Zeolites As Catalysts 1

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Zeolites as Catalysts.I
John Turkevicha
a
Princeton University, Princeton, New Jersey
To cite this Article Turkevich, John(1968) 'Zeolites as Catalysts.I', Catalysis Reviews, 1: 1, 1 — 35

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Zeolites as Catalysts.1
JOHN TURKEVICH
Princeton University
P yince ton. New Jersey
I . HISTORY ................................ 2
I1. CLASSIFICATION O F Z E O L I T E S . . . . . . . . . . . . . . . .
Downloaded At: 12:43 20 January 2011
I11. STRUCTURAL CHARACTERISTICS O F T H E FAUJASITE

ZEOLITES ............................... 4
IV . TETRAHEDRA ............................ 5
V . RINGS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
VI . CAGE UNITS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
VII . CATALYTIC STUDIES ....................... 13
.
VIII ORTHO-PARA HYDROGEN CONVERSION .......... 13
LX. HYDROGENATION .......................... 14
X. DEHYDROGENATION........................ 15
X I . CRACKING ............................... 15
XI1. DEHYDRATION ............................ 24
XI11 . OXIDATION .............................. 25
XIV . ISOMERIZATION . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
XV . ALKYLATION ............................. 32
References ............................... 33
Zeolites are crystalline aluminosilicates of the general formula

Mv(A1O.)x(SiO.)y . ZH. 0 in which M is either a monovalent o r diva-
.
lent cation In the f o r m e r case v is equal to x. whereas if M is diva-
1
2 JOHN TURKEVICH
lent v is equal to one-half x. The cation can be exchanged reversibly

without destroying the aluminosilicate framework. The water can also
be removed without destroying the framework and can be replaced by
other molecules whose molecular dimensions are smaller than the
pore size of the cavities that a r e regularly distributed in the frame-
work. The zeolites both occur naturally and can be made syntheti-
cally on either laboratory o r industrial scale. In recent y e a r s they
have assumed great technical importance as adsorbents and catalysts.
They are a l s o important from a structural point of view, since they
represent the next degree of complexity of structure after that of
large molecules.
I. HISTORY
In the middle of the eighteenth century Baron Cronstadt observed

that, on heating, c r y s t a l s of certain minerals appeared to melt and
boil at the s a m e time. This phenomenon was called intumescence and

the materials that intumesce were named zeolites by Baron Cronstadt,
from the Greek “zeo” to boil and “lithos” stone. In 1840 Damour re-
ported that zeolites underwent reversible dehydration and that during
this p r o c e s s t h e r e w a s no change in the transparency of the crystal form.
The zeolites studied at that time were chabazite, heulandite, and anal-
cite.
In the twentieth century interest developed in the adsorptive prop-
e r t i e s of zeolites. Thus in 1925 Weigel and Steinhoff discovered se-
lective adsorption properties in that chabazite rapidly adsorbed water,
methyl alcohol, ethyl alcohol, and formic acid but excluded from its
pores acetone, benzene, o r ether. This prompted J. W. McBain to
coin the term molecular sieves for materials which, like chabazite,
have the ability to separate molecules on the basis of size.
In the 1930s Pauling and Taylor determined the crystal structure
of the zeolites, analcite and natrolite, and showed the presence in
these s t r u c t u r e s of cavities whose p a r t s acted as molecular sieves.
The development of X-ray diffraction techniques in the last three
decades permitted rapid characterization and structure determination
of a large number of zeolites. In the late 1930s B a r r e r [ 11 began his
thorough investigation of the adsorptive properties of zeolites and
c a r r i e d out synthesis of numerous zeolites by high-pressure hydro-
thermal methods. In the late 1940s Milton 111 of the Linde Division of
the Union Carbide Corporation studied the u s e of naturally occurring
zeolites for the industrial separation of gases, and his colleagues em-
barked on a program of synthesis of zeolitic materials. They found
that high p r e s s u r e s were not necessary for hydrothermal synthesis
ZEOLITES AS CATALYSTS 3
and were able to p r e p a r e in the laboratory not only s o m e of the nat-

u r a l zeolites but al s o o t h e r s of completely new st ruct ure. This is
how the Linde 4A, Linde 5A, and Linde 13X zeolites w ere produced.
T he Davison Chemical Division of W. R. G race & Co. al so produced
and mar k e te d a crystalline aluminosilicate called Microtrap.
During the last decade synthetic zeolites have found application in
drying and selective s epar at i on of gases. T h e i r ability to a d s o r b
w ate r molecules and r e j e c t substances whose molecule d i a m e t e r is
g r e a t e r than the p o r e s i z e h a s made zeolites part i cul arl y useful as
drying agents. They have a l s o been used f o r ion-exchange work. The
p ar tic u lar u s e that we are concerned with i n this a r t i c l e is t hei r ap-
plication as highly active catalysts f o r a variety of reactions, partic-
u l ar ly those involved i n petroleum hydrocarbon transformations.
11. CLASSIFICATION OF ZEOLITES

About 40 zeolites which occur in nature and a number which have

been produced synthetically have been classified both on the b a s i s of
g r o s s morphological appearance and on the evidence obtained by
X -r a y s t r u c t u r e analysis. In the old morphological classification the
c l a s s e s were: fibrous zeolites (natrolite, scolecite, mesolite, thom-
sonite, and eddingtonite), the platty zeolites (heulandite, brew st eri t e,
wellsite, harmotone, stilbite, and mordenite), and three-dimensional
fr a mewo r k zeolites (chabazite, gmelinite, levynite, faujasite, and
analcite).
The newer classification is based on s i m i l ari t y of arrangem ent of
secondary s t r u c t u r a l units i n the c r y s t a l as revealed by X -ray dif-
fraction. The classification groups are analcite, natrolite, chabazite,
harmotone, heulandite, mordenite, and faujasite. The only group that
will be d is cu s s e d i n detail will be the faujasite group because this is
the group of zeolites used as catalysts. The following s h o r t charac-
terization can be made of the ot her groups. The analcite group (anal-
cite, [Na,,A1,Si,zO,,] * 16H,O; wairakite, Cag[ All6Si3,OS] * 16H,O; and
viseite, NazCal,LAl2,SifiPloH~~O~] - 16H,O) h a s a cubic (or al m ost cubic)
tridimensional f r am ew or k with identifiable four- and six- m em bered
r i n g secondary s t r uct ur e. The natrolite group consi st s of natrolite,
Nal,[A1,,Si,,08,] . 16H,O; scolecite, Ca, [Al,,Si,,O,,] * 24H,O; mesolite,
Na,,Ca,,l A148Si,20,4,,J * 64H,O; gonnardite, Na,Ca,~A1,Si,,04,] * 12H,O;

,
t hom s oni t e , N a, C a41 (Na, C a) A116 (A1,Si )4 Si 0, ,] * 12 H, 0 ; e d i ngt on ite ,
-
Ba,JA1,SiGO,o] 8H,O; laubanite, Klo(A1,,Si,,O,,) . 16H,O; mountain-
i t e, (CalNa,K)Si,,,, .24H,O; and rhodesite, (Ca,Na,%),Si,,O,, . 11H,O.
Th e s t r u c t u r e consists of chains of oxygen t et rahedra with channels
perpendicular to the chain axis. The chabazite group consi st s of the
4 JOHN TURKEVICH
following min e r al s : gmelinite, Na,[Al,Si,,O,,] . 24H,O; offrite,

-
(Ca, Mg, Na,, &)4.5[A19Siz707z]27H,O; and levynite, Ca,l AlfiSil~0,,J
. 18H,O. Th e three-dimensional s t r u c t u r e is charact eri zed by paral-
lel ar r an g emen t of s i x- m em ber ed rings. The harmotone group con-
-
sists of harmotone, B~[Al,Si,,O,] 12H,O; phillipsite,
.
(KxNal-x)loA1,0Si,,04 20H,O; gismondine, Ca,[ Al,Si,%,] 16H,O;
g ar r o n ite , NaCa,.,[Al,$,,O,,]. 14H,O; B a r r e r ’ s NaP 1 whose form ul a
is N+[Al,$i,O,,] 12H,O; and br ew s t er i t e, (Si, Ba, Ca),[Al,Si,,O,,]
- 10H,O. The s t r u c t u r e of the m i n e r a l s of this group is charact eri zed
by f o u r - memb e r ed r i ngs of oxygen t et r ahed ra that lie paral l el o r al-
m o s t p ar allel to each other. The heulandite group of m i neral s con-
s i s t s of heulandite, Ca,[A1,Si,,07,] * 24H,O; stilbite, N~Ca,[Al,,Si,,O,,]
* 2&0; and clinoptilolite, Na,Ca,[Al,Si,,O,,] .
24H,O. Brew st eri t e is
s o m e t i m e s included i n this group. A char act eri st i c s t r u c t u r a l feat ure
of these two m i n e r a l s is the pr es ence of five-membered ri ngs con-
nected via two four-membered rings. The mordenite group consi st s
of mordenite, Na,[A1,Si,,Ogs] 24H,O; dachiardite, Na,[A1,Si904,,]
- -
12H,O; epistilbite, Ca,[AlGSi,,0,,] 16H,O; ferrierite,
Na,Mg,[Al, Si,,O,,] 18H,O; ptilolite, [A12,CaK,]4[A1,Si,o09,] . 16H,O;
and bikitaite, Li,l A1,Si40,,]. 2H,O. The charact eri st i c feat ure of
m e m b e r s of the m i n e r a l s of this group is the presence of five-mem-
b er e d r in g s of oxygen t et r ahedr a. Mordenite has been used as a cat-
alyst. Me mb e r s of the faujasite group consist of faujasite (Linde X,
Linde Y), (Na,, Ca),,[A~,Si,,,O,,,] 216H,O. Linde X, Y, and A have
been extensively used f o r catalytic purposes. The s t r u c t u r a l charac-
t e r i s t i c s are truncated octahedra cages, the so-called sodalite o r
8- cages.
Zeolite s p e ci es that have not been classified are paulingite,
(Na,Ca) ,52[Al,,2 Si5zo067z] . 700H,O, whose s t r u c t u r e has recently been
analyzed; the ZK- 5, N%4LA124Si7201Y21 .90H,O; ashcroftine.
(Na,, K,, Ca, Mg, Mn)O. A1,0,. 2-5Si0,. 4H,O; and yugawaralite, CaO
. A1,0,. 5-7Si0, .4H,O.
111. STRUCTURAL CHARACTERISTICS O F

THE FAUJASITE ZEOLITES
Inasmuch as m os t of the catalytic work on zeolites involved the

use of the m e m b e r s of the faujasite c l a s s , the present discussion will
be limited to the discussion of the s t r u c t u r e s of faujasite Linde A,
Linde X, and Linde Y zeolites. P a r t i c u l a r attention will be paid to
two s t r u c t u r a l c h a r a c t e r i s t i c s which are of i n t e r e s t to catalytic chem-
i s t: (1) s t r u c t u r a l f act or s which determine the s i z e s of the p o r e s
which allow molecules to e n t e r to locations of catalytic c e n t e r s in-
side the pores and ( 2 ) the number and the location of the “active”
centers within the pores.
Structurally, the zeolites have the following building blocks in or-
der of increasingly complexity: ( a ) oxygen-silicon (aluminum)
tetrahedra; (b) rings (4-membered, 6-membered, 8-membered, and
12-membered rings); (c) primary cages (cubes, hexagonal p r i s m s ,
sodalite cages); and (d) secondary cages and channels obtained by
linking the primary cages. In addition, the following structural char-
acteristics a r e of importance to catalysis: (e) the distribution of
aluminum and silicon among the oxygen tetrahedra; (f) the location
sites of the cations; and (g) the crystallographic role of water and
other adsorbed silica.
IV. TETRAHEDRA
The oxygen tetrahedron has in its center either an atom of silicon,

SiO:-, or aluminum, A10:-. Since the charge on the aluminum oxy-

gen tetrahedron is five minus while that on the silicon-oxygen tetra-
hedron is four minus, t hi s excess negative charge on the aluminum tetra-
hedron is compensated by the presence of monovalent or “one-half”
divalent cation in close proximity to the site of the aluminum tetra-
hedron. Furthermore, it should be kept in mind that the aluminum
tetrahedron can be expanded by hydration into a n octahedron chang-
ing the coordination number of the aluminum from 4 to 6, whereas
the silicon tetrahedron cannot be expanded. Evidence for the expan-
sion of the aluminum tetrahedron on hydration has been obtained in
the author’s laboratory by means of aluminum nuclear resonance.
Aluminum nucleus h a s a nuclear moment of 5/2 and a quadrupole
moment of 0.149 unit. Because of this large quadrupole moment,
there is a fast quadrupole relaxation of the nuclear resonance of alu-
minum and a disappearance of the nuclear resonance signal if the
atomic environment about the aluminum is not spherical. Our results
show that on dehydration of a NaY zeolite at 150°C, the nuclear res-
onance of aluminum disappears. This we interpret to mean that the
atomic surroundings of the aluminum have changed on dehydration
from octahedral (i.e. , spherical) to tetrahedral.
V. RINGS
Rings a r e formed of silicon (alumina) tetrahedra by bridges of

oxygen. Rings of this type a r e observed by X-ray diffraction meth-
ods and a r e characteristic of zeolites. Their nature and arrange-
6 JOHN TURKEVICH
ment is the basis, as we have seen, of the modern classification

of zeolites, Rings undoubtedly exist in aqueous solution and must
be intermediates in the synthesis of zeolites, however, they have not
been observed in aqueous solution. Preliminary results obtained in
the author’s laboratory by Professor Ciborowski showed that the
symmetric vibration of the Al(0H); a s shown by the Raman band a t
615 cm-l in solution aluminate disappears when sodium silicate is
present in excess. Furthermore, the nuclear magnetic resonance of
the same solution observed as a 50-mG line at 11.094 Mc/sec at
10,000 G also disappears when sodium silicate solution is added. De-
tection of aluminum nuclear resonance necessitates a symmetric
atomic environment around the aluminum nucleus. It exists in
Al(0H); and must be lacking when Al(0H); is mixed with 30:- ion.
This is taken as evidence for compound formation between Al(0H);
and SiOi-.
The faujasite catalysts have 4-membered1 6-membered, 8-mem-
bered, 12-membered, and 18-membered rings. The pore opening of
the 4-membered rings is negligible. There a r e six 4-membered

rings in a cube, six in the hexagonal prism, six in the truncated octa-
hedron (sodalite cage), twelve in the octadecahedron (secondary large
cage of the Linde A zeolite), and eighteen in the large cavity of the
Linde X and Y zeolites. The distribution of aluminum and silicon
atoms in the center of the oxygen tetrahedra is of great interest since
the aluminum c a r r i e s the extra negative charge and the cation or hy-
drogen ion is located near it, However, only very laborious three-
dimensional X-ray dzfraction procedure will give atomic coordi-
nates accurate to 0 . 1 3 A . necessary to distinguish those tetrahedral
sites occupied by aluminum from those occupied by silicon. This has
been carried out in only a few cases. It seems that Al-0-A1 links a r e
forbidden. The fact that only a limited number of silicon/aluminum
ratios are observed would indicate that there is an ordering in the
rings of the A1 and Si. Thus in the Linde A and Linde X there a r e
two aluminums and two silicons alternatingly positioned in the 4-
membered ring, whereas in the Linde Y there are three silicons and
one aluminum in each of the 4-membered rings.
The six-membered rings have a pore opening of 2 . 2 - i diameter.
There are two such rings in the hexagonal prism, eight in a truncated
octahedron (sodalite cage), eight in the octadecahedron (secondary
large cage type I of the Linde A zeolite), and four in the large cage
type I1 of the Linde X and Y sieve. The distribution of the aluminum
and silicon in the six-membered rings is of interest. In the ordered
state in Linde A and Linde X where the silicon/aluminum ratio is 1,
the aluminum and silicon atoms alternate. In the disordered state,
which undoubtedly occurs in the Linde Y zeolites and in compositions
between Linde X and Y, there may be a variety of distributions of

silicon/aluminum ratio subject to the condition that the aluminum
atoms are not in neighboring tetrahedra.
Eight-membered rings have a pore size of 4.3 A . They are an im-
portant structural aspect of the Linde A zeolite when the major cage
contains six such eight-membered rings arranged on the sides of a
cube.
Twelve-membered rings have a pore diameter of 8 - 9 i . They are
present in the large cavity of the Linde X and Linde Y zeolite, where
four of them a r e arranged on the sides of a truncated tetrahedron.
VI. CAGE UNITS
The next structural units in the zeolitic structure are the cages
which are formed by combinations of the 4-, 6-, 8-, and 12-mem-
bered rings into three-dimensional open structures. We must dis-

tinguish between primary cages which cannot be broken into simpler
cages and secondary cages which result from the combination of pri-
mary cages. The following Archimedean polyhedra a r e suitable
cages for tetrahedrally coordinate frameworks which are found in
zeolites : cubes, hexagonal p r i s m s , octagonal prisms, truncated octa-
hedra, and truncated cubic octahedra.
The cube containing eight silicon (aluminum) tetrahedra has six
four-membered ring faces. It occurs in the Linde A zeolite as a con-
necting link joining the truncated octahedra (sodalite units).
Hexagonal p r i s m s of 1 2 silicon (aluminum) tetrahedra a r e com-
posed of two parallel six-ring faces and six four-membered sides.
They occur in the mineral faujasite, Linde X, and Linde Y and in the
ZK-5 material.
The truncated octahedron, also known a s the sodalite cage, /3-cage,
or cubooctahedron, contains 24 silicon (alumina) tetrahedra. It is
composed of six four-membered ringsoand eight six-membered rings.
The free diameter of the cavity is 6.6A. The sodalite unit occurs in
faujasite, Linde A, Linde X, and Linde Y sieves and also in the min-
e r a l sodalite. In the Linde A and Linde X the number of silicon atoms
is equal t o that of the aluminum atoms and the general formula
Na,,(AlO,),,(SiO,),,. The aluminum and silicon atoms must be or-
dered, occupying diagonal positions on the square faces if the rule is
obeyed that no two aluminum tetrahedra be adjacent to each other,
In the idealized Y sieve the formula for the sodalite cage would be
Na,(AlO,),(SiO,),,. In this structure there is one aluminum atom per
square face of the sodalite cage. Another idealized structure for a
sodalite unit would be Na,(AlO,),(SiO,),,, where there are two alu-
8 JOHN TURKEVICH
minum atoms a t each of the four hexagonal faces arranged in the

tetrahedral a r r a y around the sodalite cage. The analysis reported
for Linde Y gives a formula Na(A10,)7(Si0,)17 for the sodalite cage.
The analytical data should be carefully examined to see whether they
a r e c o r r e c t , f o r the X-ray analysis does not give the aluminum dis-
tribution but only the size of the unit cell. Chemical analysis and
X-ray fluorescence give an overall aluminum/silicon ratio, and this
may include silicon o r aluminum present a s an impurity. The pore
openings a r e essenti%lly those of hexagonal rings, i.e., 2.6A. The
pore diameter is 6.6A. The adsorptive capacity is four molecules
of water. The sodalite cage is the building block in the mineral soda-
lite which consists of a close packing of sodalite cages. In Linde A
the sodalite cages a r e joined together through square faces in a so-
dium chloride type a r r a y . In Linde X and Linde Y they a r e joined
through alternate hexagonal faces in a diamond-type a r r a y .
The next cage to consider is the truncated cubooctahedron, the
type 126-hedron cage. It consists of 48 silicon (aluminum) atoms,
96 oxygen atoms, and a number of sodium atoms equal to the number

of aluminum atoms. Considered in t e r m s of faces, it has 18 square
faces, 8 hexagons, and 6 octagons. The octagons a r e arranged a s
faces ofoa cube. The pore openings of these eight-membFred rings
a r e 4.3 A . The diameter of the pore in the cage is 11.4A. The ad-
sorptive capacity of this cage is 25 molecules of water; about 20
molecules of ammonia; 16 molecules of oxygen, nitrogen, or argon;
15 molecules of hydrogen sulfide; 12 molecules of methyl alcohol;
10 molecules of sulfur dioxide; 9 molecules of carbon dioxide; 5+
molecules of iodine and about the s a m e number of normal propyl
alcohol molecules; 4 molecules of normal butane. The type I 26-
hedron cage occurs in Linde A and in the ZK-5 zeolites.
The type I1 26-hedron cage, o r the faujasite cage, occurs as the
main cavity in the Linde X and Linde Y zeolites and in the faujasite
minerals. It is composed of 48 atoms of silicon (aluminum) and 96
atoms of oxygen. The number of sodium atoms is equal to the num-
ber of aluminum atoms. The cage has 18 square faces, 4 six-mem-
bered rings, and 4 twelve-membered rings. The latter a r e arranged
in the same way a s the four sides of tetrahedron and a r e the most
important ports of entry into the cavity. The type I1 26-hedron cages
a r e connected to each other by sodalite cages throug) the 4 six-mem-
bered rings. The size of the pore openings is 8 to 9 A , and this p e r -
mits entrance of branched-chain hydrocarbons and aromatic com-
pounds. The capacity of the faujasite cage is 28 molecules of water;
19 molecules of oxygen, nitrogen, or argon; 7 t molecules of iodine;
6 i molecules of sulfur hexafluoride; 5.8 molecules of fluoroethane;
5.6 molecules of cyclopentane; 5.4 molecules of benzene; 4.6 mole-
cules of toluene; 4.5 molecules of normal pentane; 0.1 molecule of

dichlorofluoroethane; 3.5 molecules of normal pentane; 3.4 mole-
cules of fluoropropane; 2.9 molecules of n-fluorobutane; 2.8 mole-
cules of isooctane; and 2.1 molecules of perfluorodimethylcyclohex-
ane. The Na Linde A zeolite o r theo4A sieve has a cubic structure
with a unit cell constant a = 12.32A, a unit cell formula
Na,,(A10z)lz(Si0,),2. 29H,O, and a space group o h = Pm314. Its struc-
ture consists of sodalite cages Na,,(AlO,),(SiO,),, attached to each
other by cubes and SO arranged in a sodium chloride lattice in which
the sodium and the chloride ions a r e replaced by sodalite cages.
These define an a-cage, the truncated cubooctahedron, and the type
126-hedron cage which i s in the center of the unit cell. There a r e
three types of cages in the Linde A zeolite listed in the order of de-
creasing s i z e : the P , p - , and y-cages. The a-cage is a s mentioned
above, located in the center of the unit cell. It is defined by six
eight-membered ring openings which a r e arranged in a cubic arrange-
ment with respect to each other. These a r e garallel to the sides of
the unit cell and have a pore diameter of 4.2A. The edges and the
c o r m e r s of the cube so formed a r e truncated. The a-cage is joined
to six other identical a-cages of neighboring unit cells through the
eightbmembered oxygen ring:. The mean diameter of the a-cage i s
11.4A and its volume is 760A3. There are eight sodalite units ( p -
cages) along the four ( 1 l l ) d i r e c t i o n s of the unit cell surrounding the
a-cages. These sodalite units have the f o r m of a !runcated octa-
hedron. The opFning into the sodalite cage is 2.3A, the diameter of
the cage is 6.6A, and the volume is 160A. There a r e 1 2 Y-cages,
cubes surrounding the ahcage. They connect the square faces of the
sodalite cage to form the 0-cage.
Eight of the sodium ions are localized at each of the six-mem-
bered rings of the sodalite unit at the c o r n e r s of the a-cage. The
other four sodium atoms are located at the center of four of the six
eight-membered rings defining the a-cage. They may be displaced
from the center of the eight-membered rings along the 100 direction.
The sodium A zeolite contains 22.2 g by weight at 25°C and the
vapor p r e s s u r e of water a t this t e F p e r a t u r e i s 24 mm of Hg. The
saturation volume of water is 833A3/unit cell. The capacity of the
sieve for water is reduced by the volume occupied by the cations.
This decrease i s linear in the volume of the ion for the same ionic
charge. It i s , however, greater for strongly hydrated and multivalent
ions. In the case of the sodium A sieve the contribution of the 12
sodium ions of radius 0.98 A i s 40 As. The available volume of the
a- and P-cages minus the so$um volume is 760 + 160 - 40 o r 880A3.
The absorption water is 833 As, indicating that the water molecules
penetrate both the a- and p-cages. A l l this water can be removed by
evacuation at m m of Hg vacuum at 350-400°C o r by heating in
a i r a t 350°C for 350 hours o r at 700°C in a i r for 6 hours. The absorp-
10 JOHN TURKEVICH
tion of oxygen i s equal to 6 l O k . This value indicates that the oxygen

atoms can penetrate only the a-cages.
The sodium ions can be replaced by Li', K ', Rb', Cs+, Tl', Ag',
NH;, Mg2' CaZ+,SrZ+,Ba2+,Hg2+, Cd2+,Zn2+,Co2+,and Ni2+. A decat-
ionated zeolite can be prepared by exchanging the sodium ions by
ammonium ion and then heating the product to 350-400°C to remove
all the ammonia. Zeolites of the Linde A type containing more than
30-35% NH; lose their zeolitic structure during this treatment. TQe
sodium A zeolite in the hydrated form has a principal line at 3.62 A
in the X-ray powder diagram.
The Linde 5A molecular sieve is prepared by replacing 75-80% of
the sodium ions of the 4A sieve by Ca2'so that the fully hydrated
commercial products have the composition
Na,. 6Ca~.,(A102)12(Si02)~23 1W.
The 13X molecular sieve is of the faujasiie type. It has a cubic
structure with a unit cell constant a = 24.95A and a unit cell formula
Na,,(AlO,),,(SiO,),, .264H,O. Its space group is Oh-Fd3m. Its struc-
ture consists of sodalite cages Nal,(A1O,),,(SiO,),, ($-cages) attached

to each other by hexagonal p r i s m s through four of the eight hexag-
onal f a c e s of the sodalite units. Thus the sodalite cages a r e ar-
ranged in a diamond-type lattice. This permits the sodalite units to
define a large supercavity, the faujasite cage, as the type I1 26-he-
dron cage. There a r e three types of cages precent in the X-type zeo-
lites: the faujasite cages, the sodalite cages, and the hexagonal
prisms. The faujasite cage is enclosed by sodalite (0-cages) linked
together by hexagonal p r i s m faces. Six sodalite units a r e linked to-
gether to form six-membered rings, and four such rings delineate
the faujasite cavity. These six-membered sodalite rings have 12
oxygenoatoms in them, and the opening of these rings has a di$meter
of 8-9A. The internal diameter of the faujasite cavity is 12.5A and
its volume is about 850 A . Each faujasite cavity i s surrounded tetra-
hedrally by four other faujasite cavities since the four twelve-mem-
bered oxygen rings a r e centered on faces of a tetrahedron. There is
a possibility of cavities l a r g e r than the faujasite and also of the cre-
ation of faults since the six-membered sodalite rings (twelve-mem-
bered rings) can have either a chair or boat configuration and can
be packed in a variety of ways, much the same way a s found in ZnS
with wurzite or zinc blend structures and associated formation of
stacking faults.
There are eight sodalite cages @-cages) defining the faujasite
cavity. They a r e :ntered by six square faces and four hexagonal
faces of 2.0-2.5-A pore diameter. The other hexagonal f a c e s enter
the hexagonal prism cavities. The volume of the sodalite cavity is
160As. The hexagonal p r i s m cavities can be entered from the fauja-
site cavities through square faces and from the soda1i:e cavities
through hexagonal faces where the opening is 2.0-2.5 A .
The saturation volume f o r water at room temperature i s 7900A3.
This water can be removed from the 13X zeolite by, heating a t 350-
400°C for 12 hours. TFe total pore volume is 8080A3and theo96 so-
dium ions occupy 290A3 so that the s y p t i o n volume i s 7790A3; this
value i s to be compared to the 7900A3 actually observed. Water
must enter both the faujasite cavity and th! sodalite units. The sat-
uration volume for oxygen a t 90°K i s 7200A3,indicating that oxygen
enters only the faujasite cages.
The sodium ion can be replaced by Li', K', Rb', Cs', Ca,', S F ,
Ba2', Cu2+, Co+, and Ni,'. The sodium can be replaced by ammo-
nium ion andthis in turn can be decomposed to give a decationated
sieve. A s much a s 5% of the sodium ions can be ammonium and
can be decationated without ruining tbe zeolite structure, The hy-
drated sodium X zeolite has a 14.47A principle line in the X-ray
powder diagram.
The cations may occupy three different positions in the zeolite.

The f i r s t type S,, 16 in number per unit cell, is located in the hexag-
onal p r i s m faces between the sodalite units. The second type SII,
32 in number per unit cell, i s located in the open hexagonal faces.
The third type S I I I ,48 per unit cell, are located on the walls of the
large cavity. The S,-type sites are so unavailable to substrate that
they do not seem to be directly active a s catalytic sites.
The sodium Y sieve has the same characteristic structure a s the
sodium X sieve except that the ratio of the aluminum to silicon is
much lower, being 12:12 in the X sieve 7:17 in the Y sieve. The for-
mula for the unit cell i s Na,,(AlO,),,(SiO,),,,. There s e e m s to be a
continuous s e r i e s of X materials whose composition ranges from
Na,,(AlO,),,(SiO,),,, to Na,,(A10,),,(Si0,),3,. The analysis of the alu-
minum/silicon ratio can be made either chemically, by X-ray flu-
orescence, or by X-ray measurement of the unit cell. The chemical
analysis i s tedious and has the disadvantage that it measures the
ratio of the whole sample including all silicon-aluminum materials
present a s impurity, starting material, o r by-product. The X-ray
fluorescence is convenient but also suffers from the disadvantage
that it gives the overall analysis of the sample. The unit cell deter-
minationuis more direct but requires careful calibration. The (55s)
line at dA of 2.87 can be used for this purpose. Using the values in
the l i t e r a t u r t a s standards, the silicon/aluminum ratio i s given by
103.1-35.7 dA.
The sodium ions, just as in the Linde X sieve, occupy three dif-
ferent sites: type S,, 16 in number in the hexagonal p r i s m s ; SII, 32
in the walls of the hexagonal faces; and S I I I ,only 8 in number lo-
12 JOHN TURKEVICH
cated on the walls of the large cavity. Some of the sodium ions have
free mobility when the zeolite is hydrated. This is shown by the nu-
clear resonance of sodium. The hydrated form shows a strong s h a r p
resonance signal at 11.3 mc at 10,00OG, indicating a sodium ion that
is free to move in the cavity. When the zeolite is dehydrated the
signal disappears. This indicates that the sodium nucleus is in an
unsymmetric molecular environment for the signal disappears due
to the fact that the quadrupole moment of the sodium nucleus inter-
acts with an unsymmetric molecular environment. This results in
a rapid relaxation of the signal. This is interpreted a s follows: on
dehydration the freedom of mobility which the sodium ion had in the
hydrate cavity is lost and the sodium ion i s attached to the surface.
The exchange of ammonium ion for the sodium ion was studied
by Turkevich and Ciborowski [3]. They found that there is a substan-
tial decrease in the equilibrium constants for the exchange between
19 and 31 exchange sites.
The r e s u l t s of the study of the temperature dependence of the
evolution of water and ammonia permitted the evaluation of the

nature of the acid s i t e s on a decationated sieve. In the case of the
sodium sieve Turkevich and Ciborowski found, using a helium flow
method, that 99.6% of the water is removed below 200°C and that no
appreciable water was evolved even at 600°C. The behavior of the
56% NH,-44% Na' sieve was quite different. A l l the ammonium is
liberated from about 100°C to about 360°C. One phase of the water
evolution takes place below 360" in much the s a m e way a s that for
the 100% Na+ sieve. Thus most of the water present in both samples
is removed from the cavities by the s a m e process. The second
phase of the water evolution in the c a s e of the 56% NH,+-44% Na'
sieve takes place in a temperature region of 48O-80O0C with the
maximum amount evolved at 600°C. The amount of water so pro-
duced in the second stage is equivalent on a molecular basis to two
molecules of ammonia. It was thus established, in the high silicon/
aluminum ratio sodium faujasite-type molecular sieves, that the ion-
exchange treatment with ammonium salts and subsequent heat treat-
ment produces Bronsted-type acid sites at temperatures a s low a s
140°C and that this process is complete at about 350°C. It takes a
temperature of over 450°C to produce the Lewis acid sites by re-
moval of hydrogen-oxygen fragments from the zeolite. This must
necessitate the rupture of a silicon-oxygen-aluminum bond and the
production of a Bronsted base in addition to a Lewis acid site. This
process is not complete until above 800°C. Therefore the usual
method of activation of ammoniated molecular sieves by heating at
450°C produces a mixture of Eronsted and Lewis acid sites and a
number of Bronsted base sites.
VII. CATALYTIC STUDIES
A number of catalytic studies have been c a r r i e d out using molec-

ular sieves as catalysts or supports. These materials have two im-
portant advantages for catalytic studies. Because of constant pore
size, they exert selective action on the type of substrate that can
enter a pore and have access to an active center. Thus they can per-
mit ingress of straight-chain compounds and reject branched-chain
hydrocarbons. In addition, because of their crystalline nature and
because the surface of the catalyst penetrates the interior of the
crystal due to the porous nature of the zeolite, the active center can
be identified with specific grouping in the walls of the cavities and
pores.
VIII. ORTHO-PARA HYDROGEN CONVERSION
Ortho-para hydrogen reaction was c a r r i e d out a t - 196°C on so-

dium Y zeolites, and a series of decationated zeolites were obtained
f r o m it by Turkevich and Ciborowski [3]. The reaction was found to
be first o r d e r . The ortho-para hydrogen conversion was independent
of the degree of decationation. It seemed to depend on impurities
since there was a variation in examples from different sources.
There was no poisoning effect at - 196°C of the hydrogen gas.
The hydrogen-deuterium equilibration w a s also studied by
Turkevich and Ciborowski a t room temperature and above. The re-
action was self-poisoned and was sensitive to evacuation technique;
an evacuation of 17 hours at a temperature of 480°C was necessary
to obtain reproducible results. This is the treatment that converts
Bronsted acid sites into Lewis acid s i t e s and Bronsted base s i t e s ,
The catalysts subjected to this treatment showed a catalytic activity
which increases linearly with the degree of decationation. Hydrogen
treatment at room temperature for several days or at 250" for 30
min completely deactivates the catalyst for reaction a t 25°C. This
activity was restored only by evacuation at 480°C. The amount of
hydrogen adsorbed was independent of the degree of decationization
and was 6 x 10l8 molecules/gram of the catalyst; the number of de-
cationated s i t e s was two o r d e r s of magnitude l a r g e r . Oxygen also
poisoned the reaction. The nature of the active site for the hydro-
gen-deuterium exchange is either a peculiar crystallographic a r -
rangement of decationated sites or an impurity associated with a
decationated site.
14 JOHN TURKEVICH
IX. HYDROGENATION
A Japanese patent [4] discloses the hydrogenation of oils at 180°C

under pressure on a nickel catalyst supported on a zeolite.
Weisz and Frillete [ 5 ] reported selective hydrogenation of a nor-
mal olefin a s compared to a branched-chain olefin over a catalyst
consisting of a platinum-impregnated A-type zeolite. Thus 50% of
butene- 1 and no 2-methylpropene w a s hydrogenated in a feed of
equal volumes of the two olefins when it was passed with hydrogen
a t 25°C and a t a contact time of about 1 sec over Pt A zeolite, Equal
quantities of both olefins were hydrogenated on a platinum-on-alu-
minum catalyst.
In dehydrosulfurization of petroleum, a U.S. patent [ 6 ] , recom-
mends preparing a catalyst by converting a Na 13X zeolite in the
cobalt form by ion exchange and then mixing with a corresponding
amount of molybdenum oxide. A catalyst so prepared, containing
0.3 wt. ?' & COO and 10% MOO,, was particularly effective in treating
W e s t Texas crude petroleum containing 0.3% sulfur. Under standard

conditions of desulfurization and with a spece velocity of 1.0 to 1.8
hour1, the sulfur content was lowered to 1.5 and 340 ppm, respec-
tively.
Borunova et al. [ 7 ] studied the hydrogenation activity of nickel
zeolite catalysts obtained by both cation exchange and precipitation.
The Ni-Na A zeolite, obtained by cation exchange and containing
3.84% N i %nd a ratio of N i to Na of 0.2 to 1.0 and having a pore diam-
eter of 4 A , hydrogenated octene at 130°C with a yield of 81.5 wt. %;
isoamylene, at 50"C, diisoamylene at 160", and benzene a t 180" were
not hydrogenated.
The Ni-Na X zeolite, obtained by cation exchange and 2ontaining
7.9% nickel and a ratio of N i to N a of 0.66 and having 10-A pore dia-
meter, hydrogenated octene at 130°C to 90% yield but obtained hydrog
enated benzene to only 5%, although the pores of the zeolite were
capable of admitting benzene. This low activity was explained by the
destruction of the pore structure of the zeolite on reduction, as
shown by a marked lowering of water vapor of the catalyst after r e -
duction.
The catalyst prepared by precipitation of 5.8% N i on N a A hydrog-
enated octene completely at 130°C and benzene to 67% at 180°C.
The alkylbenzene was hydrogenated to 36%. Thus no selectivity was
shown. A catalyst prepared by precipitation of N i to 3.65% on the
zeolite did not hydrogenate cyclohexene. This compound underwent
nonreversible hydrogenation of 87%.
A U.S. patent [8] proposed to prepare active and stable catalysts
for the hydrogenation, dehydrogenation, and dehydration of alcohols
ZEOLITES AS CATALYSTS -- 15
and f o r ammonia synthesis by introducing one o r several metals of

the iron group into an X zeolite. The process of introduction con-
sists of ion exchange of the zeolite with a solution of the salt of the
metal, or with an ammine complex or with a liquid compound of the
metal (carbonyl, hydrocarbonyl, or acetyl acetonate) in an inert at-
mosphere. The metal is then oxidized by air. A s zeolites contain-
ing cobalt oxide are used for hydrodesulfurization, those containing
f e r r i c oxide a r e used for the removal of carbon monoxide from hy-
drogen.
Breck discloses in a U.S. patent [ 9 ] the possibility of loading
zeolites of the type A, D, R, S, T, X, and Y and naturally occurring
zeolites with metallic zinc or zinc oxide for the purpose of obtain-
ing a catalyst for the synthesis of methanol.
X. DEHYDROGENATION
Galich and co-workers [ 101 studied the catalytic dehydrogenation

of n-hexane at 475-525°C at a space velocity of 0.5 hour-' over a
series of catalysts prepared from Na A, Ca A, Na X, and Ca X zeo-
lites. The Na A was modified to contain 1.5% nickel o r 11.4% cobalt,
whereas the N a X was made to contain 8.3% nickel and 9.3% cobalt.
The nickel was introduced by impregnation with nickel nitrate, the
cobalt with cobalt chloride. The Ca A and the Ca X zeolites were
impregnated with f e r r i c hydroxide to give a 5% Fe,O, zeolite and
with chromium hydroxide to give a s e t of zeolites containing 1.7 to
30% Cr,O,. The unmodified Ca A zeolite gave a high yield of gaseous
products and catalyzed the cracking reaction. Introduction of Cr,O,
favored dehydrogenation. At 500°C a maximum yield of 7.7% liquid
olefins was obtained with a Ca A zeolite containing 15% Cr,O, The .
activity became constant after 2 hours of operation. The Na-Ni A
zeolite gave 5.6% gaseous products containing 83.7% hydrogen. The
liquid contained olefins and up to 1.5% aromatics.
Galich and co-workers [ l l ]found that the Ca A zeolite, in con-
trast to aluminochromium catalysts, dehydrogenated n-olefins into
linear olefins without cyclization or carbon skeleton isomerization
Analogous results were obtained on Ca A zeolites containing Pt and
Ni.
XI. CRACKING
Weisz and Frillete [ 5 ] showed that the Na and the Ca X zeolites

had a higher activity f o r cracking a t 470°C of n-decane a t atmospher-
ic p r e s s u r e than the standard aluminosilicate catalyst (25%, conver-
16 JOHN TURKEWICH
sion). The introduction of calcium ion (39% conversion) for the so-
dium ion (32% conversion) increases the activity. The products ob-
tained with the Ca X zeolite are similar to the products obtained in
t h e presence of the aluminosilicate catalyst. On the Na X zeolite the
amount of unsaturated hydrocarbons (62%) was twice that observed
on the standard aluminosilicate catalyst (3’7%) and no isomers were
found. On the aluminosilicate catalyst, the isopentane/pentane ratio
was 3.0, whereas on the Ca form it was 2.4.
The Na form is inactive for dealkylation of isopropylbenzene
even at 510”C,although the Ca form produces “extensive conversion”
at 465°C. The conversion of a-pinene to camphene follows the same
pattern-Na form inactive, Ca form active.
A U.S. patent [ 121 discloses a process of hydrocracking of highly
aromatic crude petroleum on a catalyst obtained from the 1OX o r the
13X zeolite containing hydrogenating materials such a s MOO,
(9 wt.%) and COO (3 wt.%) o r their sulfides. The feed was a gas oil
fraction boiling in the temperature range of 204-427°C. If the crude
petroleum contained paraffin hydrocarbons, the process should be

carried out at 399-510°C.
Keovgh and Sand [ 13 ] showed an unusually high catalytic-cracking
activity of synthetic mordenite both in its N a form and H form at the
rather low temperatures of 350°C even in the presence of coke. The
acid form of the mordenite, stable to 800”C, was characterized by
adsorbent properties intermediate between those of A zeolites and
faujasite.
Wolf and Losse [14] showed, using decationated zeolites with dif-
ferent contents of aluminum oxide (20 to 80%), that there is a direct
relation between acidity and activity of the catalyst.
Galich and co-workers [ 151 investigated the nature of carbon de-
posits formed in Ca A zeolite on cracking of n-alkanes and showed
that the process of dehydrogenation-cyclization and isomerization
does take place in the pores, but due to the limited size of the open-
ings of the pores, the hydrocarbons formed do not have an opportu-
nity to leave and condense to form up t o lo%, coke, which can only be
removed by destruction of the structure of the zeolite.
Galich and Golubenko [ 16 ] investigated the transformations of
dodecane on Ca A zeolite.
Frillete e t al. [ 1 7 1 studied t he cracking of n-hexane, methylpen-
tane , n-decane, decene- 1, and cumene on N a X and Ca X zeolites,
and also on a conventional aluminosilicate catalyst. The reactions
were carried out using a 50-ml catalyst in a Pyrex reaction vessel
a t normal atmospheric pressure. The space velocity was 1 hour-‘
and the reaction period was 3 hours. The regeneration of the cata-
lyst, carried out after each run, was first at a temperature of 370-
400"C, taking care that the catalyst bed temperature never exceeded
500°C. The powder catalyst was pressed into 3-mm pellets before
use. No binder w a s used in the pelleting. The conversion of n-hex-
ane at 500°C w a s 16.4 wt.% on amorphous silica and higher at 24.59
on the Na X zeolite. On the other hand, the conversion for methyl-
pentane at 500°C was higher on amorphous aluminosilicates at 33
wt. % than it w a s on the Na X zeolite at 23.6 wt. %. Quantitative r e -
sults were presented that n-hexane was catalytically cracked on
N a X, Ca A, and Ca X zeolites but not on N a A , whereas 3-methyl-
pentane was cracked on Na X and Ca X but not on Na A and Ca A .
This i s consistent with the general observation that amorphous
aluminosilicate p r e f e r s to c r a c k branched-chain hydrocarbons over
straight-chain hydrocarbons. The Na X does not have this charac-
teristic. This result was a l s o correlated with the penetration of the
two hydrocarbons into the interior of the zeolites. n-Hexane cannot
penetrate into the Na A zeolite and the 3-methylpentane cannot pene-
trate into the N a A and Ca A zeolite. The Ca A zeolite excludes
from its pores branched-chain hydrocarbons, and the Na A lattice

excludes all hydrocarbons.
n-Decane cracked more on the Ca X zeolite than on Na X and
least of all on the amorphous aluminosilicate catalyst. At 470°C the
depth of cracking w a s 48, 32, and 26 wt. o/o, respectively. The values
for depth of cracking a t 500°C were not reported for Ca X; for N a X
they were 49 wt. a and for the amorphous aluminosilicate catalyst
they were 33 wt.%;. Another way of comparing the catalysts is to
compare the temperatures a t which the depth of cracking is 25-30
wt. % of the C,- to C,-compounds. For Ca X the temperature is 470°C
and for N a X and amorphous silica it is 500°C. Analysis of the
cracked products shows that, whereas the amorphous aluminosilicate
catalyst gives about equal amounts of C5-, C4-, and C,-hydrocarbons
(26, 28, and 31 mole % ) , a smaller C,-fraction (lo%),and a still small-
er methane fraction (5%), the Ca X zeolite produces a cracked prod-
uct with a maximum of C, (39%) and the C,-fraction remains high
at 22%, the C,-fraction is slightly smaller at 24%, the C,-fraction is
7%,,and the methane production rises to 9%. The N a X zeolite a s a
catalyst produces a product whose distribution is shifted markedly
to lower carbon values. The greatest yield is the C,-fraction at 28
mole yo, and the C, at 27 mole %. The C4-fraction drops to 18% and
the C, t o 11%.On the other hand, the methane production increases
to 16%.
The following distribution was found in the products between the
paraffins and the olefins, The amorphous aluminosilicate catalyst
gives about equal amounts of olefins and paraffins in each of the car-
bon number fractions, except in the case of the C,-fraction where
18 JOHN TURKEVICH
propylene (17 mole %) is higher than propane (14 mole %). The Ca X
zeolite produces more paraffins in each fraction than olefins. Thus
the C,-fraction has 19 mole % of paraffins and only 3.2 mole % of
olefins; the C,-fraction, 29 v e r s u s 9%; the C,, 15 versus 10%; and
the C,, 5 versus 2%. On the Na X zeolite, the C,-paraffins (5%) a r e
slightly lower than the C,-olefins (6.2%) and the C,-paraffins (7%)
are markedly lower than the C,-olefins (11%). In the C,-fraction the
olefinic component i s about the same as the paraffinic, and in the C,-
fraction ethane (19%) is more prominent than ethylene.
The distribution of the is0 compounds i s markedly affected by the
use of Na zeolite a s a cracking catalyst. Amorphous aluminosilicate
gives equal amounts of branched- and straight-chain hydrocarbons
in both the C,- and C,-fractions. Using the Ca X zeolite, iso-C,-com-
pounds were markedly greater than the normal C,, and the iso-C,
(16%) were produced to a smaller extent than normal C, (22%). The
effect of Na X zeolite on suppressing the production of is0 com-
pounds in catalytic cracking is marked, the product distribution
being 11 mole % of normal C, v e r s u s 1%of iso-C, and 18.1% of nor-

mal C, versus 0.3 iso-C,,. In contrast to the Ca X and to amorphous
aluminosilicate, the coke production on Na X is smaller.
Decene-1 is cracked more easily on amorphous silica than on
Ca X zeolite and cracks less easily on Na X. Thus the temperature
necessary for 25-30% conversion to the C,-C, products on amorphous
silica is 365°C (compared to 500°C f o r n-decane); on Ca X it is
430°C (compared to 470°C for n-decane); and on Na X it is 500°C
(compared to 500°C for decane). Data on the product distribution of
the cracking of decene on aluminosilicate is not given. On Ca X and
on Na X the carbcn number patterns of the products are the same
for decene and decane. The amount of olefins on Ca X i s twice that
produced from n-decane, and the olefins seem to be produced at the
expense of the normal paraffins. The isoparaffin production on Ca
X from decene is the same a s that produced by decane.
On Na X decene does not produce more olefins than decane, and
the general cracking pattern is similar to that produced by decane.
Again there i s a marked absence of branched-chain hydrocarbons.
Double-bond migration was noted in the butenes and pentenes since
these were found to contain the double bond in both terminal and in-
ternal positions.
Cumene cracking was found to be small at 510°C over Na X (6%),
more extensive over Ca X (59 a t . a t 470"C), but not so extensive
over amorphous aluminosilicate. The authors were not able t o mea-
s u r e it exactly but stated that it was g r e a t e r than 60% at 470°C. The
product distribution was markedly different on Na X than on the
other two catalysts. Hydrogen yield was 26 mole R of the converted
cumene, whereas this gas was not produced when Ca X was used as
a catalyst. The methane was 21 mole %, whereas it was only 1.3%
on Ca X. These cracking and dehydrogenation products were pro-
duced a t the expense of benzene and propylene. The benzene yield
was 22%, whereas on Ca X it was 49%; the propylene yield was 10
versus 38% on Ca X.
Peguzova and Vatukhina [ 181 studied the cracking of the kerosene-
gas oil fraction and showed that with increase in the degree of ex-
change of Ca for Na in the X zeolite the activity index increased
from 33.8 to 43 wt. % with the space velocity of 1 hour-l. The H and
the Ca forms of the Y zeolite give twice the yield that the Ca X zeo-
lite gives under the same conditions. None of the commonly used
aluminosilicate catalysts gives comparable activity under the same
reaction conditions. Mixed catalysts obtained by filling the silica
gel or spherical forms of aluminosilica catalysts with Ca X o r Ca Y
zeolites in amounts greater than 25% gave a lower activity index of
31-380/0. However, treatment of such catalysts with 100% water vapor
a t 650°C for 20 hours produced a catalyst of very high activity, The

product consisted of aromatic and paraffin-naphthene compounds
and a very small amount of unsaturated hydrocarbons. The iodine
number of the product was 7-9. The cracked gas was rich in is0
compounds and the yield in the C,-C, fraction was 48-55 wt. %. The
activity of the Ca X, Ca Y, and H Y form did not decrease after 4-5
cycles for the Ca form and 12 cycles for the deeply decationated Y
zeolite. Coke deposits of 4% and higher could be easily burned off
the catalyst in 1.5-2.5 hours.
Tsitsishvili and co-workers [19] reported that the zeolites
N a X, Ca X, and H X showed considerable catalytic activity for
cracking of cumene at temperatures over 400°C.
Topchieva and Romanovski [ 2 0 ] studied the cracking of cumene
and pseudocumene on Linde 1OX zeolite and amorphous aluminosilicate
catalysts. The cracking process was shown to be parallel on the two
catalysts, but the Linde 1OX catalyst showed a much lower activity
than the aluminosilicate Houdry-type catalyst.
Schwab and Sieb [21] studied the catalytic activity and the activa-
tion energy in the cracking of cumene and pseudocumene on N a X
zeolites and zeolites obtained from the Na form by replacement of
the Na by other ions. The replacement of the Na ion by divalent
cations Ca or Mg decreased the activation energy of 55 kcal/mole
by a factor of 2. The replacement of the Na by Zn and Mn also low-
ers the activation energy, and this decrease is proportionally lower
than that observed for Mg and greater than that observed for Ca in
small depths of replacement. However, in the case of the replace-
ment of N a by Cd, the activation energy increases with replacement.
20 JOHN TURKEVICH
For Mg, Ca, Zn, and Mn there is a minimum of activation energy

with replacement and then a flat region. The authers ascribe this
flat value to the fact that at large degrees of replacement the r e -
placement takes place in deeper layers of the catalyst which are not
available to the cumene.
Boreskova and co-workers [ 221 investigated cumene cracking
activity, poisoning by quinoline adsorption, and the infrared adsorp-
tion in the 1500-1650 cm-l region of a number of zeolites: Ca(930/,)-
Na(?%) zeolite, Na(57%)-NH4(43%)Y zeolite, and Na(77%)-NH4(23R)
Y zeolite. The zeolites were compressed into tablets of 10-15 mg/
cm3 by high pressure. The quinoline poisoned the cumene cracking
reaction at 419"C, the amount of quinoline just necessary to poison
being 0.9 and 0.5 mm/gram of the Na(57%] and Na(779$) Y zeolites,
respectively. Characteristic changes were observed in the infrared
spectrum which were correlated with the adsorption of quinoline on
the aprotonic sites. These sites were held responsible for the cata-
lytic activity of the decationated zeolites. The activity of the calcium
Y zeolite was attributed t o an incompletely compensated aluminum-

oxygen tetrahedron.
Oktuzhnov et al. [23] studied the dehydrodealkylation of toluene and
ethylbenzene at 420-460°C under hydrogen pressure of 10 kg/cm2
over an A zeolite impregnated with nickel. The ethylbenzene w a s
first converted into toluene and then into benzene. The amount of
ethane and benzene hydrogenation products w a s insignificant at
400°C. The extent of dehydroalkylation increased with increasing
space velocity from 1 to 2.5 hour-'. The ratio of hydrogen to hydro-
carbon was 5 and the apparent activation energies found for the two
compounds were 45 and 35 kcal/mole.
Boreskova and co-workers [ 241 studied cumene cracking on Na,
Na-Ca, Ca, and decationated zeolites. They found that the decation-
ated zeolite showed the highest activity and that the activity of the cal-
cium forms decreased with decreasing calcium content. On poison-
ing the decationated zeolite with quinoline, the activity decreased
linearly with the introduction of quinoline until 90 @ of I
quinoline
was introduced per gram of the zeolite and the activity remained
constant. The results were explained by assuming that there were
two types of sites on an active catalyst: aluminum surrounded by
tetrahedrally coordinated oxygens and aluminum coordinated in a
threefold way with oxygens. The quinoline poisoned only the latter
sites in a decationated zeolite. In the Ca X and the Ca Y zeolites,
the former type of sites were present but not the latter type.
Topchieva et al. [25] studied the cracking of cumene on a s e r i e s
of zeolitic catalysts, The X type had a Si/Al ratio of 1.2, and the Y
type had a ratio of 1.7. The Na X contained 17.8% Na,O; the Ca X-
0.5 was 49.7% exchanged and had 9.4% CaO and 9.08% Na,O. The
Ca X-0.75 w a s 66.6% exchanged and analyzed 6.1% Na,O and 12.6%
CaO. The Ca X was 83.3% exchanged and analyzed 3.3% Na,O and
15.8% CaO. The Ca Y-0.75 was 78% exchanged and analyzed 4.06%
Na,O and 14.1% CaO. The NaNH; was 50% exchanged and analyzed
9% Na,O, whereasNaNH2,‘ was 23% exchanged and analyzed 7.7%
Na,O. Linde 1OX and Linde 13X were also investigated. The cata-
lysts were heated at 500°C for 6 hours and then placed in a s t r e a m
of the inert gas. A microreactor was used and the unreacted
cumene and products were collected in a liquid-nitrogen trap. After
vaporization of the t r a p s , the products were analyzed in a gas
chromotographic column using a polar liquid u0P-7” supported on
diatomaceous earth. The products from the analytical column were
converted to carbon dioxide and then detected. A straight line was
obtained on plotting the log l/l-x (where x is the fraction of cumene
converted against the reciprocal of the velocity of the c a r r i e r gas).
The slope gave the product of the reaction constant times K, the ad-
sorption equilibrium constant. The adsorption characteristics were

determined by investigating the retention time of cumene, benzene,
and propylene in a temperature range 290-450°C below the temper-
ature of reactivity. The retention time for cumene was greater than
that for either benzene or propylene. It is greatest for the Na X and
decreases as the Na is replaced by Ca. It i s lower for Ca Y and has
the lower values for partially decationated N a X zeolite. The reten-
tion time for both cumene and benzene is lowest for the decationated
Y zeolites. The retention time for propylene is lower than that of
benzene. The heat of adsorption was determined from the variation
of the logarithm of the retention time against the reciprocal of the
absolute temperature. The heat of adsorption of cumene is indepen-
dent of the calcium content and of whether the zeolite i s an X or a Y
zeolite. It is lower for the decationated form. The heat of adsorption
of benzene is lower than that of cumene on all the zeolites. The heat
of adsorption of benzene on Linde 13X of 18 kcal/mole agrees well
with the value of 17 at 25-70°C obtained by B a r r e r and with the value
of 15.5 at 260-482°C obtained by Eberly. The heat of adsorption of
benzene increases with replacement of Na by Ca and gives the lowest
value for decationated zeolites. Thus the heat of adsorption s e e m s
to be independent of the reactivity of the zeolites, and the bulk of the
adsorption does not take place on the reactive sites in the catalyst.
Examination of Table 1 shows that the velocity constant for the
cracking of cumene increases with the degree of replacement of N a
by Ca and increases by an order of magnitude on decationization.
The dependence of the activation energy on catalyst composition is
not clear c u t . Its value for an inactive Na zeolite is 47 kcal. Intro-
TABLE la
NaX CaX-0.5 CaX-0.75 CaX CaY-0.75 CaY N ~ N H

N ~~ N H ~ i-3 x lox
K/secb 5x 9x 1.3 X lo-' 1.5 x lo-' 4.4 x 2.8 x 0.15 0.25 - 8x
E 47 40 38 38 29 31 30 32 - 39
K x 104 60 15 22 35 6.2 1.4 4.1 4.1 - 12
N
N moles/atm/g
of cumene
H cumene, 27 26 25 26 23 24 21 21 25 28
kcal/gm
H benzene 20 19 24 27 18 21 15 15 18 21
'Topchieva et al. [25].
bK is the velocity constant, E the activation energy, and H the heat of adsorption.
duction of Ca into the zeolite lowers the activation energy to 38 kcal.

However, further introduction of Ca does not affect the activation
energy. The Y zeolites have a much lower energy of activation than
the X zeolites. The decationated Y zeolites, although they have a
much greater activity than the Ca Y, have about the same activation
energy.
The authors also report titrating a decationated catalyst with
quinoline in much the same way as was carried out in the investiga-
tion of Turkevich et al. They report that for the NaNH; catalyst
0.09 mM of quinoline p e r gram lowers the cracking of cumene at
420°C from 19% to about 1%. They also report that quinoline does
not poison the Ca X and Ca Y zeolites. The conclusion is that the
active centers in the decationated zeolites a r e aluminum atoms in
a threefold coordination state and that in the cationated zeolites
there a r e aluminum oxygen tetrahedra with incompletely compen-
sated charges.
Weisz and Miale [26] compared the hexane cracking activity of a
number of natural and synthetic zeolites a s modified by cation-ex-

change processes. A flow microreactor was used in which the
stream of helium saturated with heptane vapor a t 25°C was passed
over the catalyst bed with contact time of 9 sec (superficial volume
of catalyst/gaseous volume flow rate). The yield at 5 min after the
commencement of the flow was measured. The particale size of the
catalyst was 12 mesh o r less. The catalysts were compared with an
aluminosilicate coprecipitated amorphous material which had 10%
silica and a surface area of 420 m2/g. This catalyst gave a 12.5%
conversion of n-hexane at 580°C. The temperature of investigation
for the zeolites was 275-550°C, the temperature chosen being such
that the conversion of n-hexane was from 5 to 40%. The conversions
were found to follow the Arrhenius rate equations with about the
same activation energy. The Arrhenius plot was extrapolated to
538°C and the rate constant compared at this temperature with that
obtained with alumina silica gel to give an activity-constant alpha.
The preparation of the base material, the conditions and depth of
cation exchange, and the conditions for calcining were not given. Nor
w a s there evidence given whether the crystalline structure under-
went degradation during the calcination process prior to catalyst
testing. The following base materials were used: synthetic faujasite,
Azeolite, mordenite, a ZK-5 material synthesized by Kerr, and sev-
eral naturally occurring zeolites (mordenite, chabazite, and stilbite).
The samples were exchanged with various cations. Hydrogen was in-
troduced either by acid exchange o r indirectly via exchange with NH,
ion and subsequent decomposition by calcination. The following re-
s u l t s were obtained with the various materials, the numbers in the
24 JOHN TURKEVICH
parentheses indicating the a-value for the particular zeolites. Very

low activity was shown by Ca faujasite (l.l),Ca A zeolite (0.6), and
Ca synthetic mordenite (1.8). The next group of increasing o r d e r of
activity was Ce-La-H via NH, synthetic faujasite (ZO), ZK-5 catalyst
(38), Ca-H synthetic mordenite (40-2001, and H via NH, natural stil-
bite (120). When the synthetic ZK-5 catalyst w a s hydrogen ex-
changed, it increased in activity (450). A very active group of cata-
lysts consisted of acid-treated natural mordenite (2500), H via NH,
synthetic faujasite (6400), and La-H faujasite (7000). The most ac-
tive group, characterized by the authors a s “superactive” with ac-
tivities greater than 10,000, was shown by the Ca-La acid-treated
synthetic faujasite, acid-treated mordenite, Ce-La-H via NH, syn-
thetic faujasite, acid-treated natural mordenite, H via NH, gmelinite,
and H via NH, chabazite. Weisz and Miale claim that conventional
testing involving accumulation of product may mask “superactivity”
due to rapid deactivation. However, the authors do not present any
evidence that the crystalline structures of the various samples were
preserved after cation exchange and a i r circulation.

Frilette and Rubin 1271 report that hydrogen-treated natural mor-
denite has an activity that i s comparable to HC1-promoted aluminum
chloride a s determined by cracking of n-hexane.
XII. DEHYDRATION
Weisz and Frilette [5] have c a r r i e d out the dehydration of isobu-

tanol in the presence of butanol-1 and found that the Ca A zeolite
selectively dehydrates the butanol- 1, whereas on the standard amor-
phous aluminosilicate catalyst both alcohols a r e dehydrated a t com-
parable r a t e s .
A U.S. patent [28] discloses the preparation of a cadmium catalyst
by loading an X zeolite with metallic cadmium and using it for the de-
hydration of primary alcohols. In particular this type of a catalyst
dehydrates ethanol to ethylene.
Tsitsishvili and co-workers 1,291 report that the dehydration of
isopropyl alcohol takes place more readily on decationated X than
on Na X than on Ca A zeolites. In the temperature range 240-270°C
the activiation energy for dehydration w a s equal to 7 . 4 kcal/mole on
Na X and 27 kcal/mole for decationated zeolite.
Minachev and co-workers [30] investigated the dehydration of al-
cohols on the Ca Y zeolite (Si/A1 ration = 1.7) in a flow system with
a velocity of 3.87 gram moles/hour/lO-ml catalyst. A t 250°C all the
primary alcohols dehydrate smoothly into the olefins. Thus ethyl al-
cohol gives 100& ethylene while a temperature 50” higher is neces-
s a r y to obtain complete dehydration of ethanol over the aluminosili-

cate catalyst. n-Propyl alcohol gives propylene with a 90% yield at
250°C and 100%yield at 275°C. The more reactive isopropyl alcohol
dehydrates smoothly at 230°C. Cyclohexane dehydration takes place
readily at 150°C to give 68% cyclohexene and gives 9 5 9 8 % at 160°C
and 100% a t 170°C. It was difficult to obtain a selective dehydration
of n- and isobutyl alcohols since the olefins produced underwent ex-
tensive polymerization. Isobutyl alcohol at 250°C produced only 65%
of the theoretical value of isobutylene.
Norton [31] reported at the 141st National Meeting of the American
Chemical Society that A and X zeolites a t 200-500°C and a t p r e s s u r e s
of 200- 1000 psi polymerize isobutylene more easily than propylene
and propylene more easily than ethylene. To activate the zeolites
they were dehydrated at low temperatures.
XIII. OXIDATION
Addison and Walton [ 321 report the direct oxidation of hydrogen

sulfide to sulfur dioxide and sulfur trioxide at 100°C on 4A zeolite
and at 200°C on Ca 13X zeolite. The zeolite w a s evacuated a t 300°C
and 1Od6-mmpressure before use. The hydrogen sulfide was ad-
mitted at 200°C and then the catalyst was lowered to reaction tem-
perature before oxygen was admitted. There was no decomposition
of hydrogen sulfide a t 200°C. On admission of oxygen a l a r g e r vol-
ume of oxygen was adsorbed then in the absence of preadsorbed hy-
drogen sulfide. Thus oxygen could not be desorbed at temperatures
as high a s 200"C, although some desorption could be effected
above 200°C. In the absence of hydrogen sulfide the desorption of
oxygen is reversible. The ratio of the volume of oxygen adsorbed
to the volume of hydrogen preadsorbed increases with an increase
in temperature and with a decrease of concentration of hydrogen
sulfide. It is greater in the 4 A zeolite than in the 13X zeolite. The
replacement of the Na ions by Ca ions decreases the ratio, as was
shown when the zeolite was changed from the 4 A to the 5A and from
Na 13X to Ca 13X. The products of the interaction of the hydrogen
sulfide with oxygen were analyzed by pumping off the reaction mix-
t u r e from the zeolite and analyzing it and also by treating the zeo-
lite hydrothermally and carrying out a qualitative analysis of the
aqueous extract. Sulfur dioxide was identified a s the gaseous pro-
duct by infrared analysis. Sulfur must have been deposited in the
pores of the zeolite because the sample became paraniagnetic and
also because after outgassing a t 300°C the sample adsorbed oxygen
irreversibly. This oxygen could be desorbed only at 300°C and only
as sulfur dioxide. As the ratio of oxygen to preadsorbed hydrogen
26 JOHN TURKEVICH
sulfide increased from 0.6 t o 2.0, the ratio of sulfur dioxide to sul-
fur trioxide in the product increased from z e r o to infinity, respec-
tive ly .
A U.S. patent [33] discloses the possibility of using zeolites of the
type A, D, L, R, S, T , X, and Y, and also naturally occurring zeolites
a s supports, for the oxidation of organic compounds and, in particu-
l a r , for the oxidation of ethylene to ethylene oxide.
XIV. ISOMERIZATION
Rabo and his associates [34] reported on the isomerizing action

of platinum and palladium catalysts supported by a variety of zeo-
lites on both n-pentane and n-hexane. A 100-ml stainless-steel re-
actor was used and the p r e s s u r e was 450 psi. The hydrogen-to-hy-
drocarbon ratio was 3 and the space velocity was usually 2.0 hour-l.
Three basic types of zeolites were used, type A, type X with a Si/A1
ratio of 1.2, and type Y with a Si/A1 ratio of 2.5. In addition, a stan-
dard amorphous aluminosilicate catalyst (with a Si/A1 ratio of 2.6)
was also used a s a support. The calcium form was obtained from
the sodium form by exchanging the latter with a CaC1, solution. The
decationated form was obtained from the sodium form by exchange
with ammonium ions and subsequent heating to decompose the am-
monium zeolite.
In the isomerization of n-hexane a t 450"C, the platinum on the Na
form of all the zeolites and of the amorphous aluminosilicate cata-
lyst, had no activity. The catalytic activity at 400°C of the calcium
forms differed with the nature of the zeolite. Four percent isohexane
was produced on 4w0 Na and 60% Ca amorphous aluminosilicate; 7%
isohexane on 21% N a and 79% Ca A-type zeolite with considerable
cracking since the liquid product was only 79% of the original charge.
Thirteen percent isohexane was produced on 13% Na and 8Wo Ca on
Y zeolite. The 22% Na and 78% Ca produced the high yield of 73%
isohexane and 12% 2,2-dimethylbutane at 375°C. The highest activity
in a support for Pt in isomerization of hexane was shown by the
decationated zeolites and the amorphous aluminosilicate. The latter
gave 73% yield of isohexane and 11%2,2-dimethylbutane at 425°C and
the f o r m e r on 15% Na and 85% NH, Y type gave 76% isohexane and
14% 2,2-dimethylbutane at 350°C. The 81% decationated A sieve gave
a considerable amount of cracking-the liquid yield was only 67%, al-
though it contained 47% isohexane-whereas the 76% decationated X
zeolite gave 12% isohexane. These last two supports may have de-
composed during the process since they a r e known to be sensitive to

thermal decomposition at high degrees of decationization.
A comparison was also made at 400°C of the effect of various ions
in the Y zeolite on the isomerizing activity of 0.5-wt. % platinum cat-
alyst. The monovalent ions showed low activity with the exception of
lithium, which gave a 9.2% yield of isohexane. The divalent ions pro-
duced excellent catalysts as the following listing of ion and the
amount of isohexane produced indicates: Ca, 67; Mg, 55; Zn, 60; Mn,
62: Strontium promoted cracking with only 79% of the charge remain-
ing as liquid product, although the latter contained 32% isohexane.
Whereas the catalyst containing trivalent aluminum a s cation could
not maintain its activity, the one containing trivalent cerium was ef-
fective in producing 66% isohexane. Tetravalent cerium was not ef-
fective.
Both platinum and palladium were effective as metals in concen-
trations of 0.5 wt. %. Thus Pt at 350°C produced 61% isopentane from
n-pentane, and at 340DC,14% 2,2-dimethylbutane and 76 mole % iso-
hexane from n-hexane. Space velocities were varied from 2 to 10

hour-' without appreciable change in the yield. The catalyst w a s
stable for thousands of hours on stream.
The palladium supported on decationized Y zeolite was more ef-
fective in isomerizing either n-pentane or n-hexane, operating a t a
temperature 50" lower than the platinum catalyst. It produced 64%
isopentane from n-pentane and 78% isohexane and 15% 2,2-dimethyl-
butane from n-hexane. The palladium catalyst was also stable for a
1000 hours and could tolerate small amounts of sulfur and large
amounts of water.
A s previously mentioned, the sodium form of the zeolite is inac-
tive a s a support for the palladium o r the platinum in the alkane iso-
merization process. Replacement of the sodium by calcium intro-
duces catalytic activity until 40% of t h e sodium ions had been re-
placed by the calcium at which stage the catalytic activity was
comparable to a catalyst that had 10% decationation. At 80% replace-
ment of the sodium by the calcium ions, the activity of the support
w a s equal to that of a 8w0 decationated Y zeolite. On the other hand,
the effect of decationation was more marked. Whereas the sodium
form had no isomerizing activity when it was impregnated with Pt
even at 480°C, 10%decationation produced a support which had
enough active sites to produce 50 mole % isoparaffins at 400°C.
Higher degrees of decationation produced a more active catalyst and
one that could be used at substantially lower temperatures.
Rabo and h i s associates [ 351 gave more details on the hydroiso-
merization reaction in a subsequent paper, Again they studied pen-
tane and hexane isomerization in a hyarogen atmosphere using the
same Pd catalyst on a modified zeolite support a s was reported
28 JOHN TURKEVICH
e a r l i e r . The temperature range w a s 32O-36O0C, and the ratio of hy-

drogen to hydrocarbon was 3. The p r e s s u r e ordinarily used in this
investigation was 450 psi. P r e s s u r e below 350 psi increased crack-
ing whereas above 600 psi a decrease in catalytic activity was ob-
served. A space velocity of 2 hour-l gave over 9@0 of the equilibrum
yield of the i s o m e r s . Decreasing the space velocity to 1 increased
cracking to lighter hydrocarbons and increasing it to 5 decreased the
extent of isomerization from 65 mole %J of isopentane to 62.5%; in the
case of n-hexane it decreased from 78.5 to 66.4%; 100 m l of catalyst
w a s used and no coke formation w a s noticed. The presence of con-
stituents with higher boiling points than pentane o r hexane did not af-
fect the yield. Sulfur tolerance was good. An increase of sulfur intro-
duced a s n-butyl mercaptan from 6 to 55 ppm decreased the yield of
isopentane from 62.5 to 55.0 mole %. An increase of the sulfur con-
tent to 3000 ppm dropped the isopentane yield to 27 mole %. When
the sulfur was removed from the feed, the yield jumped back to 62
mole %. Water in the feed had no effect on yield.
Typical r e s u l t s obtained with n-pentane feed containing 2.3%

methylcyclopentane at 350°C were 57.9 wt. % isopentane, 34.7% n-
pentane, 2.2yL isopentane, 1.1%butane, l.O%, propane, 0.2% ethane,
and 0.06% methane. Furthermore, some higher hydrocarbons such
a s 2,2-dimethylbutane, 2,3-dimethylbutane, 2- and 3-methylpentane
and n-hexane were also found in quantities l e s s than 1%.They were
undoubtedly produced from the methylcyclopentane in the feed be-
cause both this compound and cyclohexane a r e absent in the product.
The isomerization of n-hexane under the s a m e conditions pro-
duced 78.2-wt. %J conversion. The main products were 39.6% 2,3-
dimethylbutane and 2-methylpentane, 19.3% 3-methylpentane, and
13.9?, 2,2-dimethylbutane. The pentane yield was low-0.35% for nor-
mal and 0.64% for isopentane. The butane yield was 0.38$ normal
and 0.9% is0 compound. The propane yield was 1.55% and the ethane
yield 0.11%. The methane production was 0.03 wt. u/c. Some methyl-
cyclopentane and cyclohexane was found in the product, but it w a s
smaller than the impurity of methylcyclopentane in the feed.
A British patent 1361 discloses the possibility of carrying out in
the vapor phase at temperatures of 80 to 260°C the isomerization of
normal olefins of the C,-C, range and of branched olefins of the
C,-C, range on a 5A zeolite containing Fe, Mg, Pb, o r B. Ca and K
can be present only in trace amounts. The isomers formed are basi-
cally cis and t r a n s forms.
In connection with her thesis on the separation of isopentane-pen-
tane and isobutene-butene mixtures on a Ca A zeolite, Vinogradova
[37] found that a t 350-480°C the butenes underwent migration of the
double bond and a geometrical isomerization process whereby butene-
was formed which contained 25 c i s and 54 t r a n s isomers.

Bassett and Hapgood [ 381 studied the catalytic isomerization of
cyclopropane in a microreactor at 263-379°C on a 13X Linde zeolite
using flow techniques of 1 and 0.2 ml sec-l. The reaction was found
to be first o r d e r with an activation energy of 30 kcal/mole and with
a preexponential factor of 1.3 X lo1'. The heat of adsorption of cyclo-
propane under reaction conditions was 11 kcal. The authors propose
that the reaction proceeds through the carbonium ion intermediate.
However, they point out that the clay that i s used a s a binder in pel-
leting the zeolite may be catalytically active.
Minachev and co-workers [ 391 studied the isomerization of n-pen-
tane, n-hexane, n-heptane, and cyclohexane on Pd, Pt, Rh, and I r
catalysts supported on Y-type zeolites. The amount of metal was
usually 0.5% and the catalyst was reduced at 380°C; 10 m l of catalyst
was used. The experiments were c a r r i e d out in a flow system at 30-
atm p r e s s u r e with a space velocity of 1 hour1; the ratio of hydrogen
to hydrocarbon of 3.2 The isomerization of n-heptane does not pro-
ceed on metal catalysts produced from the Na Y zeolite. The r e s u l t s

obtained on C a Y type (with a Si/Al ratio of 1.7) at 400°C were the
same for both Pt and Pd. The total yield of isomers was about 60o/c,
consisting of 7.5% 2,2-dimethylbutane, 19.2% 3-methylpentane, and
32% 2,3-dimethylbutane and 2-niethylpentane. Increasing the Si/A1
ratio to 2.25 permitted lowering the temperature to 350°C with a to-
tal yield of isomers of 70%)with the various isomers increasing to
11, 23, and 36.4%, respectively. In the case of the palladium catalyst
in a zeolite with a Si/A1 ratio of 2.25, 88% of the equilibrium was
reached for all the isomers and 55'x of the neohexane equilibrium.
The rhodium and iridium catalysts produced, in addition to isomeri-
zation, some hydrocracking. Thus at 390°C the rhodium catalyst
gave 25.8% isomerization and 21.9% cracking, whereas the iridium
catalyst a t 310°C gave 6.6% isomerization and 26.6% cracking. A
fourfold variation of the palladium content from 0.5 to 1.0% on a Ca
Y zeolite with a Al/Si ratio of 1.7 had little effect on the isomerizing
activity.
The isomerization activity of the 0.5'& palladium on Ca Y with a
Al/Si ratio of 1.7 was also marked f o r both n-pentane and n-heptane.
For the f o r m e r the yield of i s o m e r s was 49.5% and of cracked prod-
ucts 2.58 at 400°C and increased to 52.8'h and 3.7y0, respectively at 420°C;
80% of equilibrium isomerization was reached. The results for n-
heptane at 360°C were 47.2 wt. % isomerization and 10.3 wt. % crack-
ing.
Cyclohexane is also isomerized on the platinum and palladium
catalysts to methylcyclopentane. With the 0.5% Pt on Ca Y with a
Si/Al ratio of 1.7 at 370"C, 47% methylcyclopentane and 1.8yLbenzene
30 JOHN TURKEVICH
were produced. With the same catalyst containing Pd instead of Pt,

the yield was 43% methylcyclopentane. Increasing the ratio of Si/Al
t o 2.25 permitted lowering the temperature to 300°C with a 45.7%
yield of methylcyclopentane. At 320" the yield went up to 51.5 mole
o/o and a t 330" to 57%. At the latter temperature there were 7.9%. At
cracking products. The iridium catalyst at 330" produced 52% crack-
ing and only 4% methylcyclopentane.
Minachev et al. 1391 studied the hydrogenation and hydroisomeri-
zation of benzene on Rh, I r , and Pd supported in 0.5 wt. OlO on Ca Y
zeolite which had a Si/A1 ratio of either 1.7 or 2.25. The pressure
was 30 atm, the space velocity in the flow type reactor was 0.5 hour-l.
The amount of catalyst was 10 ml. The ratio of hydrogen to benzene
was 5. The hydrogenation activity of the catalysts at 200°C was Fth,
Ir, and Pd giving a yield, on Ca Y with a Si/Al ratio of 1.7, of 97.8,
91, and 82.5 wt. 41, respectively. In the c a s e of the Pd catalyst in-
creasing the ratio 0; Si/A1 had no effect on the hydrogeneration ac-
tivity.
On increasing the temperature, a hydroisomerization reaction be-

gins to take place. Thus on the 0.5% P d on Ca Y catalyst with a Si/A1
ratio of 1.7 at 320"C, 20.1 wt. % of methylcyclopentane is produced
in addition to 63.5 wt. % of cyclohexane. Increasing the ratio of Si/&
to 2.25 increases the hydroisomerization of benzene at 320°C about
3.5 times, the yields being 67.3% methylcyclopentane, 28.4 wt. u/c
cyclohexane, and 5.7% cracked products. Lf the temperature is
raised to 370"C, the yields a r e 41.8 and 33.3 wt. qiL, respectively,
The iridium catalyst a t 320°C gave 5.8% hydroisomerization and 60
wt. u/c cracking. On the other hand, on the rhodium catalyst the values
were 12% and 16.9%, respectively,
Rabo et al. [40] studied the isomerization of n-hexane on Pt-Na-
Ca Y sieve prepared by ion exchanging the Na-Ca Y zeolite with both
the cation Pt(NH,), and the anion PtC1;- a t 350°C in a continuous flow
reactor a t atmospheric p r e s s u r e . In the first the platinum was intro-
duced by ion exchange of the Na or Ca ions by the Pt(NH,), cation,
whereas in the latter case the Pt was introduced into the catalyst by
impregnation of the PtC1, anion. Both catalysts showed steady, com-
parable activity for a period of 29 hours. The product composition
approaches the equilibrium proportions of the various isomers. The
total amount of C,-hydrocarbons v a r i e s from 92 to 87 mole o/o in the
various runs reported, and of these the amount of nonisomerized
n-hexane is 19-22 mole %; 19-22% of 3-methylpentane, 14-16"/0of
2,2-dimethylbutane, and 36-41% of 2,3-dimethylbutane and 2-methyl-
pentane. The total is0 hexane content v a r i e s from 70-72 mole %.
The amount of gas produced is small and C,-fraction is from 2-4%,
except in one short run where it is increased t o 10.8 mole %.

Introduction of 10 ppm of thiophene to the hexane feed did not af-
fect the activity of the overall conversion of n-hexane of the Pt(NH3)4-
impregnated catalyst, the conversion remaining at 79 mole YC. It did
decrease that of the catalyst prepared by impregnation with the anion
PtCl;, where the conversion dropped from 78 to 70 mole %. In the
case of the cation-impregnated catalyst the total C,-fraction re-
mained unchanged on introduction of the s u l f u r compound into the
feed, being 87-92 mole % before introduction and changing t o 86-93
mole % after. On the anion-impregnated catalyst the total C,-hydro-
carbons changed slightly from 88-9W0 before sulfur compound intro-
duction to 84-94% after contamination of the feed. Thus there was
no difference in the two types of preparation so far as the effect of
sulfur compounds on the overall destruction of the six-carbon chain.
There was little difference in the C,-production between the two cat-
alyst preparations before and after sulfur introduction of sulfur into
the feed. The effect of the sulfur was, however, noticeable in the
isomerization of the C,- compounds on the anion- impregnated cata-

lyst, the yield of iso-C, dropping from 70-71 to 62-66%. In the case
of the platinum catalyst obtained by cation impregnation, the product
analyzed 70-72% iso-C, before introduction of the sulfur impurity
and 68-72% after. The effect of the sulfur contamination expresses
itself particularly in the case of the anion-impregnated catalyst on
the yield of 2,Z-dimethylbutane with a change of yield of this isomer
from 14-15 to 7.1-14%. In the case of the cation-impregnated cata-
lyst the yield held up from 14-16% before introduction of the contam-
ination to 1 5 1 6 % after. The production of the other isomers of hex-
ane was not affected by the sulfur impurities, nor was the cracking
o r any coke production affected by sulfur introduction.
The sulfur poisoning is claimed to be reversible, with the small
change in the yield of 2,Z-dimethylbutane being restored on removal
of the sulfur from the feed. It is also claimed by the authors that if
the sulfur content is raised from 10 to 1000 ppm the activity reduc-
tion is irreversible. NO data is presented to support these claims.
In a further investigation Habgood and George [41] studied the
effect on the cyclopropane isomerization of the nature of the cation
in the zeolite. This was carried out in the presence of a small par-
tial pressure of water, and it was found that variation of the latter
from 0.0 to 3.6 t o r r increased the absolute rate of the reaction by a
factor of 5 without changing the activation energy. The activity in the
temperature range 150-400°C was in the following increasing order:
K X, N a X, N a Y , and Li X. The catalysts were activated by heating
in a stream of helium at 500°C. The decationated zeolites had a much
higher activity than the other materials. The activity was so high
that reaction products were only partially recovered, and f o r this
32 JOHN TURKEVICH
reason the rate constants could not be obtained. The catalyst color
turned dark after a few pulses. However, regeneration with oxygen
cleared the catalyst of color and restored the activity. The results
were reproducible, although the catalyst darkened in color with use.
The materials showed variability in catalytic properties from batch
to batch of catalyst.
With Li X the rate constant has a preexponential constant of
6.0 X 10l2 and an activation energy of 39,100 cal. The data on Li Y
was not reported, whereas for Na X the preexponential constant was
1.2 X 10l2 and the activation energy 40,500 cal. However, other lots
of Na X gave activation energies ranging from 34 to 46 kcal. The
Na Y was a slightly more active catalyst than the Na X and gave a
lower activation energy of 24.6 kcal. The activity of K X after stan-
dard activation was below detection. The deuterium exchange was
studied on a catalyst saturated with D,O at 2.8 t o r r . At 160"C, under
conditions when there was no isomerization, cyclopropane did not
undergo deuterization. However, a sample of propylene passed
through the catalyst showed considerable deuterization. At 317, 340,

and 374°C where the percent isomerization w a s 8, 11, and 36%, sig-
nificant dueterization of both unreacted cyclopropane and the propy-
lene product took place.
XV. ALKYLATION
In a patent Mattox and Arey [42] disclosed the alkylation of aro-

matic hydrocarbons by oAefins using X zeolites with a Si/A1 ratio of
1.25 and pore size of 13 A . On alkylating benzene with propylene at
250°C with a ratio of benzene to propylene of 1.5 and at atmospheric
pressure. Mattox and Arey obtained a 9 vol. % yield of an alkylate
comprising 83 vol. % isopropylbenzene and 17 vol. % polyalkylben-
zenes.
Minachev and co-workers [39] alkylated benzene with ethylene or
propylene in the vapor phase at atmospheric pressure on zeolites.
The authors report a yield of 45% of ethylbenzene in one passage with
a space velocity of 0.6 hour-l at 300°C In the case of alkylation with
a propylene-propane mixture, the Na Y zeolite was inactive. How-
ever, decationation via the ammonium form produces 50% yield
when t h e ratio of benzene to aliphatic hydrocarbons is 2. The Ca Y
form gives a 64% yield under these conditions. The optimal tempera-
t u r e for this catalyst is 250-300°C. On increasing the space velocity
calculated on benzene from 0.3 to 1.2 hour-', the yield of isopropyl
benzene decreases. On changing the molar ratio of benzene t o olefin
from 2 to 6, the yield of alkylbenzenes increases; however, the mono-
alkybenzene is the main product. The activity of the zeolite increases

with increase of the Si/Al ratio. The reaction products contain a
small percentage of C,-hydrocarbons (about 3%) and some polyalkyl-
benzenes. However, by proper choice of conditions a selectivity of
95-100yc for the production of monoalkylbenzene can be obtained. It
was also observed that the decationated zeolite obtained from the
Ca Y form is more active (at 250°C giving 66% yield) than the deca-
tionated catalyst obtained from the Na Y (at 300°C giving 50% yield).
A U.S. patent [43] discloses a process of alkylation using a 13X
zeolite at atmospheric p r e s s u r e at 204°C with the ratio of aromatic
to olefinic hydrocarbons of 1.5. At a conversion of 9.0 vol. % the
alkylate consisted of 83 vol. o/G monoisopropylbenzene and 17 vol. %
polyalkylbenzenes. The 4A zeolite was reported to be inactive. The
magnesium X zeolite was the most active. To obtain comparable
yields with conventional catalysts consisting of phosphoric acid on
keselguhr, one must use the more drastic conditions of 28 a t m ,
268"C, and a molar ratio of benzene to propylene of 5:lO.
Mays and Pickert [44] report that high activity for alkylation of
aromatic hydrocarbons with C,-C,, olefins o r alkyl halides can be
obtained at low temperatures and p r e s s u e s using catalyst prepared
from multivalent cation-exchanged or decationated Y-type zeolites.
The activity of such catalysts is comparable to that of aluminum
chloride promoted by HCl and is greater than that of amorphous alu-
minosilicate. Thus at 1-atm pressure and 150-250°C with a benzene-
to-olefin ratio of 5 and a benzene space velocity of 2-5 hour-l, using
ethylene o r propylene, a conversion of 80% based on the olefin was
obtained. The reactivity of the olefin in this reaction increases in
the o r d e r : propylene, butene- 1, butene-2, isobutylene.
REFERENCES
[ I ]R. M. B a r r e r , P r e p r i n t s of Society of Chemical Industvy Con-

f e r e n c e on Molecular S i e i ~ s London,
, 1967.
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141 Japan. Pat. 336 ( 1 9 5 5 ) .
151 P. B. Weisz and V . J . Frilette, J . Phys. Chem.,64, 382 (1960).
161 U. S. Pat. 2,967,159 ( 1961) .
171 N. V. Borunova, L. Kh. Freidlin, I. E . Neimark, V . G. Il'in, and
L. I. Gvinter, in l'siolity, ikh Sintcz, Siioistiia, i Prirnenenii,
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34 JOHN TURKEVICH
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V. G. Il'in, I. T., Golubchenko, and V. S. Frolova, Neftekhimiya
A k a d . Nauk, Soedin. ( U k r . S S R Inst. Khirn. Vysokomolekul .),
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1111 N. P. Galich, A. A. Gutyrya, V. S. Gutyrya, and I. E . Neimark,
Dokl. Akad. Nauk. SSSR, 144(1), 147 (1962).
[12] U.S. P a t . 2,983,670(1961).
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[14] F. Wolf and A. Losse, C h e m . Zng, Tech., 33, 6, 1442 (1961).
[15] P. N. Galich, Gutyrya e t al., Neftekhimiya, 2, 193 (1962).
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Academy of Sciences, Moscow, 1962 (in Russian).
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301 (1962).
[18] L. I. Peguzova and A. S. Vatukhin, C h e m . T e c h . F u e l s Oils,
6,17 (1963);Russ. Pat. 845,219-845,223(1964).
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(1963).
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149(3), 644 (1963).
[21] M.Schwab and B. Sieb, 2 . Naturforsch., 18a, 164 (1964).
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Kataliz, 5(6), 1115 (1964).
[23] A. M.Oktuzhnov, R. I. Izmailov, and R. A. Virobyants,
Neftekhimiya, 4,677 (1964).
[24] E. G. Boreskova, K. V. Topchieva, and L. I. Pigusova, Kinetika
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1251 K.V. Topchieva, E . G. Boreskova, and L. I. Pigusova, Study
and Uses of A d s o r h e n t s , Zeolity Nauka, Moscow, 1965.
I261 P. B. Weisz and J. N. Miale, J . Catalysis, 4,527 (1965).
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1341 J . A . Rabo, P. E. Picker t, D. Stamir e s, and J . E. Bogle, A c t e s
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Zeolites As Catalysts 1

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I11. STRUCTURAL CHARACTERISTICS O F T H E FAUJASITE

Zeolites are crystalline aluminosilicates of the general formula

lent v is equal to one-half x. The cation can be exchanged reversibly

In the middle of the eighteenth century Baron Cronstadt observed

boil at the s a m e time. This phenomenon was called intumescence and

and were able to p r e p a r e in the laboratory not only s o m e of the nat-

11. CLASSIFICATION OF ZEOLITES

About 40 zeolites which occur in nature and a number which have

Na,,Ca,,l A148Si,20,4,,J * 64H,O; gonnardite, Na,Ca,~A1,Si,,04,] * 12H,O;

following min e r al s : gmelinite, Na,[Al,Si,,O,,] . 24H,O; offrite,

111. STRUCTURAL CHARACTERISTICS O F

Inasmuch as m os t of the catalytic work on zeolites involved the

The oxygen tetrahedron has in its center either an atom of silicon,

SiO:-, or aluminum, A10:-. Since the charge on the aluminum oxy-

Rings a r e formed of silicon (alumina) tetrahedra by bridges of

ment is the basis, as we have seen, of the modern classification

the 4-membered rings is negligible. There a r e six 4-membered

between Linde X and Y, there may be a variety of distributions of

VI. CAGE UNITS

bered rings into three-dimensional open structures. We must dis-

minum atoms a t each of the four hexagonal faces arranged in the

96 oxygen atoms, and a number of sodium atoms equal to the number

cules of toluene; 4.5 molecules of normal pentane; 0.1 molecule of

tion of oxygen i s equal to 6 l O k . This value indicates that the oxygen

ture consists of sodalite cages Nal,(A1O,),,(SiO,),, ($-cages) attached

The cations may occupy three different positions in the zeolite.

evolution of water and ammonia permitted the evaluation of the

VII. CATALYTIC STUDIES

A number of catalytic studies have been c a r r i e d out using molec-

VIII. ORTHO-PARA HYDROGEN CONVERSION

Ortho-para hydrogen reaction was c a r r i e d out a t - 196°C on so-

A Japanese patent [4] discloses the hydrogenation of oils at 180°C

W e s t Texas crude petroleum containing 0.3% sulfur. Under standard

and f o r ammonia synthesis by introducing one o r several metals of

Galich and co-workers [ 101 studied the catalytic dehydrogenation

Weisz and Frillete [ 5 ] showed that the Na and the Ca X zeolites

petroleum contained paraffin hydrocarbons, the process should be

from its pores branched-chain hydrocarbons, and the Na A lattice

being 11 mole % of normal C, v e r s u s 1%of iso-C, and 18.1% of nor-

a t 650°C for 20 hours produced a catalyst of very high activity, The

For Mg, Ca, Zn, and Mn there is a minimum of activation energy

Y zeolite was attributed t o an incompletely compensated aluminum-

sorption equilibrium constant. The adsorption characteristics were

NaX CaX-0.5 CaX-0.75 CaX CaY-0.75 CaY N ~ N H

duction of Ca into the zeolite lowers the activation energy to 38 kcal.

number of natural and synthetic zeolites a s modified by cation-ex-

parentheses indicating the a-value for the particular zeolites. Very

preserved after cation exchange and a i r circulation.

Weisz and Frilette [5] have c a r r i e d out the dehydration of isobu-

s a r y to obtain complete dehydration of ethanol over the aluminosili-

Addison and Walton [ 321 report the direct oxidation of hydrogen

Rabo and his associates [34] reported on the isomerizing action

composed during the process since they a r e known to be sensitive to

hexane from n-hexane. Space velocities were varied from 2 to 10

e a r l i e r . The temperature range w a s 32O-36O0C, and the ratio of hy-

Typical r e s u l t s obtained with n-pentane feed containing 2.3%

was formed which contained 25 c i s and 54 t r a n s isomers.

ceed on metal catalysts produced from the Na Y zeolite. The r e s u l t s