz
in 1845 by heating a "gel" silica with water in an autoclave (ref. 7). Way and Thompson (1850)
clarified the nature of ion exchange in soils (ref. 8). Eichhorn in 1858 showed the reversibility of
ion exchange on zeolite minerals (ref. 9). St. Claire Deville reported the first hydrothermal
synthesis of a zeolite, levynite, in 1862 (ref. 10). In 1896 Friedel developed the idea that the
structure of dehydrated zeolites consists of open spongy frameworks after observing that various
liquids such as alcohol, benzene, and chloroform were occluded by dehydrated zeolites (ref. 11).
Grandjean in 1909 observed that dehydrated chabazite adsorbs ammonia, air, hydrogen and other
molecules (ref. 12), and in 1925 Weigel and Steinhoff reported the first molecular sieve effect
(ref. 13). They noted that dehydrated chabazite crystals rapidly adsorbed water, methyl alcohol,
ethyl alcohol and formic acid but essentially excluded acetone, ether or benzene. In 1927 Leonard
described the first use of x-ray diffraction for identification in mineral synthesis (ref. 13). The first
structures of zeolites were determined in 1930 by Taylor and Pauling (ref. 15,16). In 1932
McBain established the term "molecular sieve" to define porous solid materials that act as sieves
on a molecular scale (ref. 17).
Thus, by the mid-1930's the literature described the ion exchange, adsorption, molecular
sieving and structural properties of zeolite minerals as well as a number of reported syntheses of
zeolites. The latter early synthetic work remains unsubstantiated because of incomplete
characterization and the difficulty of experimental reproducibility.
Barrer began his pioneering work in zeolite adsorption and synthesis in the mid-1930's
to 1940's. He presented the first classification of the then known zeolites based on molecular size
considerations in 1945 (ref. 18) and in 1948 reported the first definitive synthesis of zeolites
including the synthetic analogue of the zeolite mineral mordenite (ref. 19).
16
3. INDUSTRIAL HISTORY
4. HISTORY OF M O L E C U L A R SIEVE M A T E R I A L S
The theme and research on molecular sieve materials over the last fifty year period has
been a quest for new structures and compositions. The major discoveries and advances in
molecular sieve materials during that period are summarized in Table 1.
Table 1.
Evolution of Molecular Sieve Materials
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . , . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . -----=- ........... - .....
The history of commercially significant molecular sieve materials from 1954 to 1979 was
reviewed by this author in 1980 (ref. 24). Highlights from that review and the subsequent history
are presented here. The reader is referred to Cpt. 3 in this volume by Baerlocher and McCusker
for the structures of the materials.
Table 2.
The evolution of molecular sieve materials
Composition and examples
"Low" S i/A1 Zeolites (1 to 1.5)" A, X
Table 3.
The transition in properties as framework Si/A1 increases from 1 to oo
Property Transition
Stability From < 700~ to -- 1300~
Surface selectivity From hydrophilic to hydrophobic
"Acidity" Increasing strength, decreasing number
Cation concentration Decreasing
Structure From 4, 6, and 8-rings to 5-rings
The low silica zeolites represented by zeolites A and X are aluminum-saturated, have the
highest cation concentration, and give optimum adsorption properties in terms of capacity, pore
size and three-dimensional channel systems. They represent highly heterogeneous surfaces with
19
a strongly hydrophilic surface selectivity. The intermediate Si/A1 zeolites (Si/A1 of 2-5) consist
of the natural zeolites erionite, chabazite, clinoptilolite and mordenite, and the synthetic zeolites
Y, mordenite, omega and L. These materials are still hydrophilic in this S i/A1 range.
The high silica zeolites with Si/A1 of 10-100 can be generated by either thermochemical
framework modification of hydrophilic zeolites or by direct synthesis. In the modification route
stabilized, siliceous variants of Y, mordenite, erionite, and over a half-dozen other zeolites have
been prepared by steaming and acid extraction. These materials are reported to be hydrophobic
and organophilic and represent a range of pore sizes from 0.4-0.8 nm. A very large number of
high silica zeolites prepared by direct synthesis have now been reported, including beta, ZSM-5,
-11, -12, -21, -34, NU-1 and FU-1, and ferrisilicate and borosilicate analogs of the aluminosilicate
structures. Typical of the reported silica molecular sieves are silicalite, fluoride silicalite,
silicalite-2 and TEA-silicate. ZSM-5 and silicalite have achieved commercial significance.
The difference in surface selectivity between the hydrophobic silica molecular sieve,
silicalite, and the highly hydrophilic zeolite NaX can be observed by comparing their equilibrium
adsorption isotherms for water, oxygen and n-hexane (Fig. 4). The hydrophilic NaX pore fills at
0.4
H20____._._.__.___------a
on NaX ----~
t3~ O~ on NaX
O3
0.3 ~ ~ o ~ o
E n-Hexaneo n NaX
O
n-Hexane on silicalite
o 0.2 9 A ~_A
"O I. I-
t'- f 0 e on silicalite
O
E
< 0.1
H20 on silicalite
m .,.
, , , , l , , , , l , , , , l , , , , l , , , i
0.0
0.0 0.2 0.4 0.6 0.8 1.0
low partial pressures with all three adsorbates giving a typical Langmuir-type isotherm shape. On
silicalite, n-hexane and oxygen show a similar typical molecular sieve pore filling at low partial
pressures, but illustrative of the hydrophobic characteristic of silicalite, only a small amount of
water (-0.05 cc/g) is adsorbed even at a relative partial pressure near 1. It should be noted that
20
Ge and As (ref. 26). These new generations of molecular sieve materials designated A1PO4-based
molecular sieves comprise more than two dozen structures and two hundred compositions.
Table 4.
Typical structures in A1PO4-based molecular sieves
Species Structure Pore Sat'n H20 Species Structure Pore Sat'n H20
Type size, Pore vol. Type size, Pore vol.
nm cc/g nm cc/g
Very Large Pore Small Pore
VPI-5 Novel 1.25 0.35 14 Novel 0.4 0.19
8 Novel 0.9 0.24 17 ERI 0.43 0.28
18 Novel 0.43 0.35
26 Novel 0.43 0.23
Large Pore 33 Novel 0.4 0.23
5 Novel 0.8 0.31 34,44,47 CHA 0.43 0.3
36 Novel 0.8 0.31 35 LEV 0.43 0.3
37 FAU 0.8 0.35 39 Novel 0.4 0.23
40 Novel 0.7 0.33 42 LTA 0.43 0.3
46 Novel 0.7 0.28 43 GIS 0.43 0.3
52 Novel 0.43 0.3
56 Novel 0.43 0.3
The over two dozen structures of A1PO4-based molecular sieves reported to date include
zeolite topological analogues and a large number of novel structures. The major structures are
shown in Table 4. They include fifteen novel structures as well as seven structures with
framework topologies related to those found in the zeolites, CHA (-34, -44, -47), ERI (-17), GIS
(-43), LEV (-35), LTA (-42), FAU (-37), and SOD (-20). Also shown is the pore size and
saturation water pore volume for each structure type. The structures include very large pore (1.25
nm), large pore (0.7-0.8 nm), intermediate pore (0.6 nm), small pore (0.4 nm), and very small
pore (0.3 nm) materials. Saturation water pore volumes vary from 0.16 to 0.35 cc/g comparable
to the pore volume range observed in zeolites. The novel structures which have been determined
include types 5, 11, 14, 16, 22, 33, 39, 46, 50, 52 and 56. The A1PO4-based structures have been
reviewed by Bennett et al. (ref. 28) and are described in this volume in Cpt 3 by Baeflocher and
McCusker.
4.2.1.1.1. AIPO4
The new family of aluminophosphate materials (A1PO4-n) includes the first very large
pore material, VPI-5 reported by Davis et al. (ref. 29). The VPI-5 structure is outlined by a
unidimensional channel of an 18-membered ring with a free pore diameter of 1.25 nmo There is
22
one 12-membered ring structure, A1PO4-5, with a pore size of 0.8 nm; several medium pore
structures outlined by 10-membered rings or elliptical 12-rings with pore diameters of 0.6-0.65
nm, for example, A1PO4-11, -31 and -41; and small pore size materials such as A1PO4-17 (ERI),
with 8-membered ring pores and pore sizes of 0.4-0.43 nm in diameter.
The product composition expressed in terms of oxide ratios is:
xR'A1203" 1.0-k_0.2 P205 "yH20
where R is an amine or quaternary ammonium ion. The A1PO4 molecular sieve as synthesized
must be calcined at 400 to 600~ to remove the R and water yielding a microporous
aluminophosphate molecular sieve.
The characteristics of aluminophosphate molecular sieves include a univariant framework
composition with A1/P = 1, a high degree of structural diversity, a wide range of pore sizes and
volumes exceeding the pore sizes known previously in zeolite molecular sieves with the VPI-5
18-membered ring material. They are neutral frameworks and therefore have nil ion-exchange
capacity. Their surface selectivity is mildly hydrophilic. They exhibit excellent thermal and
hydrothermal stability, up to 1000~ (thermal) and 600~ (steam).
selectivity of the MeAPO's are similar to those described for the SAPO's. The observed catalytic
properties vary from weakly to strongly acidic and are both metal and structure dependent. The
thermal and hydrothermal stability of the MeAPO materials is somewhat less than that of the
A1PO4 and S APO molecular sieves.
The MeAPO molecular sieves exhibit a wide range of compositions within the general
formula 0 - 0.3R(MexAlyPz)O2. The value of x, the mole fraction of Me, typically varies from
0.01 to 0.25. Using the same mechanistic concepts described for SAPO, the MeAPO's can be
considered as hypothetical A1PO4 frameworks that have undergone substitution. In the MeAPO's
the metal appears to substitute exclusively for aluminum resulting in a negative (Me2+), or neutral
(Me 3 framework charge. Like SAPO, the negatively charged MeAPO frameworks possess
ion-exchange properties and Bronsted acid sites.
A1PO 4
I
SAPO I E1aPo I
Me = Co, Fe, E1 = As, B, Be,
M g, Mn, Zn Ga, Ge, Li, Ti
[~ MeAPSO I E1APSO I
I I
+ Me', Me" + El', Me'~ M e "
chromium, arsenic, gallium and germanium. Most of the work has been reported with structures
of the MFI type. Others include metallosilicate analogues of ZSM-11,-12, Theta-1, ZSM-34 and
beta. In only a limited number of the reported metal incorporations has sufficient characterization
been presented to establish proof of incorporation. To date, only B, Ga, Fe and Ti have been
sufficiently characterized to confirm structural incorporation. The metallosilicate molecular sieves
are reviewed in detail by Szostak (ref. 27). The titanium-silicalite composition, TS-1, has
achieved commercialization in selective oxidation processes, and iron-silicalite in ethylbenzene
synthesis.
unstable.
Table 5 lists some of the major new structures reported in the 90's. Interestingly, there
were no new aluminum-rich synthetic zeolites reported in either the 80's or the 90's. The new
aluminosilicate structures were all high silica or pure silica in composition.
Table 5.
Major new synthetic structures of the 90's
Species Structure Type Pore size, nm Ring Size . . . . Ref=
MCM-22, 49 MWW 0.6 10 48,49
UTD-1 DON 1.0 14 46
CIT-5 CFI 0.8 14 50
EMC-2 EMT 0.7 12 51
Cloverite -CLO 1.3 20 45
Not to be outdone by humankind there were a number of new zeolite minerals discovered
in nature during the 90' s. The zeolite mineral boggsite has a novel framework topology with 3-
dimensional pores combining 10R's and 12R's, and has not yet been reproduced synthetically
(ref. 52). Tschernichite is an aluminum-rich mineral analogue of the synthetic zeolite beta (ref.
53). Gottardiite is a new mineral analogue of synthetic zeolite Nu-87 (ref. 54). The zeolite
mineral terranovaite has a novel structure with pentasil chains and a two-dimensional 10R
channel (ref. 55). Mutinaite is a high silica zeolite mineral analogue of ZSM-5 with the highest
silica content of all known zeolite minerals (Si/A1 = 7.7) (ref. 56). The structure of the zeolite
mineral perlialite was reported (ref. 57) to be the same as that of the synthetic zeolite L (LTL),
some 35 years after the synthesis of zeolite L.
Tschortnerite surely is the most remarkable novel zeolite mineral discovered (ref. 58). Its
unique framework topology contains five different cages, D-6R's, D-8R's, sodalite cages,
truncated cubo-octahedra, and a unique 96-membered cage. Cu-containing clusters are
encapsulated within the truncated cubo-octahedra. The pore structure is a 3-dimensional 8-R, and
the framework density of 12.2 is among the lowest known for zeolites. The framework is
alumina-rich with an Si/A1 = 1, unusual for zeolite minerals.
nm and 0.8 nm. ETS-4 is the synthetic analogue of the rare titanosilicate mineral zorite. The novel
structure ETS-10 contains a 3-dimensional 12-R pore system and shows a high degree of disorder
(ref. 61). ETS-10 has achieved commercial status in adsorption applications.
4.4. Applications
Applications of zeolites and molecular sieves in the 80's and 90's showed a growth in
petroleum refining applications with emphasis on resid cracking and octane enhancement. ZSM-5
was commercialized as an octane enhancement additive in fluid catalytic cracking where
Si-enriched Y zeolites serve as the major catalytic component in high-octane FCC catalysts. The
use of zeolite catalysts in the production of organic (fine) chemicals appeared as a major new
direction. Zeolites in detergents as a replacement for phosphates became the single largest volume
use for synthetic zeolites worldwide (see Maesen and Marcus in this volume, Cpt. 1). Zeolite ion
exchange products, both synthetic and natural, were used extensively in nuclear waste cleanup
after the Three Mile Island and Chemobyl nuclear accidents. New applications emerged for
zeolite powders in two potentially major areas, odor removal and as plastic additives.
In adsorption and separation applications the 80's and 90's saw a major growth in the use
of pressure swing adsorption for the production of oxygen, nitrogen and hydrogen. Processes for
the purification of gasoline oxygenate additives were introduced. Recent environmentally driven
applications have arisen using the hydrophobic molecular sieves, highly siliceous Y zeolite and
silicalite, for the removal and recovery of volatile organic compounds (VOC) that offer promise
for significant market growth.
An exciting new scientific direction emerged in the 80's and 90's for exploring molecular
sieves as advanced solid state materials. In a 1989 review, Ozin et al. (ref. 68) speculate "that
zeolites (molecular sieves) as microporous molecular electronic materials with nanometer
dimension window, channel and cavity architecture represent a 'new frontier' of solid state
chemistry with great opportunities for innovative research and development". The applications
described or envisioned include: molecular electronics; "quantum" dots/chains; zeolite electrodes;
batteries; non-linear optical materials; and chemical sensors.
Zeolites have also been used as raw materials for ceramic compositions relevant to the
electronic industry. Bedard et al. reported the high temperature processing of Mg-exchanged
zeolite B (P) to form cordierite ceramic compositions (ref. 69).
5. HISTORY OF SYNTHESIS
A brief description of the history of the synthetic methods developed for the molecular
sieves previously described is given here. The reader is referred to Chapter 5 in this volume by
Jansen and Wilson for a detailed discussion of synthesis.
The method developed by Milton in the late 1940's involves the hydrothermal
crystallization of reactive alkali metal aluminosilicate gels at low temperatures and pressures. The
synthesis mechanism is generally described as involving solution mediated crystallization of the
amorphous gel, involving concepts of cation templating. In the early alkali aluminosilicate
synthesis of the low silica zeolites, it has been proposed that the hydrated alkali cation "templates"
or stabilizes the formation of the zeolite structural sub-units. A schematic for the early zeolite
28
synthesis is shown in Figure 6. Alkali hydroxide, reactive forms of alumina and silica, and H20
are combined to form a gel. Crystallization of the gel to zeolite occurs at a temperature near
100~
The addition of quaternary ammonium cations to alkali aluminosilicate gels occurred in
Alkali Hydroxide +
Alumina Alkali Hydroxide Silica Alumina QuaternaryAmmonium Silica
Gel Gel
~ -100~ ~ 100-200~
Zeolite Zeolite
Amine or Quaternary
Ammonium Template
Alumina Metal salt
H3PO4 Silica
as ~eq~ired)
Reactive Gel
/
the early 1960's, first to produce intermediate silica zeolites, e.g., omega and N-A or ZK-4, and
subsequently led to the discovery of the high silica zeolites and silica molecular sieves. A
schematic for the synthesis of the siliceous zeolites is shown in Figure 6. The synthesis of high
silica zeolites and silica molecular sieves involves synthetic chemistry similar to the initial low
silica zeolite method with two important differences: the addition of the quaternary ammonium
cation, and a crystallization temperature higher than 100~ typically 125 to 200~ The pH in
both the low silica and the siliceous synthesis is basic with pH's in the region of 10 to 14.
A schematic of the synthesis method developed in the late 70's for the AIPOn-based
molecular sieves is shown in Figure 7. A reactive source of alumina is combined with phosphoric
acid and an amine or quaternary ammonium template added to form a reactive gel. Silica or a
29
metal salt is added optionally. The reactive gel is heated to 100 to 200~ for 4 to 48 hours to
crystallize the molecular sieve product.
There are important differences in the A1POa-based synthesis compared to the
aluminosilicate and silica systems: the amine or quaternary ammonium ion is frequently the only
template species (no alkali metal); and the initial pH in the gel is typically mildly acidic to mildly
basic.
The synthesis scheme for the mesoporous molecular sieves is shown in Figure 8. The
structure directing species or template is typically a surfactant molecule.
Table 6.
History of cation templates .
.....Composition Caiion Types ......... Examples a Structures ............
Low Si/A1 Alkali Na A, X, Y
K L
Flanigen and Patton first reported the use of fluoride as mineralizer in molecular sieve and
30
zeolite synthesis, in the synthesis of F-silicalite (ref. 70). Subsequently, Guth and Kessler greatly
expanded and developed this synthetic technique. The fluoride synthesis can be carried out in
acidic pH's, unlike the basic pH's resulting when OH- is used as the mineralizing species.
Typically the fluoride route leads to larger, more perfect and often single crystals of silicate- and
phosphate-based compositions, and in some cases novel structures. Cloverite was discovered
using the fluoride synthesis technique. The fluoride ion seems to also play a templating role. A
review of the fluoride synthesis methodology is contained in reference 71.
The history of cation templates used in molecular sieve synthesis is summarized in Table
6. Over the period of nearly fifty years of molecular sieve synthesis a number of concepts have
been developed by various workers in cation-structure specificity. These are variously described
as structure-directing, the templating effect, clathration phenomena, steriospecific replication, and
nucleation effects. See Chapter 5 in this volume for a detailed discussion.
6. THE FUTURE
6.1. Materials
As noted in Sections 4.2.1. and 4.2.2. the 80's and 90's have seen an explosive and
accelerating increase in discovery of new compositions and structural topologies. Based on the
very high activity in this area in the last two decades, we can expect a continuation of the
proliferation of new molecular sieve compositions and structures. Further advances can also be
expected in novel compositions derived from modification and secondary synthesis chemistry.
When we consider the very large number of structures and compositions now reported in the
molecular sieve area and compare that with the number of commercial molecular sieves, what is
the probability of future commercialization of a new material? There are many factors affecting
achievement of commercial status: unique and advantageous properties of the material; the
market need; the market size; the costs of development and marketing; and the cost and degree
of difficulty in manufacturing. As a result it is likely, based on historical experience, that no more
than a few of the prolific number of new molecular sieve materials of the 80's and 90's will
achieve commercial status in the new millennium.
6.2. Applications
Molecular sieve adsorbents will continue to be used in the now-practiced separation and
purification applications throughout the chemical process industry. New directions in the 90's
include environmental and biopharmaceutical applications which have only recently received
attention. Future trends in catalysis beyond the 90's include: a continuing accelerated discovery
of new catalytic materials; an expanded use in petroleum refining particularly in the area of high
octane gasoline and in the development of reformulated gasoline; commercial development in
conversion of alternate resources to motor fuels and base chemicals; and as routes to organic
chemical intermediate or end products.
The large application of zeolites as ion exchangers in detergents has leveled off in demand
in North America, Western Europe and Japan in the late 90' s, but should continue to grow during
the 2000' s, particularly in Asia, Australia and Latin America (ref. 21). The other applications of
zeolites as ion exchangers in the nuclear industry, in radioactive waste storage and cleanup, and
in metals removal and recovery, will probably remain a relatively small fraction of the worldwide
market for molecular sieve materials.
31
Among the new application areas that could become large volume applications are the use
of molecular sieves as functional powders, in odor removal, and as plastic additives. The use of
zeolites in solid state applications is highly speculative, ff ever practically realized that application
would most probably represent a relatively small volume of the total zeolite consumption.
7. HISTORY OF I N T E R N A T I O N A L C O N F E R E N C E S AND O R G A N I Z A T I O N S
In 1957 the first informal molecular sieve conference was held at Pennsylvania State
University in the U.S.A. In 1967 the first of a series of international molecular sieve conferences
chaired by Professor R.M. Barrer was held in London. Subsequently, international meetings have
been held every several years - in 1970 at Worcester, 1973 at Zurich, 1977 at Chicago, 1980 at
Naples, 1983 in Reno, 1986 in Tokyo, 1989 in Amsterdam, 1992 in Montreal, 1994 in Garmisch-
Partenkirchen, 1996 in Seoul, and 1998 in Baltimore.
An international molecular sieve organization was first formed in 1970 in conjunction
with the Worcester Conference, and called the International Molecular Sieve Conference (IMSC).
Its responsibility was to continue the organizational implementation of future international
molecular sieve conferences on a regular basis. In 1977 at the Chicago meeting the name of the
organization was changed to the International Zeolite Association (IZA) and its scope and purpose
expanded to "promote and encourage all aspects of the science and technology of zeolitic
materials", as well as organizing "International Zeolite Conferences" on a regular basis. The term
zeolite in the new organization "is to be understood in its broadest sense to include both natural
and synthetic zeolites as well as molecular sieves and other materials having related properties
and/or structures" (ref. 72). International Zeolite Association regional affiliates have been
established, and include: the British Zeolite Association (BZA), in 1980; the Japan Association
of Zeolites (JAZ), in 1986; and regional zeolite associations in France, Italy, Hungary and
Germany in the late 80's and early 90's. In 1995, a Federation of European Zeolite Associations
(FEZA) was formed and presently includes the British, Bulgarian, Dutch, French, German,
Hungarian, Italian, Romanian, Spanish, Polish and Georgian Zeolite Associations. FEZA
sponsors several workshops in Europe each year, coveting various aspects of zeolite science, and
held its first International FEZA Conference in Hungary in 1999. The Northeast Corridor Zeolite
Association (NECZA) was established in the United States in 1997 and holds an annual
Symposium.
In addition to these organizations the IZA has several established Commissions. The first
is the Structure Commission formed in 1977, which has published four editions of the Atlas of
Zeolite Structure Types (1978, 1987, 1992, 1996). It should be noted that an up-to-date version
of the Atlas is maintained on the World Wide Web at the Structure Commission's Web site (ref.
73). Subsequently commissions were established in the area of catalysis (1988) and synthesis
(1992). An adsorption and ion exchange commission has been proposed. In 1988 the Consortium
for Theoretical Frameworks was organized by J. V. Smith at the University of Chicago.
8. HISTORICAL E P I L O G U E
Key factors in the growth of molecular sieve science and technology include: the
pioneering work of Barrer: the key discoveries of Milton and Breck and associates at Union
Carbide: the rapid commercialization of the new synthetic zeolites and their applications by
32
Union Carbide (1949-1954); the major development at Union Carbide in adsorption process
design and engineering technology; major discoveries in hydrocarbon conversion catalysts at
Union Carbide, Exxon, Mobil Oil, Shell and other industrial laboratories; the discovery and
commercialization of sedimentary zeolite mineral deposits in the United States in the 60's; and
last, but not least, the dedication and contribution of so many high quality scientists and
engineers. It is estimated that by the end of the twentieth century there were over ten to twenty
thousand such scientists and engineers in industry and academia dedicating a significant portion
of their work to zeolite and molecular sieve science and technology.
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