Section 111 - Paper 16
u. s.A.
MOLECULAR SIEVES IN PETROLEUM AND NATURAL GAS PROCESSING
T. L. Thomas*
Abstract. Molecular Sieves are discussed i n terms of
their basic physical properties which are related to ad-
sorption and catalytic applications in the petroleum and
natural gas industries. An up-to-date review of the struc-
tural and chemical properties of Molecular Sieve mat-
erials is presented including new Molecular Sieve products
such as Types 3A, 1OX, AW-500 and Y. Fundamentals of
adsorption with Molecular Sieves are discussed with
emphasis on molecular sieving effect, preferential polar
adsorption, zeolitic adsorption and rates of adsorption.
A schematic representation o f a petroleum refinery shows
where Molecular Sieve adsorbents and catalysts are being
employed in commercial processes today and where they
have potential use in the future. Basic adsorption process
cycles used in these refinery applications are described
with advantages and disadvantages of each. The technical
and economic aspects of some of the more important
Molecular Sieve refinery processes are presented, in-
cluding the Linde IsoSiv process for recovery of normal
paraffins in the c5-ClO and CiO-ci6 ranges. Molecular
Sieve catalysts are discussed in as far as they have been
developed and revealed up to the present time.
Molecular Sieves in P e t r o l e u m and
Natural Gas Processing
Molecular Sieves were introduced to the industry
by Linde Company, Division of Union Carbide Cor-
poration, late in the year 1954. Since that time they
have been applied commercially by the process
industries to the drying and purification of a large
variety of gas and liquid streams. In ad,dition, many
petroleum and chemical companies are now devel-
oping proprietary processes for the recovery of
* Thomas, Tudor L. / USA / Physical Chemist /
BS, MS, PhD., University
of Michigan / Manager, Molecular Sieves Development, Linde Com-
pany Division, Union Carbide Corporation.
Résumé. On décrit les Tamis Moléculaires du point de
vue des propriétés physiques qui sont en rapport avec
leur emploi comme adsorbants ou catalyseurs dans I’in-
dustrie du pétrole e t celle du gaz naturel. On présente un
sommaire d’après les données les plus récentes des pro-
priétés structurelles et chimiques des Tamis Molécu-
laires, y compris des produits nouveaux tels que Types
3 A , I O X , AW-500 et Type Y. On discute les principes de
l’adsorption avec les Tamis Moléculaires, en soulignant
la séparation produite par la différence de dimension
moléculaire et de polarité, ainsi que l’adsorption zéoli-
tique et la vitesse d’adsorption. Un tableau schématique
d’une raffinerie de pétrole montre où les adsorbants et
les catalyseurs à basr de Tamis Moléculaires peuvent
être utilisés dans les procédés commerciaux actuels,
ainsi que leur emploi potentiel dans l’avenir. On décrit
des procédés d’adsorption employés dans ces raffineries,
en relevant les avantages et les désavantages respectifs.
On présente les aspects techniques et économiques de
quelques procédés à Tamis Moléculaires plus importants,
y compris le Procédé IsoSiv de Linde pour la récupération
des paraffines normales dans les fractions C5-Ci0 et
ciO-Cl6. On présente les catalyseurs de type Tamis Molé-
culaires et leur développement jusqu’à l’heure actuelle.
components present in refinery or plant process
streams at concentrations of up to 50 O/o or more. With
Molecular Sieve a,dsorption processes, the chemical
engineer is now finding at his command a tool as
potent as distillation, liquid absorption or fractional
crystallization.
In th,epast several years, Molecular Sieves, proper-
ly modified, have been found to have novel catalytic
prope,rties which have or will soon find their way
into new or improved refinery processes.
The purpose of this paper is to: (1) present an up-
to-date review of the structural and chemical proper-
ties of the various Molecular Sieve materials; (2)
discuss fundamentals of Molecular Sieve adsorption;
115
(3) project these materials and processes employing
them into an integrated petroleum refinery operation
summarizing the present commercial and future po-
tential points of application; (4) from this refinery
review present operating and economic data on
several new Molecular Sieve edsorption processes of
current interest; and (5) discuss application of Mole-
cular Sieves as catalysts in petroleum processing.
Molecular Sieves - Structure and Properties
Molecular Sieve materials belong to a class of
compounds known technically as zeolites. These ma-
terials are hydrated, crystalline, metal aluminosili-
cates. Their outstanding characteristic is their ability
to undergo dehydration with little or no change in
their crystalline structure. These dehydrated crystals
are interlaced with regularly spaced channels of uni-
form molecular dimensions in which adsorption can
occur. Depending on the size of these intracrystal
voids, molecules may be readily adsorbed, slowly
adsorbed or completely excluded.
The zeolite crystal structure consists of a three-
dimensional framework of si04 and A104 tetrahedra.
The alumina tetrahedron is slightly larger than the
silica tetrahedron. In the zeolite structure, however,
an aluminum ion can isomorphously replace the sili-
con ion in the silica tetrahedron. The alumina tetra-
hedra carry a negative charge, and, therefore, a posi-
tive charge supplied by a metal cation must be asso-
Figure 1
Molecular S i e v e T y p e A Crystal M o d e l
116
ciated with each alumina tetrahedron in the crystal.
These metal cations in the zeolite structure are
responsible for some of the pore size variations
possible in these materials. They are also probably
responsible for the very strong and selective adsorp-
tive forces which are unique with Molecular Sieve
adsorbents. In the case of Molecular Sieve catalysts,
catalytic activity can be controlled and varied by the
nature of the cations in the crystal.
Although similar in composition, these crystalline
zeolites are completely $differentin structare from the
gel type amorphous aluminosilicates commonly re-
ferred to as zeolites. These amor2hous zeolites have
been available for many years as water softeners. In
adsorption applications, they are very similar to some
silica gels. They have the same broad spectrum of
pore sizes as the silica gels (20-10,000 angstroms
typically) and, therefore, do not exhibit any molecu-
lar sieving activity.
Molecular Sieve Type A: The following formula
shows the chemical composition for one unit cell of
the Type A crystal 1, 2) :
Meldn [(Aloz) iz(SiO2)12] 27 H 2 0
Each unit cell contains 24 tetrahedra, 12 of silica and
12 of alumina, with each oxygen shared between two
tetrahedra. Sufficient metal cations Me of charge n
are available to balance the charge of the alumina
tetrahedra. This material on heating loses its water
of hydration without loss or change of its crystal
structure. The dehydrated or activated crystal is the
111116
active adsorbent which in commercial form is pellet-
ed or beaded with 20 O / o inert clay binder.
Figure 1 shows a model of the basic unit cell of
this material. The white spheres represent oxygen
atoms and the dark spheres sodium cations. The very
small silicon and aluminium ions in the tetrahedral
holes are not shown. The cubic unit cell is 12.32
angstroms on a side with 8-membered oxygen rings
in each of the six faces. These 8-membered oxygen
rings of about 4.2 angstrom diameter afford openings
which lead into a large 11.4 anstrom $diametercavity
in the center of the unit cell where adsorption occurs.
In order to be adsorbed, the molecule must be small
enough to enter through the 8-membered oxygen
ring.
Figure 2 shows a projection of two adjacent unit
cells so that the relative size of the openings and the
O EXTENT O F CALCIUM ION EXCHANGE
4 A*
Figure 2
Projection o f two adjacent unit cells of Type 4 A . Open
circles represent oxygen ions. Shaded circles represent
sodium cations.
cavity can be visualized. Eight (only four actually
shown in each unit cell in Figure 2) of the twelve
sodium cations in each unit cell are located in each
of the eight 6-membered oxygen rings located at each
corner of the threefold axes. Each of the remaining
four sodium cations in the unit cell occupies a posi-
tion adjacent to an 8-membered oxygen ring. In these
positions, the sodium cations restrict the size of the
molecule which can enter through the opening and be
adsorbed in the cavity. This sodium form of the Type
A Molecular Sieve will exclude all molecules larger
than about 4 angstrom in diameter and is designated
as Type 4A. It will adsorb all simple compounds, such
as HeO, COe, H2S and hydrocarbon molecules con-
taining less than three carbon atoms.
111/16
The Molecular Sieve zeolite materials are easily
ion exchanged. By ion exchanging the sodium ions of
the Type 4A structure with calcium cations, the
sodium ions restricting the entrance of a molecule
through the 8-membered oxygen are removed. As a
result, only molecules larger than about 5 angstroms
are excluded. Figure 3 shows the effect of the per
c3
n
a
n
w i2-
I-
(2C0"/(2Co"+ No')
Figure 3
Elfeci of calcium ion exchange on pore size of Molecular
Sieve Type A. Data at 25O C. and 700 mm Hg for: ( a ) iso-
butane (5.6 A diameter); ( b ) n-butane (4.9 A diameter);
(c) carbon dioxide (2.8 A diameter).
cent calcium ion exchange. The Type A Molecular
Sieve with more than about 30 O/o of the sodium ex-
changed for calcium cations will adsorb molecules
up to about 5 angstrom and is designated LINDE
Molecular Sieve Type 5A'. As seen in Figure 3, car-
bon dioxide with a 2.8 angstrom diameter is adsorbed
equally well on both Type 4A and Type 5A. Iso-
butane with a 5.6 angstrom diameter is excluded from
both. On the other hand, n-butane with a 4.9 angstrom
diameter is excluded until 30 calcium exchange is
reached. With a greater per cent calcium exchange,
'Commercial LINDE M o l e c d a r Sieve Type 5A is about
70 O/O calcium exchanged.
117
 it is adsorbed very rapidly. This Molecular Sieve diameter, essentially only water and carbon dioxide,
Type 5A adsorbs the same molecules as Type 4A, and and is designated LINDE Molecular Sieve Type 3A'.
in addition, it will adsorb straight chain hydrocar- Types 4A and 5A have excellent thermal stability.
bons excluding both the branched chain hydrocar- They may be heated to 700' C. for limited periods of
bons and those cyclic hydrocarbons with more than time with no effect on their crystallinity or adsorp-
3-membered rings. tion properties; however, since the alumina content
of these Type A materials !is relatively high, they are
If the sodium ions of the Type 4A are replaced by
susceptible to 'degradation by acids or adsorption of
potassium cations, the effective size of molecules
strong acid \gases. Drying of chlorine-, hydrogen chlo-
that can be adsorbed i s reduced. This is probably due
ride-, sulfur dioxide-, or nitrogen oxide-containing
to replacing the sodium ions adjacent to the 8-mem-
gases causes rapid deteriorahion of crystallinity and
bered oxygen rings with larger potassium ions. As
adsorption capacity.
the extent of the potassium exchange increases, there
Molecular Sieve Type AW-500: Whereas, Molecu-
is no discontinuous change in the size of the mole-
lar Sieve Type A has a Sioz to AhOs ratio of about 2,
cules that are adsorbed as was the case with the cal-
Molecular Sieve Type AW-500 has a ratio of about
cium exchange. The graidual change in effective size
6.7. This decreaseld alumina content of the alumino-
t- 30
2
W
I I I
more stable to acid solutions and to adsorption of
m strong acbd gases than Type A materials. The effec-
a ,
2O tive pore size of Type AW-500 is about 4.7 angstroms,
a 25- -
that is, slightly smaller than that of Type 5A; how-
D
W
t-
ever, Type AW-500 will adsorb practically the same
ft size molecules as Type 5A including normal paraf-
u
a
v)
I
4
œ
O
0
a
W
a
n
W
m
a
O
ö
Q

5a
œ
c
l

Effect of potassium i o n exchange on pore size of Moie-
cular Sieve T y p e A. ( a ) water (3.2 A diameter) at 700 mm
Hg, 25' C.; (b) methanol (4.0 A diameter) at 4 mm Hg,
25' C.; ( c ) carbon dioxide (2.8 A diameter) at 700 mm Hg,
25O C.; ( d ) acetylene (2.4 A diameter) at 700 mm Hg,
25' C.; (e) ethane (4.0 A diameter) at 700 rnm Hg, 25' C.;
. ( f ) o x y g e n (2.8 A diameter) at 700 mrn Hg, - 183' C.
of the molecules which can be adsorbed is shown in
Figure 4. This potassium exchanged material will
a,dsorb readily those molecules about 3 angstroms in
-
areas where the smaller pore sizes are ineffective.
The following formula shows the chemical compo-
sition of a unit cell of the Type X crystal:
Mess/n [AlOz)ss (Si02)106] 276 HzO
The unit cell contains 86 alumina tetrahedra and 106
silica tetraheldra with sufficient metal cations of
'Commercial LINDE Molecular Sieve Type 3A is about
10 "/o exchanged with potassium.

118 111116
valence n to balance the charge of the alumina tetra- Molecular Sieve Adsorption
hedra. On heating, the crystal loses its water of hy-
dration. This dehydrated or activated material is the Molecular Sieves act as physical adsorbents in al-
active adsorbent. The sodium form has been de- most all cases. This means that a molecule is held
signated LINDE Molecular Sieve Type 13X and the within the Molecular Sieve crystal by relatively
calcium form as LINDE Molecular Sieve Type 10Y. weak, physical forces of the van der Waals type.
Type 13X is stable thermally to 700'C.; however, When the molecule is desorbed by the application of
Type 1OX loses its crystallinity and adsorption capa- heat or by 'displacement with another material which
city at temperatures over 500' C. is adsorbeid more strongly, it leaves the Molecular
Sieve crystal in the same chemical state as when it
The adsorption occurs through 12-membered oxy-
entered.
gen rings which, in the case of Type 13X, will pass
Adsorption on Molecular Sieves is characterized
molecules up to about 10 angstroms in diameter and,
by a Langmuir type isotherm, where the amount of
in the case of Type lOX, will pass molecules of 9
a given compound adsorbed increases rapidly to a
angstroms and less, The pores of these materials are
saturation value as its pressure or concentration in-
of sufiicient size so that, in addition to those mole-
creases in the external bulk phase. Any further in-
cules adsorbed by Type 5A, most of the other com-
crease in pressure at constant temperature causes no
mon chemical compounds can be adsorbed, including
further increase in the amount adsorbed. With Mole-
branched chain paraffins, naphthenes and aromatic
cular Sieves this equilibrium saturation value usually
hydrocarbons.
corresponds to completely filling the internal void
Molecular Sieve Type Y : Molecular Sieve Type Y** volume with the material adsorbed. The desorption
has the same crystal structure as Type X but has from Molecular Sieves shows no hysteresis, that is,
different chemical composition. This chemical differ- the adsorption and desorption are completely rever-
ence is due to the iisomorphous replacement of sili- sible with the respective isothermal curves coin-
con ions for aluminum ions in the alumina tetrahedra ciding completely. With the pelleted Molecular Sieve
of crystal. As a consequence of the fewer alumina material, however, some further adsorption may
tetraheldra in Type Y , there is a corresponding reduc- occur at pressures near the saturated vapor pressure
tion in metal cations. Whereas Type X has a SiOz due to the condensation of liquid in the intercrystal-
to Alzo3 ratio of about 2.5, the Type Y may have ratios line voids in the pellet.
of from 3 to about 6 depen'ding on the extent of the The external surface area of the Molecular Sieve
isomorphic replacement of silica for alumina within crystal is available for adsorption of molecules of all
the crystal structure. sizes, whereas .the internal area is available only to
Whereas the intracrystalline diffusion in Type Y molecules small enough to enter the Molecular Sieve
through 12-member oxygen rings is the same as in pores. The external area is only about 1 O/o of the total
Type X, other properties which are influenced basic- surface area. Materials which are too large to be ad-
ally by chemical nature of the crystal lare differ- sorbed internally will commonlv be adsorbed ex-
ent. The lower metal cation content of Type Y ternally to the extent of 0.2-1 wt. O / o .
results in less selective adsorption than in Type X. For Molecular Sieves are effective adsorbents because
example, the relative adsorptivity of ethylene over of two unique characteristics: (a) they are capable of
ethane is less on Type Y than on Type X. The rela- separating materials based on their molecular size
tively higher silica content of Type Y makes it more and configuration; and (b) they adsorb molecules,
stable to acidic solutions and adsorption of strong particularly polar and polarizable molecules, with a
acid gases. In addition, the catalytic activity of Type tenacity not found with conventional adsorbents. The
Y , probably resulting from the particular location of effects of these characteristics are discussed below.
the alumina tetrahedra in the crystal3), is greater Molecular Sieving: Based upon the size and confi-
than that of Type X. guration of the molecules, Type 4A will readily ad-
sorb materials such as HzO, C O Z ,HzS, SOz, and all
*Commercialform of LINDE Molecular Sieve Type 1OX is hydrocarbons containing one or two carbon atoms.
70 O/o exchanged with calcium. Propane and higher hydrocarbons are physically ex-
** This material not as yet available commercially. cluded with the exception of propylene, which is ad-

111/16 119
sorbed much more strongly and, therefore, can enter
the pore system. Type 5A, in addition to adsorbing the
same compounds asType4A,will take up straight chain
paraffins, olefins, andalcohols up to at least Czz. With
the exception of cyclopropane, it will exclude all
branched chain, naphthenic, and aromatic molecules.
Type 13X will adsorb molecules with diameters up
to about 10 angstroms. Type 1OX will adsorb mate-
rials of 9 angstroms diameter and less. Di-n-propyla-
TABLE I
SELECTIVE ADSORPTION BY MOLECULAR SIEVE
Adsorbed on 4A, Adsorbed on 5A, lOX,
5A, lOX, and 13X and 13X, but not on 4A
Water n-Butanol and higher n-alcohols
Methanol n-Butene and higher n-olefins
Ammonia Propane and higher n-paraffins up
Hydrogen sulfide to a t least C,,
Sulfur dioxide Cyclopropane
Carbon dioxide Refrigerant-12
Propylene
Ethylene
Ethane
Adsorbed on 13X
but not on 4A, 5A, or 1OX
Di-n-propylamine
Di-n-butylamine
Molecules larger than 9 but less than 10A
molecules which have been used to determine the
effective pore size of these materials.
Preferential Adsorption of Polar, Unsaturated, and
Aromatic Compounds: Not only are Molecular Sieves
capable of separating molecules based on their size
and configuration, but also, if two molecules are
small enough to enter the pore system, the Molecu-
lar Sieve will adsorb one preferentially to the other
based on polarity or degree of unsaturation. Polar
and unsaturated molecules are selectively adsorbed.
The more polar or the more unsaturated the molecule,
the more tightly it is held within the crystal.
The inorganic gel adsorbents, such as silica gel and
activated alumina also exhibit this preference for
polar molecules, but to a far lesser extent than do
Molecular Sieve adsorbents. The very strong adsorp-
tive forces in Molecular Sieves are due primarily to
the cations which are exposed in the crystal adsorp-
120
mine with a critical diameter of 9.1 angstroms is ex-
cluded from Type 1OX but is readily adsorbed by
Type 13X. Type 1OX will adsorb ( C B F ~ ) ~ N Cwhich
~HÏ
has a (diameter of 8.7 angstroms. Type 13X will not
adsorb (C4Fg)3N with a critical diameter of 11.5
angstroms.
Table I summarizes the common materials which
are aidsorbed by each type of Molecular Sieve and
includes in the case of Types 1OX and 13X those
Adsorbed on 1OX and 13X,
but not on 4A or 5A
i-Butane and all i-paraffins
Benzene and all aromatics
Cyclohexane and all cyclics with at least
4-membered rings
Molecules larger than 5.0 but less than 9 A
(CPS),NC,H,
Not Adsorbed
on 4A, 5A, 1OX or 13X
(C4F913N
Molecules larger than 10A
tion surface. These cations act as sites of strong,
localized positive charge which electrostatically
attract the negative end of polar molecules. The more
polar the molecule, i.e., the greater the dipole moment,
the more strongly will it be attracted by the cationic
charge and the more strongly it will be adsorbed.
’
Polar molecules are generally those which contain O,
S, C1, or N atoms a n d o r are asymmetrical.
In addition to polar molecules, polarizable mole-
cules are strongly adsorbed. Under the influence of
the localized, strong positive charge of the cations,
molecules can have dipoles induced in them. This
polarized molecule is then adsorbed strongly due to
the electrostatic attraction of the cation. The more
unsaturated the molecule, the more polarizable it is
and the more strongly it is adsorbed in the Molecular
Sieve adsorbent. Figure 5 shows the adsorption of
two molecules, carbon monoxide and argon, which
111116
 W
m
u

I
0.8 3
MOL FRACTION ETHANE I N ADSORBATE
Figure 6
Relative adsorptivity of ethane-ethylene mixtures on:
( a ) Molecular Sieve Type 4 A, 730 mm H g , 25' C.; (b) si-
lica gel, 360 mm Hg, 25O c.; (c) Columbia G carbon,
360 mm H g , 25' C.
I-
z
PRESSURE mm Hg
~ W
m
œ
Figure 5 O
rn
Adsorption of polar compounds. Isotherms on Molecular 0
a
Sieve Type 5 A at - 3 5 T . ( a ) carbon monoxide, polar,
o
boiling point - 194' C.; (b) argon, non-polar, boiling w
l-
point - 186O C. a
2
I-
V
have approximately the same volatility. The carbon a
rn
monoxide molecule is polar and is adsorbed to a H
a.
much greater extent than is the argon which is non- œ
<3
polar. O
0
Molecular Sieves will effectively recover acety- œ
lene and olefins, such as ethylene and propylene, a
from saturated hydrocarbons. Figure 6 shows the n
w
m
very high selectivity which Molecular Sieves have œ
for ethylene in preference to ethane compared with v:o
that of silica gel and activated carbon. a
LL
Water is a strongly polar molecule. As a conse- w
quence, Molecular Sieves are excellent desiccant à
3
materials for the drying of gases and liquids. LL
O
Zeolitic Adsorption: The isotherms for the adsorp- VI
tion of polar molecules on Molecular Sieves are quite 3n O'
o 5
I
IO 15 20 25
different from the adsorption isotherms for the con- <3
H20 PRESSURE, mm Hg
ventional adsorbents such as silica gel, activated
Figure 7
alumina, and activated carbon. These zeolitic iso-
Equilibrium water adsorption capacities at 25' C. (a) si-
therms rise very steeply at relatively low prL nssures lica gel; (b) Molecular Sieve Type 5 A ; (c) activated
or concentrations as can be seen from Figure 7. Mole- alumina.

111/16 121
cular Sieves, therefore, have high adsorption capa-
city for water and other polar molecules at low pres-
sures. This means that Molecular Sieves can be used
to remove these materials to very low concentrations
(often to a few p.p.m. or less) from gas or liquid mix-
tures with high adsorption capacities.
Another important feature of zeolitic adsorption is
the fact that the adsorption is much less sensitive to
i
3 cules, the adsorption will be faster than if the mole-
100 200 300
TEMPERATURE "C
Figure 8
Equilibrium water adsorption capacities as a function of
temperature at 10 mm Hg water pressure (a) Molecular
Sieve T y p e 5 A ; ( b ) silica gel; (c) activated alumina.
temperature than is the case with other adsorbents.
Molecular Sieves adsorb more material at higher
temperatures than is possible with silica gel, activat-
ed alumina, or carbon. This may be seen from the
water adsorption isobars presented in Figure 8. This
characteristic of Molecular Sieves is particularly im-
portant when adsorptive separations must be carried
out at unusually high temperatures.
122
Rate of A d s o r p t i o n : The rate at which a given
material will be adsorbed on Molecular Sieve pellets
in any operation is dependent primarily on four var-
iables: (a) the rate at which the material being ad-
sorbed can diffuse to the activated Molecular Sieve
crystals within the pellets; (b) the relative size of the
molecule and the Molecular Sieve pore; ( c ) the
strength of the adsorptive forces between the Mole-
cular Sieve and the adsorbate; and (d) the tempera-
ture.
In all systems using Molecular Sieve, care must be
taken to provide conditions necessary for rapid dif-
fusion of the adsorbate to the Molecular Sieve crystal
in the pellet. This assures that external resistance to
diffusion is not the limiting rate factor. In those cases
where the adsorbate molecule has nearly the same
diameter as the Molecular Sieve pore, the adsorption
rate may be slowed appreciably. An example of this
latter effect is the adsorption of propane on Type
4A. In these cases, however, if the molecule is
strongly a,dsorbed, as with polar or unsaturated mole-
cule is less strongly adsorbed. This is illustrated by
the fact that propylene is readily adsorbed on Type
4A, but propane is adsorbed so slowly as to be prac-
tically excluded.
The rate of adsorption may in some cases be u s d
to practical advantage. Within the time of a given
adsorption operation, one material may be adsorbed
rapidly to give a practical separation from another
which is adsorbed very slowly. In other cases an ad-
sorbate may be adsorbed so slowly as to be com-
pletely excluded for all practical purposes. In cases
in which the adsorption is slow, it is usually found
that the 'desorption is particularly slow and difficult.
Isobaric Effect: In physical adsorption it is ther-
400
modynamically necessary that the amount adsorbed
decreases as the temperature increases. This, of
course, refers to equilibrium conditions and in no way
preidicts what may occur due to rate effects. It is be-
lieveld that such rate effects cause the anomalous
effect observed with the adsorption of carbon mono-
xide, nitrogen, and argon on Type 4A in the tempe-
rature range of -193 to about -80' C., as shown in
Figure 9. Instead of increasing monotonically as the
teimperature is lowered, in these cases the adsorption
capacity passes through a maximum. Since these
molecules, CO, Nz, and A, are very close to the pore
size lof the Type 4A pore, it appears that they do not
have sufficient activation energy at these low tem-
111116
peratures to readily enter the pores and be adsorbed. Molecular Sieve units in present day refineries have
They are probably adsorbed, at an extremely slow been installed primarily to provide drier and purer
rate, if at all. Oxygen, on the other hand, has a smal- feed and product streams. As petroleum catalytic
ler molecular diameter and is adsorbed in the normal processes continue to be improved and new proces-
manner over this entire temperature range. ses are developed, high purity feedstocks will be-
come even more essential; and, therefore, critical
removal of feed contaminant is the solution. Mole-
cular Sieves because of their wide range of adsorp-
tion selectivities are and will be a primary solution.
a 12
O As seen from Figure 10, Molecular Sieve processes
v)
P
a have already demonstrated their ability to handle
n
W
i-
s
c
4 \
such requirements. It is also evident that the ever in-
creasing demand for tighter product specifications
is making adsorption processing prominent in pro-
O
a duct finishing operations.
v) In addition, in the past year, Molecular Sieve pro-
I
2CY cessing has entered the petroleum refinery with pro-
prietary, bulk separation processes developed by a
O
0 number of different companies. These processes are
a primarily for two different separations, one for the
W
n removal and/or recovery of normal paraffins in the
n range of from C4 through C20, and second, for the
W
m
a upgrading of hydrogen in various hydrogen process
O
v)
o
streams to purities of 90-99.9 f O / o hydrogen. In the
a modern refinery there is growing demand for: (a)
v)
new sources of hydrogen; and (b) new methods of
5a upgrading hydrogen already available.
W
The remaining sections of this paper will discuss:
-200 -160 -120 -80 -40 O 40
(1) basic adsorption process cycles; (2) the technical
TEMPERATURE, OC
and economic aspects of some of the more important
Figure 9 Molecular Sieve adsorption processes shown in Fig-
Adsorption isobars on Molecular Sieve T y p e 4 A ai 700 ure IO; and 3) Molecular Sieve catalysts as far as
mm Hg (a) oxygen; ( b ) carbon monoxide; ( c ) nitrogen; they have been developed and revealed up to the
( d ) argon.
present time.
This isobaric effect, that is, the existence of a
maximum in the adsorption isobar, for Nz, CO, and
Process Cycles
ar,gon has also been noted with other systems, such
as propane an,d butane on Type 4A at elevated tem-
Molecular Sieve fixed-bed operation encompasses
peratures.
a wide variety of process cycles. Adsorption on
Molecular Sieves proceeds easily and with a high
Molecular Sieve Processing in the degree of efficiency; however, this advantage is usu-
Petroleum Industry ally counterbalanced when the time comes to reverse
the process and desorb. Since desorption is usually
Figure 10 depicts the place of Molecular Sieves in the most inefficient step in the cycle, the various
the petroleum industry. This schematic representa- cycles differ primarily in the manner by which de-
tion of a petroleum refinery shows where these cry- Sorption is accomplished. These cycles can be classi-
stalline adsorbents are being employed in commer- field into the following types and their combinations:
cial processes to,day and where they have potential 1. Thermal swing cycles using either direct heat
use in the future. Study of this Figure 10 reveals that transfer by contacting the bed with a hot fluid,

111/16 123
 il n ABSORBER O I L DRYING
ETHYLENE REMO VAL
PROPYLENE REMOVAL
CRACKED GAS D R Y I N G
N A T U R A L GAS DRYING
PROPYLENE DRYING
C$ RECOVERY
HzS RECOVERY B U T Y L E N E DRYING
N - H E P T A N E DRYING
E T H Y L E N E DICHLORIDE DRYING
PROPYLENE DICHLORIDE DRYING
P H E N O L DRYING
A C R Y L O N I T R I L E DRYING
IsoSiv -N-PARAFFIN SEPARATION CYCLOHEXANE DRY1 NG
FEEDSTOCK DRYING B U T A D I E N E DRYING
FE E DSTOCK DESU L F U RI Z A T ION R E F R I G E R A N T DRYING
CA T A L Yric CONVERSION CO2 R E M O V A L FROM Cp H a
PETROCH E M IC A L
I S 0 BUTYLENE PURIFICATION
ISOPRENE PURIFICATION
PROPANE- PROPYLENE SPLITTING
ETHANE - ETHYL EN€ SPLITTING
UNSATURA TE RECOVER1ES
I s o S i v - N - P A R A F F I N SEPARATION SYN. GAS SWEETENING
RECYCLE Hp DRYING NATURAL GAS SWEETENING
CATALYTIC RECYCLE H p SWEETENING TAIL GAS CLEAN-UP
COZ FROM NATURAL GAS
REFORMING FEEDSTOCK DESULFURIZATION Fz IFGRADING
FEEDS TOCK D ENI TROGENTION
HzS REMOVAL I N HYDROTREATING
CATALYTIC CON VERSION
HYDROGEN UPGRADING

PROPANE S W E E T E N I N G
B U T A N E S'N E E T E N I N G
L P G DRYING
-
IsoSiv BUTANE S P L I T T I N G
B E N Z E N E DRYING
F E E D S T O C K DRYING
X Y L E N E DRYING
CATALYTIC CONVERSION S O L V E N T DRYING
J E T F U E L DRYING
LPG SWEETENING
NA PH THA SWEETENING
PEROXIDE REMOVAL
HYDROGEN PURIFICATION DIOL € F I N REMOVAL
Hz UPGRADING
FEEOSTOCK PURlFl CA TI ON
RECYCLE Hp DRYING
n
TRANSFORMER OIL DRYING
LUBE OIL DEWAXING

V hI
CATALYTIC
CRACKING
UNSATURATE RECOVERY
Hz RECOVERY
CRACKING CATALYST
HzS REMOVAL
MERCAPTAN REMOVAL
CATALYTIC
CATALYTIC CONVERSION

*
COMMERCIAL APPLICATIONS AROMATICS EX TRA C TI O N
PO T E N T I AL APPLICATIONS

RESIDUUM PROCESSING

Figure 10
Molecular Sieve processing in the petroleum industry.
124
 or indirect heat transfer by heating the bed
through a surface such as finned tubes.
2. Pressure swing cycles.
3. Purge gas stripping cycles using an essentially
nonadsorbed pmge gas.
4. Displacement cycles where the adsorbed phase
is displaced by an adsorbable purge.
Thermal Swing Cycles: The first type of cycle, a
thermal swing cycle, is defined as any cycle which
employs different temperature levels for adsorption
and desorption. Temperature of desorption is always
higher than that for adsorption. A major feature of a
thermal swing cycle is that high design loadings can
usually be obtained on the adsorbent; however, a
cooling step must be considered as an additional item
of expense.
Two methods for transferring heat required to
raise and lower adsorbent temperature are by direct
and indirect heating. An example of direct heating is
the passage of hot gas through the adsorbent bed.
In the latter case, the heating fluid does not come in
contact with the solid adsorbent. From a process
standpoint, the methods differ primarily in quantity
and type of purge gas used. This, in turn, affects type
and size of auxiliary process equipment required.
Pressure Swing Cycles: The second type of cycle,
a pressure swing cycle, can be operated at nearly
isothermal conditions. A temperature level is select-
ed such that by conducting adsorption at an elevated
pressure, desorption can be accomplished by a reduc-
tion in total pressure. For high design loadings, va-
cuum desorption may be useful. A pressure swing
cycle is simple because no heating and cooling steps
are involved. Any heat requirements to maintain
bed temperature can be provided by the adsorber
feed stream itself. Because additional time is not re-
quired for heating and cooling the beds, the pressure
swing cycle, as well as other adiabatic cycles, can
generally be designed to operate rapidly. A fast cycle
reduces adsorber dimensions and Molecular Sieve in-
ventory. In addition to the advantages of a rapid
cycle, pressure swing cycles have the following two
features:
1. Direct production of a high purity product.
2. Ability to utilize gas compression as the main
source of energy.
Purge Gas Stripping Cycles: The third type of pro-
cess cycle, purge gas stripping, employs a non-ad-
sorbable purge gas for desorption. The purge gas
111/16
reduces the partial pressure of the adsorbed com-
ponent and causes desorption to occur. Adsorbates
pass from the adsorbent into the vapor over the bed,
are pickeld up by the purge gas, and swept from the
bed. Purge gas stripping of Molecular Sieves is more
efficient the higher the operating temperature and
the lower the operating pressure.
The use of a condensable gas to strip Molecular
Sieve beds is advantageous for Iwo reasons:
1. Power requirements for fluid circulation are
reduced substantially when a liquid pump in-
stead of a gas blower can be used to circulate
the purge.
2. The effluent stream may be condensed and the
desorbeid material separated from the purge
fluid by simple distillation.
A passible application of a non-condensable strip-
ping gas is the use of recycle hydrogen where a re-
sulting mixture of n-paraffins and hydrogen could
be fed directly to a conversion process such as cataly-
tic reforming.
Displacement Cycles: A displacement cycle, the
fourth process cycle, employs an adsorbable fluid to
displace all or part of the material loaded on the bed.
Often, the displacement fluid must be separated from
both the adsorbate as well as the non-adsorbed pro-
ducts. A displacement fluid may be classed as either
more strongly or less strongly adsorbed than the
material loaded on the bed. When a more strongly
adsorbed fluid is used, it will be immediately ad-
sorbed on the Molecular Sieves, and so displace the
less strongly held adsorbate. Little or no partial pres-
sure stripping action occurs. When a less strongly
adsorbed fluid is used, the desorption which occurs
is due to both displacement and purge stripping.
Generally, the more strongly adsorbed the displac-
ing agent, the more complete the desorption of the
previously adsorbed component, and the less the
amount of displacing agent required. Use of a more
strongly adsorbed displacement agent, however, in-
troduces the problem of subsequently removing the
agent from Molecular Sieves before the next adsorp-
tion phase of the cycle.
Although use of a less strongly adsorbed gas as a
displacement fluid entails a higher displacement gas
circulation, a major advantage accrues from its use.
The advantage is due to the relative ease with which
the displacing agent may be finally removed from
the Molecular Sieve bed. This is usually accomplish-
125
ed by n-paraffin displacement during the adsorption
phase of the cycle.
Molecular Sieve Adsorption Processes
be treated are light and heavy naphthas, kerosenes,
and gas oils. The recovery of high purity normal par-
affin product is accomplished through proprietary
application of the selective adsorption properties of
LINDE MoTecular Sieves. The non-normals pass

Cs are removed from naphtha stocks for use as sol- 10. l l l l l I I I 1 I I I I 1 1 l 1

vents and as selective cracking stocks in manufacture -

-
of olefins. The non-normal product from the process - C5-CIo n-PARAFFIN CONC
- -
is used directly for gasoline blending or reformer - I N F E E D 15-40 LIQ. V O L %
feed. In the Ci0 through Cis range the recovered nor- - -
mal paraffins are finding large, new markets as raw $ - -
materials for “biologically soft” detergents and pla- i
z
sticizers and as chemical intermediates for a variety w
1.0:
of other purposes. 0 -
IsoSiv is a pressure swing adsorption process for 1
‘;I -
recovery of normal paraffins from branch chain and 5
cyclic hydrocarbons. Operating conditions of pres-
sure and temperature are within the ranges of usual
refinery practice. Typical charge stocks which may

F
o. I
100 1,000 10,oO0
BARRELS PER DAY-NORMALS
CYCLICS
Figure 12
IsoSiv process - T o t a l plant i n v e s t m e n t f o r r e c o v e r y of
CS-Cio normal paraffins.

The investment and operating expense for processing

Figure 1 1
I s o S i v process - simplified f l o w diagram.
feedstocks of C5 through C104)are presented in Figu-
res 12 and 13. These values are based on processing
streams concentrated in the C5-C7 range with Ci0
fraction being only 1-2 O / o .
For the recovery of normal paraffins in the
ciO-ci6 range from typical kerosene feedstock, the
IsoSiv process can produce 95-98O/o pure normal
paraffins with greater than 90 O / o recovery. Typical
economics for a turn-key plant to produce 125 mil-
lion pounds per year of normal product is $2,700,000

126 111/16
 Molecular Sieves have been installed to dry the
-
-
-- unsaturate feed to an HF alkylation unit6) and the
- - -
Cg CIO n PARAFFINS CONC. -
- - process is operating economically. Reduction of the
IN FEED 15-40 L I O . V O L . % - water content to 1 p.p.m. provided in this process
- will minimize critical corrosion problems. This op-
- eration is more difficult than drying a saturated hydro-
carbon such as normal butane. The unsaturates are
- much more strongly adsorbed and are therefore more
-
- difficult to dry. In addition, the adsorption of the un-
-
- saturated feed stream results in very high heat
-
- release unless proper processing steps are employed.
- One such step which is necessary is that the bed be
preloafdedwith a low concentration of unsaturate be-
-
fore passing the main stream into the bed for drying.
The removal of water from the feed to sulfuric acid
IO' I I I I I I I I I I I I I I I I I alkylation processes might also prove to be important
not only in the control of corrosion, but also in re-
duction of acid consumption.
Molecular Sieve Catalysts: Molecular Sieves
Types A, X and Y have all been found to have specific
Catalytic activities both in the metal-loaded and non-
metal-loaded forms. These catalysts are different
including Molecular Sieve inventory, and excluding from conventional catalysts in the following ways:
off-sites. Complete operating cost, including amor- (a) They are crystalline with uniform, internal pores
tization, interest, taxes, overhead, etc., is $ 200 per of molecular dimensions. This provides a uniformity
barrel of normal product. of active sites with consequential benefit on cataly-
Light Products Finishing: The drying and sweeten- tic selectivity; (b) Strong dipoles3) exist in the cry-
ing of such liquid products as propane, butane and stalline structure providing the catalyst with strong
LPG by Molecular Sieve processes are in commercial carbonium ion activity; and (c) The exchangeable
practice. For example, the United States natural gas cations in the zeolite structure facilitate introduction
in,dustry has already converted more than 5Oo/o of of catalytic metals in the highest degree of disper-
its liquid propane sweetening units to Molecular sion. Proper catalytic activity and selectivity are de-
Sieve. This application was described in a recent pendent on the particular zeolite structure, the pro-
publication5) and the operational steps of the process per cations in the structure and the metal, if re-
are given in Figure 14. quired, properly loaded into the structure.
Metal-loeding of Molecular Sieve crystals can be
LIQUID REMOVAL COOLING AND
ADSORPTION AND DEPRESSURIZATION DESORPTION REPRESSURIZATION
carried out in essentially four different ways:
PURGE GAS SOUR
4M)-550aF Liauio Direct transfer of the metal into the Molecular
W-IW PSIG FEED
SOUR HIGH 20-25MOLS/lOO 2 0 - 3 0 GAL/IOO Sileve crystal by vaporization of the metal and

i GoA
LiauiD PRESSURE LB ACTIVATED L B ACTIVATED
ADSORBENT ADSORBENT adsorption an,d condensation of the metal vapor
within the Molecular Sieve crystal.
ADSO~BENT
BED T Y P E 13X Ion exchange of the desired metal cation into
MOLECULAR
SIEVE PELLETS the Molecular Sieve crystal by conventional
ion exchange techniques followed by reduction
t SWEET VAPOR
of the metal cation to free metal with hydrogen.
SWEET INTERSTIT~L LiauiD XI FUEL
PRWUCT
LIQUID To RECOIERI
(AND VAPOR)OR FUEL TO RECOVERY
Adsorption of easily decomposable compounds
Figure 14 into the Molecular Sieve crystal followed by
Operating steps in Molecular Sieve liquid sweetening decomposition to the metal. Metal carbonyls
process. are good examples of such compounds.

I IV16 1 27
 4. Ion exchange of a complex amine metal cation
into the Molecular Sieve crystal. The complex
is decomposed by heat and purged to leave a
fine dispersion of metal on the internal Mole-
cular Sieve surface.
The effect of crystal structure and chemical com-
position of the various Molecular Sieve zeolites on
catalytic activity in hydrocarbon conversion reac-
tions has been discussed by Rabo et al3). Linde Iso-
merization Catalyst MB 53907) was developed speci-
fically as an intermediate temperature catalyst for
isomerization of C5 and Ce paraffins. Data for this
catalyst are presented in Table II.

TABLE II
ISOMERIZATION WITH LINDE CATALYST MB 5390

Pentane Hexane
Isomerization Isomerization

Temperature -'F. ........................................ 698 698 626 635

Pressure -psi. ............................................ 450 450 450 450
W.H.S.V.-g/g/hr. ........................................ 2 5 1 5
H,/Hydrocarbon - M/M. ................................... 3 3 3 3
Total liquid product - wt. yo
c,-c, .................................................. 1.1 0.5 1.5 0.3
c, ..................................................... 3.6 1.8 1.4 0.2
c, + .................................................. 95.3 97.7 97.1 99.5
Composition of C, fraction - mol. yo
Isopentane ............................................. 65.2 62.5
n-pentane .............................................. 34.8 37.5
Composition of C, fraction - mol. yo
n-hexane ............................................... 20.7 33.6
3-methylpentane ........................................ 21.5 20.8
2-methylpentane ........................................ 32.9 30.8
2,3-dimethylbutane ..................................... 8.6 5.8
2,2-dimethylbutane ..................................... 16.4 9.0

Bibliography drocarbons," Chem. Eng. Progress, 56, 132-140 (Sep-

1. Breck, D. W., Eversole, W. G., Milton, R. M., Reed,
T. B., Thomas, T. L., "Crystalline Zeolites I. The Pro-
perties of a New Synthetic Zeolite, Type A," J . Am.
Chem. Soc., 38, 5953 (1956).
2. Reed, T. B., Breck, D. W., "Crystalline Zeolite 11. Cry-
sta1 Structure of Synthetic Zeolite, Type A," J . Am.
Chem. Soc., 78, 5972 (1956).
3. Rabo, J . A., Pickert, P. E., Stamires, D. N., and Boyle,
J. E., "Molecular Sieve Catalysts in Hydrocarbon
Reactions," Actes du Deuxieme Congres Internafio-
nul de Catalyse, Part A, 2055, Editions Techniq, Pa-
ris (1961).
4. Avery, W. F., M. N. Y. Lee, "IsoSiv Goes Commer-
cial," Oil and Gas Journal, 60, 121 (June 4, 1962), and
Chem. Eng., 69, 58 (April 30, 1962).
5. Clark, E. L., Rhodes, H. B., Raidt, R. A., Lawrie, J. A . ;
"Molecular Sieve Process for Sweetening Liquid Hy-
tember, 1960).
6. Collins, J. J., "Superdrying Alkylation Feed Trims
Operating Costs," Oil and Gas Journal, 60, 92-99
(July 2, 1962).
7. Rabo, J. A., Pickert, P. E., Mays, R. L., "Pentane and
Hexane Isomerization," Ind. Eng. Chem., 53, 733
(1961).
This paper was presented on June 26, 1963, by
T. L. THOMAS.
Discussion
R. J. H. GILBERT (British P e t r o l e u m Co. U d . , Stai-
nes, M i d d l e s e x , Great Britain). Dr. Thomas has very
ably summarised the range of application of mole-

î 28 IIWV
cular sieves in the petroleum and allied industries.
The ability to separate specific molecular species in
this way is obviously an important advance in pro-
cessing technology.
The purification of hydrogen is a very immediate
problem and I was interested to see the summarised
data in Table III of the preprinted paper. In processes
using hydrogen recycle, large volumes of gas are
circulated. As the purity of the recycle gas falls, so
unproductive heat and energy are used in gas cir-
culation. Operating pressures may have to be in-
creased to compensate for the fall in hydrogen par-
tial pressure.
Continuous removal of methane and ethane from
the recycle gas would be of great value, A loss of
even 5O/o of circulating hydrogen in these circum-
stances is, however, a serious matter in relation to
the net hydrogen consumption or production in the
unit. I should like to ask whether it can be regarded
as feasible to purify recycle gas using a molecular
sieve process, while maintaining nearly 100°/o hy-
drogen recovery.
T. L. THOMAS replies. We thank Mr. Gilbert for
his kind remarks, In answer to his question, recoverv
of hydrogen above 95 " l o is possible, but economics
going upward from 95 O/o increase rapidly. This effect
may be seen in Table III of the preprinted paper in
going from 85 to 95Oío recovery. Recoveries above
97 - 98 O/o are probably technically and economically
impractical.
H. PEREIRA (Companhia Uniao Fabril, Lisbon, Por-
tugal). Is it possible to purify ammonia synthesis gas
obtained by steam reforming hydracarbons, i. e. con-
taining H2 and N2 i n the ratios of 3 : l ? In other words,
is it possible to remove CO and CO2 and to leave Hz
and Nz in the gas?
T. L. THOMAS replies. An indication of the sepa-
ration and possible economics of a Molecular Sieve
process for this separation can be seen in Table III
of the preprinted paper, substituting in the steam re-
formed natural gas column a feed mixture of Hg to
Na ratio of 3 : 1. As mentioned in the talk, these hy-
drogen upgrading processes are not as yet developed,
with Table III giving only preliminary separations
and economics.
C. BOST (Centre de Recherches Esso SAF, Mont-
Saint-Aignan, France). L'auteur peut-il nous dire
quels types de produits plus adsorbables que les
produits déjà retenus par les molecular sieves peu-
vent être utilisés pour la désorption?
T.L.THOMAS replies. The use of more strongly
adsorbed material to desorb a less strongly adsorbed
material from Molecular Sieve is a process technique
worth consideration in some cases. For strongly held
materials, such as heavier paraffins and olefins, de-
Sorption agents might be water or ammonia, For more
weakly adsorbed materials, such as light paraffins
of C5 or less, carbon dioxide may be a good example.
E. C . HUGHES (The Standard Oil Co., Cleveland,
Ohio, USA). 1. Can you describe some of the tech-
niques and precautions you use, in the pressure cycle,
to obtain and to maintain high product purities in the
up-tO-ci6 fractions?
2. Do you now have sieves that are operable in
fluid beds?
T. L. THOMAS replies, 1. High product purities can
be obtained in pressure swing processes by proper
balancing of process variables, particularly tempera-
ture and pressure levels, and in some cases by the
appropriate use of purge gases.
2. In answer to your second question, we do not
have Molecular Sieves available in fluidizable form.
W e could make such a material available if there
were definite markets of sufficient size to warrant
our technical and plant investment in such a product.
129