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Studies in Surface Science and Catalysis 137

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

Zeolites and Molecular Sieves: An Historical Perspective

Edith M. Flanigen, UOP Research and Development (retired)

White Plains, NY 10603-3136, U.S.A.

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.

1. R E V I E W OF M O L E C U L A R SIEVE AND Z E O L I T E FUNDAMENTALS

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.

1.1. Molecular Sieves


Molecular sieves are porous solids with pores of the size of molecular dimensions, 0.3-2.0
nm in diameter. Examples include zeolites, carbons, glasses and oxides. Some are crystalline with
a uniform pore size delineated by their crystal structure, e.g., zeolites. Others are amorphous, e.g.,
carbon molecular sieves. Most current commercial molecular sieves are zeolites. The pore size
distribution for representative commercial adsorbent types (Fig. 1) contrasts the singular pore size
of zeolites 5A and X or Y, with the broader distribution and larger mean pore diameter of the
amorphous activated carbon and alumina adsorbents. The carbon molecular sieve has a mean pore
diameter intermediate between that of 5A and X or Y zeolite but has a significantly broadened
pore size distribution.

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)

Figure 1. Pore size distribution of representative adsorbents. A) 5A (CaA) zeolite; B) X or


Y zeolite; C) carbon molecular sieve; D) activated carbon; E) porous alumina

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

adsorption and catalytic applications.


In most zeolite structures the primary structural units, the A104 or SiO4 tetrahedra, are
assembled into secondary building units which may be simple polyhedra such as cubes, hexagonal
prisms, or cubo-octahedra. The final framework structure consists of assemblages of the
secondary units. (See Cpts. 3 and 4 in this volume.)
More than 70 novel, distinct framework structures of zeolites are known. They exhibit
pore sizes from 0.3-1.0 nm, and pore volumes from about 0.10 to 0.35 cc/g. Typical zeolite pore
sizes using oxygen-packing models are shown in Figure 2. They include small pore zeolites with
eight-ring pores with free diameters of 0.30-0.45 nm, e.g., zeolite A; medium pore zeolites
formed by a ten ring, 0.45-0.60 nm in free diameter, e.g., ZSM-5; large pore zeolites with 12-ring
pores, 0.6-0.8 nm, e.g., zeolites X and Y; and extra-large pore zeolites with fourteen-ring pores,
e.g., UTD-1. The molecular sieve effect is illustrated in Figure 3 for calcium A zeolite with an
eight-ring pore of oxygens. Normal octane readily accesses the intemal void through the pore
whereas iso-octane is larger than the pore and is totally excluded.
The zeolite framework should be viewed as somewhat flexible, with the size and shape
14

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

3.1. Synthetic Zeolites


Barrer's work in the mid to late 1940's inspired Milton of the Linde Division of Union
Carbide Corporation to initiate studies in zeolite synthesis in search of new approaches for
separation and purification of air. Between 1949 and 1954 R. M. Milton and co-worker D. W.
Breck discovered a number of commercially significant zeolites, types A, X and Y. In 1954 Union
Carbide commercialized synthetic zeolites as a new class of industrial materials for separation
and purification. The earliest applications were the drying of refrigerant gas and natural gas. In
1955 T. B. Reed and D. W. Breck reported the structure of the synthetic zeolite A. In 1959 Union
Carbide marketed the "ISOSIV" process for normal-isoparaffin separation, representing the first
major bulk separation process using true molecular sieving selectivity. Also in 1959 a zeolite
Y-based catalyst was marketed by Carbide as an isomerization catalyst (ref. 20).
In 1962 Mobil Oil introduced the use of synthetic zeolite X as a cracking catalyst. In 1969
Grace described the first modification chemistry based on steaming zeolite Y to form an
"ultrastable" Y. In 1967-1969 Mobil Oil reported the synthesis of the high silica zeolites beta and
ZSM-5. In 1974 Henkel introduced zeolite A in detergents as a replacement for the
environmentally suspect phosphates. By 1977 industry-wide 22,000 tons of zeolite Y were in use
in catalytic cracking. In 1977 Union Carbide introduced zeolites for ion-exchange separations.
Since their introduction as a new class of industrial materials in 1954, the annual market
for synthetic zeolites and molecular sieves has grown immensely, to $1.6-1.7 billion worldwide
in 1998 (ref. 21). The major application areas are as adsorbents, catalysts, and ion exchange
materials. The largest single market by volume is the detergent application where zeolite A (and
recently Type P) functions as an ion exchanger. In 1998, 2.3 billion pounds were consumed in that
application. Although the second largest volume use is as catalysts, this is the largest value market
for zeolites, about 55% of the total. Fluid catalytic cracking (FCC) catalysts, containing primarily
silica-enriched forms of zeolite Y, represent more than 95% of total zeolite catalyst consumption,
with smaller volumes used in hydrocracking and chemical and petrochemical synthesis. Catalyst
consumption in 1998 is estimated at 360 million pounds (ref. 21).
Adsorption applications are varied, and include: drying and purification of natural gas,
petrochemical streams, e.g., ethylene and propylene, refrigerants, and insulated windows; bulk
separations, e.g., xylenes and normal paraffins; and in air separation to produce oxygen by
pressure swing adsorption (PSA) or vacuum pressure swing adsorption (VPSA) processes.
Adsorbent consumption in 1998 is estimated at 200 million pounds (ref. 21).

3.2 Natural Zeolites


For 200 years following their discovery by Cronstedt, zeolite minerals (or natural zeolites)
were considered to occur typically as minor constituents in vugs or cavities in basaltic and
volcanic rock. Such occurrences precluded their being obtained in mineable quantities for
commercial use. From the late 50's to 1962 major geologic discoveries revealed the widespread
occurrence of a number of natural zeolites in sedimentary deposits throughout the Western United
States. The discoveries resulted from the use of x-ray diffraction to examine very fine-grained
(1-5 um) sedimentary rock. Some zeolites occur in large near mono-mineralic deposits suitable
for mining. Those that have been commercialized for adsorbent applications include chabazite,
17

erionite, mordenite and clinoptilolite (ref. 22).


Japan is the largest user of natural zeolites (see Cpt. 1 in this volume by Maesen and
Marcus). Mordenite and clinoptilolite are used in small volume in adsorbent applications
including air separation and in drying and purification (ref. 23). Natural zeolites have also found
use in bulk applications as fillers in paper, in pozzolanic cements and concrete, in fertilizer and
soil conditioners and as dietary supplements in animal husbandry. World production of natural
zeolites is estimated at 7.2 billion pounds in 1998, with the bulk applications representing most
of that consumption (ref. 21).
The price of zeolites varies considerably depending on the application. The price of
catalysts vary from about $1/pound for FCC to tens of dollars/pound for specialty catalysts;
adsorbents from about $1.50 to $2/pound, up to tens of dollars/pound for specialty adsorbents;
and about $0.30/pound for detergents. Natural zeolites in bulk applications sell for $0.02-
0.10/pound, and in industrial adsorbent applications for $1-1.50/pound (ref. 21).

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
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . , . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . -----=- ........... - .....

Time of Initial Discovery Composition


Late 40's to Early 50's Low Si/A1 Ratio Zeolites
Mid 50's to late 60's High Si/A1 Ratio Zeolites
Early 70's SiO2 Molecular Sieves
Late 70's A1PO4 Molecular Sieves
Late 70's to Early 80's SAPO and MeAPO Molecular Sieves
Late 70's Metallo-silicates, -aluminosilicates
Early to Mid 80's A1PO4-based Molecular Sieves
Early to Mid 90's Metallophosphates
Mesoporous Molecular Sieves
Octahedral-tetrahedral Frameworks

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.

4.1. Aluminosilicate Zeolites and Silica Molecular Sieves


The evolution of aluminosilicate zeolites is summarized in Table 2 based on increasing
framework Si/A1 composition. The four somewhat arbitrary categories are: 1) "low", 2)
18

"intermediate", 3) "high" silica zeolites, and 4) "silica" molecular sieves.

Table 2.
The evolution of molecular sieve materials
Composition and examples
"Low" S i/A1 Zeolites (1 to 1.5)" A, X

"Intermediate" Si/A1 Zeolites (--2 to 5):


A: Natural Zeolites: erionite, clinoptilolite, mordenite
B. Synthetic Zeolites: Y, L. large pore mordenite, omega

"High" Si/A1Zeolites (--10 to 100):


A. By thermochemical framework modification:
Highly siliceous variants of Y, mordenite, erionite
B. By direct synthesis: ZSM-5, beta

Silica Molecular Sieves: silicalite

The transition in properties accompanying the increase in the framework Si/A1 is


summarized in Table 3. The latter are generalized and should only be viewed as trends. The
thermal stability increases from about 700~ in the low silica zeolites to 1300~ in the silica
molecular sieves. The surface selectivity, which is highly hydrophilic in the low silica zeolites,
is hydrophobic in the high silica zeolites and the silica molecular sieves. The acidity tends to
increase in strength with increasing Si/A1 ratio. As the Si/A1 ratio increases, the cation
concentration and ion exchange capacity (proportional to aluminum content) decreases. The
structures of the low silica zeolites are predominantly formed with 4-, 6-, and 8-rings of
tetrahedra. In the intermediate silica zeolites we see the onset of 5-rings in mordenite and omega
zeolite. In the high silica zeolite structures and the silica molecular sieves we find a predominance
of 5-rings of tetrahedra.

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

Relative pressure, P/Po

Figure 4. Comparison of adsorption equilibrium isotherms for water, oxygen, and n-


hexane on NaX zeolite and silicalite. Water and n-hexane at 25C and oxygen at -183C.

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

the pore volume of silicalite is substantially smaller than that of NaX.


In summary, if we compare the properties of the low and intermediate zeolites with those
of the high silica zeolites and silica molecular sieves, we find that their resulting properties allow
the low and intermediate zeolites to remove water from organics and to carry out separations and
catalysis on dry streams. In contrast, the hydrophobic high silica zeolites and silica molecular
sieves can remove and recover organics from water streams and carry out separations and
catalysis in the presence of water.

4.2. The 80's and the 90's


Overall the 80's and 90's can be described as a period of explosion in the discovery of
new compositions and structures of molecular sieves. This can perhaps be seen most vividly by
comparing the numbers of structure types contained in the various editions of the Atlas of Zeolite
Structure Types. One hundred twenty-five structure type codes have been assigned through early
2000. The 1978 1st Edition contained 38 structure types, the 1987 2 nd Edition 64, the 1992 3 rd
Edition 85, and the last 1996 4 th Edition 98. Thus 87 new structure types have been discovered
since 1978. However, the reader should be cautioned that a significant number of the structure
types included in the Atlas are not truly microporous or molecular sieve materials, i.e., they are
not stable to removal of the as-synthesized guest species, typically water or organic templates, and
therefore cannot reversibly adsorb molecules or carry out catalytic reactions. Unfortunately, the
Atlas does not give any information on the stability of the structures described.

4.2.1. The 80's


In the 1980's there was extensive work carried out on the synthesis and applications of
ZSM-5 and a proliferating number of other members of the high silica zeolite family. In 1982
microporous crystalline aluminophosphate molecular sieves were described by Wilson et al. (ref.
25) at Union Carbide, and additional members of the aluminophosphate-based molecular sieve
family, e.g., SAPO, MeAPO, MeAPSO, E1APO and E1APSO, subsequently disclosed by 1986
(ref. 26). Considerable effort in synthesizing metallosilicate molecular sieves was reported where
the metals iron, gallium, titanium, germanium and others were incorporated during synthesis into
silica or aluminosilicate frameworks, typically with the ZSM-5 (MFI) topology (ref. 27).
Additional crystalline microporous silica molecular sieves and related clathrasil structures were
reported.
The 80's saw major developments in secondary synthesis and modification chemistry of
zeolites. Silicon-enriched frameworks of over a dozen zeolites were described using methods of:
thermochemical modification (prolonged steaming); mild aqueous ammonium fluorosilicate
chemistry; and by high temperature treatment with silicon tetrachloride and low temperature
treatment with fluorine gas. Similarly, framework metal substitution using mild aqueous
ammonium fluorometallate chemistry was reported to incorporate iron, titanium, chromium and
tin into zeolite frameworks by secondary synthesis techniques. A review of modification and
secondary synthesis chemistry is given in Cpt. 6 in this volume by Szostak.

4.2.1.1. Aluminophosphate-Based Molecular Sieves


In 1982 a major discovery of a new class of aluminophosphate molecular sieves was
reported by Wilson et al. (ref. 25). By 1986 some thirteen elements were reported to be
incorporated into the aluminophosphate frameworks, Li, Be, B, Mg, Si, Ti, Mn, Fe, Co, Zn, Ga,
21

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

Very Small Pore


Intermediate 16 Novel 0.3 0.3
11 Novel 0.6 0.16 20 SOD 0.3 0.24
31 Novel 0.65 0.17 25 Novel 0.3 0.17
41 Novel
. . . . . . . . . . . ,,, ,,,,, .... . . .
0.6. . . . . . . .
0.22 28 Novel 0.3 0.21

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).

4.2.1.1.2. Silicoaluminophosphates (SAPO)


The next family of new molecular sieves are the silicoaluminophosphates (SAPO).
Sixteen microporous structures have been reported to date, eight of which were never before
observed in zeolites. The SAPO family includes a silicon analogue of the 18-ring VPI-5, Si-VPI-5
(ref. 29), a number of large pore 12-ring structures including the important SAPO-37 (FAU),
medium pore structures with pore sizes from 0.6-0.65 nm, and small pore structures with pore
sizes of 0.4-0.43 nm including SAPO-34 (CHA). The SAPO's exhibit both structural and
compositional diversity.
The SAPO anhydrous composition is 0-0.3R(SixAlyPz)O2 where x, y and z are the mole
fraction of the respective framework elements. The mole fraction of silicon, x, typically varies
from 0.02 to 0.20 depending on synthesis conditions and structure type. Martens et al. have
reported compositions with the SAPO-5 structure with x up to 0.8 (ref. 30). Van Nordstrand et
al. have reported the synthesis of a pure silica analogue of the SAPO-5 structure, SSZ-24 (ref. 31).
The introduction of silicon into hypothetical phosphorus sites produces negatively charged
frameworks with cation exchange properties and weak to mild acidic catalytic properties. Again,
as in the case of the aluminophosphate molecular sieves they exhibit excellent thermal and
hydrothermal stability.

4.2.1.1.3. Metal Aluminophosphates (MeAPO)


In the metal aluminophosphate (MeAPO) family the framework composition contains
metal, aluminum and phosphorus (Ref. 26). The metal (Me) species include the divalent forms
of Co, Fe, Mg, Mn and Zn, and trivalent Fe. As in the case of SAPO, the MeAPO's exhibit both
structural diversity and even more extensive compositional variation. Seventeen microporous
structures have been reported, eleven of these never before observed in zeolites. Structure types
crystallized in the MeAPO family include framework topologies related to the zeolites, e.g., -34
(CHA) and-35 (LEV), and to the A1PO4's, e.g.,- 5 and-11, as well as novel structures, e.g.,-36
(0.8 nm pore) and -39 (0.4 nm pore). The MeAPO's represent the first demonstrated incorporation
of divalent elements into microporous frameworks.
The spectrum of adsorption pore sizes and pore volumes and the hydrophilic surface
23

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.

4.2.1.1.4. Other AIPO4-Based Compositions


The MeAPSO family further extends the structural diversity and compositional variation
found in the SAPO and MeAPO molecular sieves. These quaternary frameworks have Me, A1,
P, and Si as framework species (Ref. 26). The MeAPSO structure types include framework

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 "

Figure 5. Schematic representation of the relationships in the aluminophosphate-


based molecular sieves.
topologies observed in the binary A1PO4 and temary (SAPO and MeAPO) compositional systems
and the novel structure -46 with a 0.7 nm pore. The structure of-46 has been determined (ref. 32).
Quinary and senary framework compositions have been synthesized containing aluminum,
phosphorus and silicon, with additional combinations of divalent (Me) metals. In the E1APO and
E1APSO compositions the additional elements Li, Be, B, Ga, Ge, As, and Ti have been
incorporated into the A1PO4 framework (ref. 26). Figure 5 shows the compositional relationships
among the aluminophosphate-based families of molecular sieves.

4.2.1.2. Metallosilicate Molecular Sieves


A large number of metallosilicate molecular sieves have been reported particularly in the
patent literature. Those claimed include silicates containing incorporated tetrahedral iron, boron,
24

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.

4.2.1.3. Other Framework Compositions


Crystalline microporous frameworks have been reported with compositions of:
beryllosilicate, lovdarite (ref. 33); beryllophosphate (ref. 34); aluminoborate (ref. 35);
aluminoarsenate (ref. 36); galloarsenate (ref. 37); gallophosphate (ref. 38); antimonosilicate (ref.
39); and germanosilicate (ref. 40).
Harvey et al. (ref. 34) reported the synthesis of alkali beryllophosphate molecular sieves
with the RHO, GIS, EDI, and ANA structure topologies, and a novel structure, BPH.
Simultaneously, the first beryllophosphate mineral species were reported, tiptopite, with the
cancrinite (CAN) topology by Peacor et al. (ref. 41), and pahasapaite, with the RHO topology by
Rouse et al. (ref. 42).
In the late 1980's Bedard et al. reported the discovery of microporous metal sulfides,
based on germanium (IV) and Sn (IV) sulfide frameworks (ref. 43). The microporous sulfides are
synthesized hydrothermally in the presence of alkylammonium templating agents. The GeSa-
based compositions include one or more of framework incorporated metals: Mn, Fe, Co, Ni, Cu,
Zn, Cd, and Ga. Over a dozen novel structures were reported which have no analogues in the
microporous oxides. Ozin et al. have extended this work to a large number of microporous
sulfides and selenides (ref. 44). It should be noted that the microporous sulfides and selenides are
prone to structure collapse upon calcination to remove the template species.

4.2.2. The 90's


The explosion in the discovery of new compositions and structures observed in the 80's
continued through the 90's.
Some three dozen or more novel tetrahedral structures were synthesized in the 90's, based
on aluminosilicate, silica, metallosilicate, and metallophosphate frameworks. Two are especially
noteworthy. The gallophosphate cloverite has the first 20-ring pore, 0.4 x 1.32 nm in diameter,
and the lowest observed framework density (number of T-atoms per 1000 A3), 11.1 (ref. 45). The
cloverite structure contains the D-4R and alpha cages reminiscent of the aluminum-rich zeolite
Type A (LTA), combined with the rpa cage found in the aluminophosphate structures. It is an
interrupted framework structure and thus has somewhat limited thermal stability. The siliceous
zeolite UTD-1 contains a 14-ring pore 0.75 x 1.0 nm in diameter, and is the first aluminosilicate
with a pore size larger than a 12-ring (ref. 46). CIT-5, a second 14-R structure with a pure silica
composition and a 0.8 nm pore, was reported by Wagner et al. (ref. 50).
Gier et al. reported zinc and beryllium phosphates and arsenates with the X (FAU), ABW
and SOD structures reminiscent of the early aluminum-rich synthetic zeolite chemistry. The
synthesis of ZnPOa-X (FAU) is especially spectacular. Crystallization occurs almost
instantaneously at 0~ (ref. 47). Concurrent with ease of synthesis, the structure is thermally
25

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.

4.2.2.1. New Directions in the 90's


Two major new classes of molecular sieve type materials were reported in the 90's,
microporous frameworks based on mixed octahedral-tetrahedral frameworks in contrast to the
previously described tetrahedral frameworks, and mesoporous molecular sieves with pore sizes
ranging from about 2 nm to greater than 10 nm.

4.2.2.1.1. Octahedral-Tetrahedral Frameworks


The microporous materials described heretofore were all based on tetrahedral frameworks.
Microporous titanosilicate materials with mixed octahedral-tetrahedral frameworks were reported
in the 90' s. The framework linkage is through TiO6 octahedra and SiO4 tetrahedra. Chapman and
Roe described the titanosilicate GTS-1, a structural analogue of the mineral pharmacosiderite,
with a 3-dimensional channel system and 8-R pores (ref. 59). Kuznicki and co-workers reported
the synthesis of the titanosilicates ETS-4 and ETS-10 (ref. 60). Their respective pore sizes are 0.4
26

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.

4.2.2.1.2. Mesoporous Molecular Sieves


A major advance in molecular sieve materials was reported in 1992 by researchers at
Mobil. Kresge et al. and Beck et al. describe a new family of mesoporous silicate and
aluminosilicate materials, designated M41S (ref. 62). The members of the family include: MCM-
41, with a unidimensional hexagonal arrangement of uniform open channels 0.2-10 nm in
diameter: a cubic structure, MCM-48, with a 3-dimensional channel system with pore sizes -0.3
nm; and a number of lamellar structures. The order in the structure is derived from the channel
arrangement. The silica or aluminosilicate wall outlining the channel is disordered and exhibits
properties much like amorphous silica or silica-alumina.
Within the same time frame and independently, Inagaki and co-workers reported a
mesoporous material designated FSM-16, prepared by hydrothermal treatment of the layered
sodium silicate kanemite, NaHSiEOs.3H20 (ref. 63). Chen et al. substantiate that FSM-16 and
MCM-41 bear a strong resemblance to each other, both with narrow mesopore distributions and
similar physicochemical properties, but with FSM-16 having higher thermal and hydrothermal
stability due to the higher degree of condensation in the silicate walls (ref. 64).
Both mesoporous materials are synthesized hydrothermally with a surfactant liquid crystal
as the template (see section 5 below). They exhibit very high surface areas and pore volumes, of
the order of 1000 mE/g and 1.5 cc/g, respectively.
Since this initial work there has been a plethora of literature on mesoporous molecular
sieves. In addition to the silica and aluminosilicate frameworks similar mesoporous structures of
metal oxides now include the oxides of Fe, Ti, V, Sb, Zr, Mn, W, and others. Templates have
been expanded to include nonionic, neutral surfactants, and block copolymers. Pore sizes have
broadened to the macroscopic size length, in excess of 40 nm in diameter. A detailed review of
the mesoporous molecular sieves is given in ref. 65. To date no commercial applications of the
mesoporous molecular sieves have emerged.
In a tour-de-force of detective work, Di Renzo et al. uncovered an obscure US Patent filed
in 1969 and issued in 1971 to Chiola et al., describing a low density silica. Reproduction of that
patent resulted in a product having all of the properties of MCM-41 (ref. 66).

4.3. Characterization Techniques


The basic characterization techniques for zeolites and molecular sieves developed in the
50's and 60's, particularly by the Union Carbide workers, were x-ray powder diffraction,
gravimetric adsorption measurements on multi-tube McBain-Bakr balances using different
molecular-sized adsorbates, and various tests to screen applications. The characteristic x-ray
powder diffraction pattern served as a structural identifier, and adsorption measurements gave the
pore size and pore volume. A number of detailed structures were solved by the then known x-ray
structure determination techniques. All of these basic characterization techniques are of course
still in use today.
Application of state-of-the-art sophisticated characterization and structural techniques to
molecular sieve materials in the 1980's and 1990's resulted in a major advance in our
understanding of the structure and chemistry of molecular sieve materials. These include: the
27

systematic development of hypothetical frameworks (ref. 67); the application of computational


chemistry, computer modeling and ab initio calculations; the application of solid state NMR and
high resolution electron microscopy techniques; 129XeNMR characterization; and the use of high
energy radiation (synchrotron and intense pulsed neutron) and ab initio structural techniques to
solve zeolite structures.

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

Early Zeolite Synthesis Siliceous Zeolite Synthesis

Alkali Hydroxide +
Alumina Alkali Hydroxide Silica Alumina QuaternaryAmmonium Silica

Gel Gel
~ -100~ ~ 100-200~

Zeolite Zeolite

Figure 6. Schematic representation of synthesis methods for zeolite synthesis

Amine or Quaternary
Ammonium Template
Alumina Metal salt
H3PO4 Silica

as ~eq~ired)

Reactive Gel
/

100 - 200~ ~ 4 - 48h

Product = Template 9 [TO2] 9 H20


Figure 7. Schematic representation of the synthesis method for A1POn-based molecular
sieves. The template and H20 are removed by calcination at 400-600~

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.

Figure 8. Schematic representation of the synthesis of MCM-41. Route 1 is a liquid


crystal initiated mechanism; route 2 is a silicate anion initiated mechanism. Adapted
from ref. 62

Table 6.
History of cation templates .
.....Composition Caiion Types ......... Examples a Structures ............
Low Si/A1 Alkali Na A, X, Y
K L

High silica zeolites Alkali + Quaternary N a + Pr4N ZSM-5


Silica molecular sieves Ammonium Silicalite
Metallosilicates TS- 1 (Ti-silicalite)

Aluminophosphate-based Quaternary Ammonium PraN A1PO4-5


Molecular sieves or Amines n-Pr2NH VPI-5

Mesoporous molecular Alkali + surfactant Na + MCM-41, FSM-16


Sieves molecules CTMA
a. PrnN tetrapropylammonium; n-Pr2NH, di-n-propylamine; CTMA cetyltrimethyl-
ammonium.

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.

REFERENCES

1. D.W. Breck, Zeolite Molecular Sieves, Structure, Chemistry and Use, John Wiley & Sons,
New York, 1974; reprinted by Krieger, Malabar, Florida, 1984.
2. R.M. Barrer, Pure and Appl. Chem., 51 (1979) 1091-1100.
3. D.S. Coombs, A. Alberti, T. Armbruster, G. Artioli, C. Colella, E. Galli, J.D. Grice, F.
Liebau, J.A. Mandarino, H. Minato, E.H. Nickel, E. Passaglia, D.R. Peacor, S.
Quartieri,R. Rinaldi, M. Ross, R.A. Sheppard, E. Tillmanns, G. Vezzalini, Can. Mineral.
35 (1997) 1571-1606.
4. A.F. Cronstedt, Akad. Handl. Stockholm, 18 (1756) 120-130.
5. F. Fontana, Memorie Mat. Fis. Soc. Ital. Sci., 1 (1777) 679.
6. A. Damour, Ann. Mines, 17 (1840) 191.
7. G.W. Morey and E. Ingerson, Econ. Geol., 32 (1937) 607.
8. H.S. Thompson, J. Roy. Agr. Soc. Engl., 11 (1850) 68; J.T. Way, ibid. p. 313.
9. H. Eichhorn, Poggendorf Ann. Phys. Chem., 105 (1858) 126.
10. H. de St. Claire-Deville, Compt. Rend., 54 (1862) 324.
11. G. Friedel, Bull. Soc. Franc. Mineral. Cristallogr., 19 (1896) 94-118.
12. F. Grandjean, Compt. Rend., 149 (1909) 866-68.
13. O. Weigel and E. Steinhoff, Z. Kristallogr., 61 (1925) 125-54.
14. R.J. Leonard, Econ. Geol., 22 (1927) 18-43.
15. W.H. Taylor, Z. Kristallogr., 74 (1930) 1.
16. L. Pauling, Proc. Nat. Acad. Sci., 16 (1930) 453; Z. Kristallogr., 74 (1930) 213.
17. J.W. McBain, The Sorption of Gases and Vapors by Solids, Rutledge and Sons, London,
1932, Chap. 5.
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