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Applied Aspects of Zeolite Adsorbents

HANJU LEE
W. R. Grace & Co., Davison Chemical Division, Washington Research Center,
Clarksville, Md. 21029
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New applications of zeolite adsorption developed recently for sep

Publication Date: June 1, 1973 | doi: 10.1021/ba-1973-0121.ch028

aration and purification processes are reviewed. Major

commercial processes are discussed in areas of hydrocarbon
separation, drying gases and liquids, separation and purification
of industrial streams, pollution control, and nonregenerative
applications. Special emphasis is placed on important
commercial processes and potentially important applications
Important properties of zeolite adsorbents for these applicatio
are adsorption capacity and selectivity, adsorption and desorp-
tion rate, physical strength and attrition resistance, low catalyti
activity, thermal-hydrothermal and chemical stability, and
particle size and shape. Apparent bulk density is important
because it is related to adsorptive capacity per unit volume and
to the rate of adsorption-desorption. However, more important
factors controlling the raies are crystal size and macropore size
distribution.

/ ~ V n e of t h e m a j o r i n d u s t r i a l a p p l i c a t i o n s of zeolites is i n t h e a r e a of a d -
s o r p t i o n processes. Zeolite adsorbents are n o t o n l y t h e m o s t i m p o r t a n t
adsorbents t o d a y , b u t t h e i r i m p o r t a n c e is i n c r e a s i n g , m a i n l y because of t h e
following unique adsorptive properties: (a) selective a d s o r p t i o n of m o l e -
cules based o n m o l e c u l a r dimensions, (b) h i g h l y p r e f e r e n t i a l a d s o r p t i o n of
p o l a r molecules, (c) h i g h l y h y d r o p h i l i c surface, a n d (d) v a r i a t i o n of p r o p -
erties b y i o n exchange.
C o n t r a r y t o c a t a l y t i c a p p l i c a t i o n s , zeolite adsorbents are m o s t l y a p -
p l i e d i n a fixed-bed o p e r a t i o n . A n u m b e r of c o l u m n s p a c k e d w i t h zeolite
adsorbent (s) are i n t e r c o n n e c t e d w i t h a n a u t o m a t i c v a l v e s y s t e m t o f a c i l i -
t a t e a c o n t i n u o u s flow of t h e i n d u s t r i a l s t r e a m b e i n g processed. E a c h b e d ,
however, goes t h r o u g h a stepwise c y c l i c o p e r a t i o n , a n d d u r i n g each c y c l e
t h e adsorbed molecules i n t h e zeolite b e d are desorbed b y r a i s i n g t h e b e d
t e m p e r a t u r e , l o w e r i n g t h e b e d pressure, d i s p l a c i n g t h e a d s o r b a t e w i t h
a n o t h e r adsorbate, or c o m b i n a t i o n .
311

In Molecular Sieves; Meier, W., et al.;

Advances in Chemistry; American Chemical Society: Washington, DC, 1973.
 312 MOLECULAR SIEVES

F o r a fixed-bed o p e r a t i o n , zeolite adsorbents s h o u l d h a v e a reasonable

size t o a v o i d a n excessive pressure d r o p . S y n t h e t i c zeolites a n d some n a t ­
u r a l zeolites p r o d u c e d i n a fine size powder h a v e t o be f o r m e d i n t o spheres,
e x t r u d a t e s , o r pellets u s u a l l y w i t h a n i n e r t b i n d e r . S o m e c o m m e r c i a l
m o l e c u l a r sieve adsorbents, however, are called " b i n d e r l e s s " because t h e y
c o n t a i n a m u c h higher (up t o 9 5 % ) zeolite c o n t e n t t h a n most zeolite a d ­
sorbents.
I m p o r t a n t properties of zeolite adsorbents for a fixed-bed a p p l i c a t i o n
are a d s o r p t i v e c a p a c i t y a n d s e l e c t i v i t y , a d s o r p t i o n - d e s o r p t i o n r a t e ,
p h y s i c a l s t r e n g t h a n d a t t r i t i o n resistance, l o w c a t a l y t i c a c t i v i t y , t h e r m a l -
h y d r o t h e r m a l s t a b i l i t y , c h e m i c a l s t a b i l i t y , a n d p a r t i c l e size a n d shape.
A p p a r e n t b u l k d e n s i t y of zeolite adsorbents i s i m p o r t a n t because i t is r e ­
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l a t e d t o t h e a d s o r p t i v e c a p a c i t y per u n i t v o l u m e a n d also somewhat t o r a t e

of a d s o r p t i o n a n d d e s o r p t i o n . H o w e v e r , m o r e i m p o r t a n t properties r e ­
Publication Date: June 1, 1973 | doi: 10.1021/ba-1973-0121.ch028

l a t e d t o t h e rates a n d therefore t o t h e a c t u a l useful c a p a c i t y w o u l d be t h e

zeolite c r y s t a l size a n d t h e macropore size d i s t r i b u t i o n . A l t h o u g h t h e
u l t i m a t e basis i n selecting a zeolite adsorbent f o r a specific a p p l i c a t i o n
w o u l d be t h e performance, t h e p r i c e , a n d t h e p r o j e c t e d service life of a
p r o d u c t , these factors depend l a r g e l y u p o n t h e a b o v e properties.
M a j o r i n d u s t r i a l a d s o r p t i o n processes u s i n g zeolite adsorbents m a y be
classified as f o l l o w s : (I) h y d r o c a r b o n s e p a r a t i o n processes, (II) d r y i n g
gases a n d l i q u i d s , ( I I I ) s e p a r a t i o n a n d p u r i f i c a t i o n of i n d u s t r i a l streams,
( I V ) p o l l u t i o n c o n t r o l a p p l i c a t i o n s , a n d ( V ) nonregenerative a p p l i c a t i o n s .
Some i m p o r t a n t c o m m e r c i a l processes i n each of these areas are d i s ­
cussed b r i e f l y .

Hydrocarbon Separation Processes

π-Paraffin S e p a r a t i o n . η-Paraffins are separated f r o m a m i x t u r e of

paraffins b y u s i n g a C a A m o l e c u l a r sieve w hich h a s a n effective p o r e
T

d i a m e t e r of about 5 A . Because of i t s pore size, a C a A m o l e c u l a r sieve

adsorbs o n l y η-paraffins, a n d t h e effluent f r o m a m o l e c u l a r sieve b e d c o n ­
t a i n s m a i n l y isoparaffins a n d a s m a l l a m o u n t of a r o m a t i c s e x i s t i n g i n t h e
feed s t r e a m . T h e adsorbed η-paraffins are l a t e r desorbed f r o m t h e b e d a n d
recovered.
T h e use of n-paraffins recovered i n c l u d e octane v a l u e enhancement of
gasoline, solvents a n d r a w m a t e r i a l s for biodegradable detergents, fire r e ­
t a r d a n t s , plasticizers, a l c o h o l , f a t t y acids, s y n t h e t i c p r o t e i n s , l u b e o i l
a d d i t i v e s , a n d α-olefins. A d e t a i l e d discussion o n n-paraffin s e p a r a t i o n
processes is a v a i l a b l e (1).
M a j o r c o m m e r c i a l processes i n η-paraffin s e p a r a t i o n a r e U . O . P . ' s
M o l e x process (2-5), B . P . ' s process (6-8), E x x o n ' s E n s o r b process (9, 10),
U n i o n C a r b i d e ' s I s o S i v process (11-13), T e x a c o ' s T . S . F . process (14, 15),
Shell's process (16), a n d V E B L e u n a W e r k e ' s P a r e x process (17). E x c e p t

In Molecular Sieves; Meier, W., et al.;

Advances in Chemistry; American Chemical Society: Washington, DC, 1973.
 28. LEE Applied Zeolite Adsorbents 313

for t h e M o l e x process, a l l others operate u n d e r v a p o r phase a n d use t h e

fixed-bed, c y c l i c a d s o r p t i o n technology. T h e processes are different, h o w ­
ever, i n o p e r a t i n g pressure a n d t e m p e r a t u r e , m e t h o d of τι-paraffin desorp­
t i o n , a n d o t h e r o p e r a t i n g c o n d i t i o n s . M o s t processes operate u n d e r i s o ­
t h e r m a l a n d isobaric c o n d i t i o n s w i t h desorption of η-paraffins b y displace­
m e n t . D i s p l a c e m e n t agents often m e n t i o n e d i n p a t e n t l i t e r a t u r e are l o w
b o i l i n g η-paraffins s u c h as n - p e n t a n e a n d n-hexane, a n d a m m o n i a or a l k y l -
amines. I n e r t gases s u c h as n i t r o g e n or h y d r o g e n are m e n t i o n e d also, b u t
t h e y m a y serve as c a r r i e r gases r a t h e r t h a n displacement agents. Some
processes u t i l i z e a pressure s w i n g o p e r a t i o n , especially for s e p a r a t i n g l o w
c a r b o n n u m b e r η-paraffins. I n pressure s w i n g o p e r a t i o n , t h e d e s o r p t i o n
pressure is s u b s t a n t i a l l y lower t h a n t h e a d s o r p t i o n pressure t o f u r n i s h
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enough d r i v i n g force for a r e a s o n a b l y fast mass t r a n s f e r .

I n cases where p r o d u c t p u r i t y is i m p o r t a n t , a n i n t e r m e d i a t e step
Publication Date: June 1, 1973 | doi: 10.1021/ba-1973-0121.ch028

(purge step) is used between a d s o r p t i o n a n d d e s o r p t i o n steps. P u r g i n g

removes isoparaffins e x i s t i n g i n t h e v o i d space between m o l e c u l a r sieve
adsorbents a n d macropores w i t h i n each adsorbent p a r t i c l e p r i o r t o desorp­
t i o n step. Because most i m p u r i t i e s c a n be r e m o v e d f r o m t h e adsorbent b e d
i n t h e p u r g i n g step, t h e η-paraffins recovered i n t h e subsequent d e s o r p t i o n
w o u l d be r e l a t i v e l y p u r e . T h e o p e r a t i n g t e m p e r a t u r e for v a p o r - p h a s e
o p e r a t i o n m u s t be a b o v e t h e highest b o i l i n g p o i n t of t h e feed s t r e a m b u t
generally lower t h a n 800° F t o a v o i d c r a c k i n g .
T h e M o l e x process developed b y U . O . P . is u n i q u e n o t o n l y i n i t s
l i q u i d - p h a s e o p e r a t i o n b u t also i n i t s a d s o r p t i o n s y s t e m (1-3). Its ad­
s o r p t i o n s y s t e m consists of a single a d s o r p t i o n t o w e r w i t h m u l t i p l e i n l e t -
o u t l e t p o i n t s a n d a special r o t a r y v a l v e . T h e a d s o r p t i o n t o w e r has m a n y
smaller a d s o r p t i o n chambers i n t e r c o n n e c t e d i n series, a n d i t operates
under t h e so-called " s i m u l a t e d m o v i n g b e d " o p e r a t i o n . I n s t e a d of m o v i n g
t h e adsorbent bed, t h e s i m u l a t e d m o v i n g b e d operates b y s i m u l t a n e o u s l y
a d v a n c i n g i n l e t - o u t l e t p o i n t s p e r i o d i c a l l y . A t a n y t i m e , t h e adsorber
has four zones—viz., a d s o r p t i o n , p r i m a r y r e c t i f i c a t i o n , d e s o r p t i o n , a n d
secondary r e c t i f i c a t i o n zones, a n d these zones a d v a n c e s i m u l t a n e o u s l y as
t h e r o t a r y v a l v e t u r n s p e r i o d i c a l l y . D e s o r p t i o n of ra-paraffins is a c h i e v e d
b y displacement.
T h e r a t e of τι-paraffin d e s o r p t i o n generally controls t h e o v e r a l l p r o ­
d u c t i o n r a t e (18, 19). T h e diffusion of τι-paraffins i n c o m m e r c i a l 5 A m o ­
lecular sieves is r e p o r t e d t o be c o n t r o l l e d b y either m i c r o p o r e diffusion or
macropore diffusion, or b o t h , depending o n t h e m o l e c u l a r sieve c r y t a l size
a n d macropore size d i s t r i b u t i o n of t h e adsorbent (20). A 5 A molecular
sieve adsorbent w i t h s m a l l e r c r y s t a l size a n d o p t i m u m m a c r o p o r e size d i s ­
t r i b u t i o n w o u l d h a v e a faster a d s o r p t i o n - d e s o r p t i o n r a t e a n d , therefore,
a higher effective c a p a c i t y .
^-Xylene Separation-U.O.P.'s P a r e x Process. T h e continued rapid
increase i n t h e p - x y l e n e d e m a n d as a r a w m a t e r i a l for p o l y e s t e r p r o d u c t s i n

In Molecular Sieves; Meier, W., et al.;

Advances in Chemistry; American Chemical Society: Washington, DC, 1973.
 314 MOLECULAR SIEVES

recent y e a r s necessitated t h e d e v e l o p m e n t of a n e w x y l e n e s e p a r a t i o n
process. U . O . P . developed a n e w a d s o r p t i o n process for s e p a r a t i n g p-
xylene from a C 8 aromatics mixture containing xylenes and ethylbenzene
(21, 22). ( U . O . P . ' s P a r e x process s h o u l d n o t be confused w i t h V E B L e u n a
W e r k e ' s ( E . G e r m a n y ) P a r e x process w h i c h is a n n - p a r a f f i n s e p a r a t i o n
process (see p r e c e d i n g section).) T h e h a r d w a r e for t h e P a r e x process seems
t o be s i m i l a r t o t h a t for t h e U . O . P . M o l e x process for n - p a r a f f i n s e p a r a t i o n ,
a n d i t uses t h e c o n t i n u o u s l i q u i d phase, s i m u l a t e d m o v i n g b e d o p e r a t i o n .
T h i s process, i n a p i l o t - p l a n t o p e r a t i o n , d e m o n s t r a t e d t h a t i t c a n separate
p - x y l e n e f r o m v a r i o u s t y p e s of feedstocks w i t h 9 9 . 5 % p u r i t y a n d r e c o v e r y
as h i g h as 9 8 . 4 % (21). T h e h i g h p - x y l e n e r e c o v e r y i n p a r t i c u l a r is be-
l i e v e d t o be a significant i m p r o v e m e n t over c o n v e n t i o n a l c r y s t a l l i z a t i o n
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processes. P a t e n t s issued t o U . O . P . i n r e g a r d t o a r o m a t i c s e p a r a t i o n
suggest t h a t t h e adsorbent u s e d is a s y n t h e t i c f a u j a s i t e c o n t a i n i n g c a t i o n s of
Publication Date: June 1, 1973 | doi: 10.1021/ba-1973-0121.ch028

g r o u p I A , g r o u p I I A , or b o t h (23-25). R e c e n t p a t e n t l i t e r a t u r e (27, 28)

also c l a i m s t h a t s o d i u m m o r d e n i t e a n d m o d i f i e d t y p e - Y zeolite c o n t a i n i n g
p r e d o m i n a n t l y p o t a s s i u m ions c a n separate p - x y l e n e f r o m a x y l e n e m i x t u r e
a n d a C aromatic mixture, respectively.
8 H o w e v e r , n e i t h e r is k n o w n t o
be c o m m e r c i a l i z e d y e t .
Olefin Separation. U.O.P.'s OLEX PROCESS. U.O.P.'S other h y d r o -
c a r b o n s e p a r a t i o n process d e v e l o p e d r e c e n t l y — i . e . , t h e O l e x process—is
u s e d to separate olefins f r o m a feedstock c o n t a i n i n g olefins a n d paraffins.
T h e zeolite adsorbent used, a c c o r d i n g t o p a t e n t l i t e r a t u r e (29, 30), i s a
synthetic faujasite w i t h 1-40 w t % of at least one c a t i o n selected f r o m
groups I A , I I A , I B , a n d I I B . T h e O l e x process i s also b e l i e v e d t o use t h e
same s i m u l a t e d m o v i n g - b e d o p e r a t i o n i n l i q u i d phase as U . O . P . ' s o t h e r
h y d r o c a r b o n s e p a r a t i o n processes—i.e., t h e M o l e x a n d P a r e x processes.
UNION CARBIDE'S OLEFINSIV PROCESS. U n i o n Carbide's OlefinSiv
process is used m a i n l y t o separate n - b u t y l e n e s f r o m i s o b u t y l e n e (31). The
basic h a r d w a r e is t h e same as for t h e I s o S i v process for n - p a r a f f i n s e p a r a -
t i o n , a n d t h e process uses a r a p i d cycle, fixed-bed adsorption. Since t h i s
process separates s t r a i g h t - c h a i n olefins f r o m b r a n c h e d - c h a i n olefins, i t is
reasonable t o assume t h a t a 5 A m o l e c u l a r sieve is used as t h e adsorbent.
P r o d u c t p u r i t i e s are c l a i m e d t o be a b o v e 9 9 % for b o t h n - b u t y l e n e a n d
i s o b u t y l e n e streams.

Drying Gases and Liquids

A l l zeolites h a v e a h i g h l y h y d r o p h i l i c surface a n d are v e r y efficient

desiccants. C o n t r a r y t o o t h e r n o n z e o l i t i c desiccants such as s i l i c a gel a n d
a c t i v a t e d a l u m i n a , zeolite adsorbents h a v e t y p e I a d s o r p t i o n i s o t h e r m s for
w a t e r — i . e . , a h i g h w a t e r a d s o r p t i o n c a p a c i t y at a l o w c o n c e n t r a t i o n of
water. T o o b t a i n e x t r e m e l y d r y gases a n d l i q u i d s , therefore, zeolite a d -
sorbents are s t r o n g l y preferred over a m o r p h o u s desiccants. The 3A mo-

In Molecular Sieves; Meier, W., et al.;

Advances in Chemistry; American Chemical Society: Washington, DC, 1973.
 28. LEE Applied Zeolite Adsorbents 315

l e c u l a r sieve adsorbent i n p a r t i c u l a r has t h e a d d i t i o n a l a d v a n t a g e of selec-

t i v e a d s o r p t i o n of w a t e r because of i t s s m a l l pore size, a n d i t is v e r y useful
i n d r y i n g p o l a r l i q u i d s a n d gases.
C r a c k e d G a s D r y i n g . E t h y l e n e a n d p r o p y l e n e are t w o of the m o s t
i m p o r t a n t p e t r o c h e m i c a l r a w m a t e r i a l s t o d a y . T h e y are m a n u f a c t u r e d
b y a t h e r m a l c r a c k i n g of ethane, p r o p a n e , or n a p h t h a . O n e of t h e i m -
p o r t a n t s e p a r a t i o n - p u r i f i c a t i o n steps i n t h e p r o d u c t i o n of e t h y l e n e a n d
p r o p y l e n e is r e m o v a l of w a t e r before l o w t e m p e r a t u r e s e p a r a t i o n . A l -
t h o u g h a l u m i n a has been t h e m o s t c o m m o n l y u s e d desiccant i n d r y i n g
c r a c k e d gas i n t h e past, 3 A m o l e c u l a r sieve adsorbents h a v e a n o v e r a l l
economic a d v a n t a g e (32), a n d m a n y c r a c k e d gas p l a n t s are u s i n g t h e 3 A
m o l e c u l a r sieves t o d a y .
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T h e m a i n advantages of 3 A m o l e c u l a r sieve o v e r a l u m i n a a n d s i l i c a
gel are i t s higher c a p a c i t y a n d , therefore, s m a l l e r a d s o r p t i o n t o w e r size a n d
Publication Date: June 1, 1973 | doi: 10.1021/ba-1973-0121.ch028

i t s longer service life. T h e d e g r a d a t i o n of 3 A m o l e c u l a r sieve i n c r a c k e d

gas d r y i n g is n o t f r o m a c h e m i c a l d e s t r u c t i o n of zeolite c r y s t a l s b u t r a t h e r
f r o m a n a c c u m u l a t e d deposit of c a r b o n m a t e r i a l o n t h e zeolite. Since a
regular 3 A — i . e . , p o t a s s i u m - e x c h a n g e d t y p e A , is n o t t h e r m a l l y stable
enough t o w i t h s t a n d a n in situ c a r b o n burnoff o p e r a t i o n , i t is r e p l a c e d w i t h
a fresh charge of 3 A m o l e c u l a r sieve w h e n i t has a c c u m u l a t e d excessive
c a r b o n a n d other h y d r o c a r b o n d e r i v a t i v e s . A recent p a t e n t (33), h o w e v e r ,
described a r a r e e a r t h c o n t a i n i n g 3 A m o l e c u l a r sieve h a v i n g sufficient
t h e r m a l s t a b i l i t y t o w i t h s t a n d n o r m a l c a r b o n burnoff c o n d i t i o n s . T h i s
s h o u l d p r o l o n g t h e service life of t h e zeolite adsorbent a n d , therefore,
enhance t h e a d v a n t a g e of zeolite adsorbent i n c r a c k e d gas d r y i n g o v e r n o n -
zeolitic desiccants.
O t h e r L i q u i d a n d G a s D r y i n g . A p p l i c a t i o n s of zeolite adsorbents i n
d r y i n g other i n d u s t r i a l gases a n d l i q u i d s are w e l l k n o w n a n d h a v e been
discussed i n R e f s . 34~36. T h e r e f o r e , a l t h o u g h i t is a n i m p o r t a n t a p p l i c a -
t i o n , i t is n o t discussed here.

Separation and Purification of Industrial Streams

P u r i f i c a t i o n of A i r P r i o r to L i q u e f a c t i o n . S e p a r a t i o n of a i r b y c r y o -
genic f r a c t i o n a t i o n processes requires r e m o v a l of w a t e r v a p o r a n d c a r b o n
d i o x i d e t o a v o i d heat exchanger freeze-up. M a n y p l a n t s t o d a y are u s i n g a
1 3 X ( N a - X ) m o l e c u l a r sieve adsorbent t o r e m o v e b o t h w a t e r v a p o r a n d
c a r b o n d i o x i d e f r o m a i r i n one a d s o r p t i o n step. S i n c e t h e r e is no necessity
for size selective a d s o r p t i o n , 1 3 X m o l e c u l a r sieves are generally p r e f e r r e d
over t y p e A m o l e c u l a r sieves. T h e 1 3 X m o l e c u l a r sieves h a v e n o t o n l y
higher a d s o r p t i v e capacities b u t also faster rates of C 0 a d s o r p t i o n t h a n
2

t y p e A m o l e c u l a r sieves. T h e r a t e of C 0 a d s o r p t i o n i n a c o m m e r c i a l 1 3 X
2

molecular sieve seems t o be c o n t r o l l e d b y m a c r o p o r e diffusion (37). The

o p t i m u m o p e r a t i n g t e m p e r a t u r e for C 0 r e m o v a l b y 1 3 X m o l e c u l a r sieve is
2

r e p o r t e d as 1 6 0 - 1 9 0 ° K (38).

In Molecular Sieves; Meier, W., et al.;

Advances in Chemistry; American Chemical Society: Washington, DC, 1973.
 316 MOLECULAR SIEVES

Natural Gas Purification. N a t u r a l gas c o n t a i n i n g w a t e r v a p o r , s u l f u r

c o m p o u n d s ( m o s t l y h y d r o g e n sulfide), a n d c a r b o n d i o x i d e i s p u r i f i e d b y
m o l e c u l a r sieve adsorbents. S i n c e , w i t h t h e e x c e p t i o n of feed p r e p a r a t i o n
for L N G , t h e complete r e m o v a l of c a r b o n dioxide i s u s u a l l y n o t necessary,
t h e m o l e c u l a r sieve b e d i s used m a i n l y t o r e m o v e w a t e r v a p o r a n d s u l f u r
compounds. T h e a d s o r p t i o n step is c o n t i n u e d e v e n after t h e c a r b o n d i -
oxide b r e a k t h r o u g h b u t i s s t o p p e d before t h e h y d r o g e n sulfide b r e a k -
through. 4 A a n d 5 A m o l e c u l a r sieves are generally used t o r e m o v e w a t e r
a n d h y d r o g e n sulfide f r o m n a t u r a l gas a l t h o u g h 1 3 X c a n be used w h e n t h e
n a t u r a l gas c o n t a i n s a significant a m o u n t of large s u l f u r compounds.
T h e r e is, h o w e v e r , some evidence t h a t N a - X c a n p r o d u c e C O S c a t a l y t i c a l l y
from H S and C 0 . O t h e r i m p o r t a n t a p p l i c a t i o n s of m o l e c u l a r sieves i n
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2 2

n a t u r a l gas p u r i f i c a t i o n i n c l u d e p u r i f i c a t i o n of p i p e l i n e n a t u r a l gas f o r
l i q u e f a c t i o n , d r y i n g n a t u r a l gas p r i o r t o cryogenic h y d r o c a r g o n recovery
Publication Date: June 1, 1973 | doi: 10.1021/ba-1973-0121.ch028

u s i n g a t u r b o e x p a n d e r , a n d sweetening n a t u r a l gas feed t o a m m o n i a p l a n t s

(89-42).
Oxygen Enrichment of Air. R e c e n t d e v e l o p m e n t s i n a p p l i c a t i o n of
oxygen or oxygen-rich air i n biological wastewater treatment plants gen-
e r a t e d a necessity for a l o w cost, on-site o x y g e n generator. M a n y waste-
w a t e r t r e a t m e n t s i n t h e U . S . r e q u i r e less t h a n 100 t o n s p e r d a y of c o n -
tained oxygen. F o r t h e l o w - t o - i n t e r m e d i a t e range, t h e pressure s w i n g
a d s o r p t i o n process u s i n g zeolite adsorbents i s c o m p e t i t i v e w i t h , o r a d -
v a n t a g e o u s over, t h e c o n v e n t i o n a l c r y o g e n i c a i r s e p a r a t i o n process (48, 44)·
C o m m e r c i a l processes k n o w n t o d a y a r e : E s s o R e s e a r c h a n d E n g i n e e r -
i n g processes (45-48), t h e W . R . G r a c e process (43), t h e U n i o n C a r b i d e
process (49), t h e L ' A i r L i q u i d e process (50), t h e B a y e r - M a h l e r process
(51), a n d t h e N i p p o n S t e e l process (52, 53). Differences b e t w e e n these
processes a r e t y p e of zeolites used, n u m b e r of adsorbent beds, o p e r a t i n g
pressures, a n d c y c l i c o p e r a t i n g steps. T h e pressure s w i n g a d s o r p t i o n p r o -
cess c a n produce u p t o 9 5 % oxygen, t h e r e m a i n d e r m a i n l y a r g o n , a n d i s
d e f i n i t e l y advantageous over t h e cryogenic a i r s e p a r a t i o n process a t b e l o w
25 t o n s - p e r - d a y c a p a c i t y . O t h e r p o t e n t i a l a p p l i c a t i o n s of o x y g e n r i c h a i r
p r o d u c e d b y pressure s w i n g a d s o r p t i o n processes a r e p o l l u t i o n c o n t r o l i n
t h e p u l p a n d p a p e r i n d u s t r y , secondary s m e l t i n g p l a n t s , r i v e r a n d p o n d
a e r a t i o n , feed gas t o ozone generators, m e d i c a l a p p l i c a t i o n s a n d c h e m i c a l
o x i d a t i o n processes.
Pollution Control. Z e o l i t e adsorbents c a n effectively remove pol-
l u t a n t s s u c h as S 0 , H S , a n d N O * f r o m i n d u s t r i a l off-gas s t r e a m s a t near
2 2

a m b i e n t t e m p e r a t u r e (54-57). Since w a t e r v a p o r u s u a l l y exists a l o n g w i t h

these a c i d i c c o m p o u n d s , a n a c i d - s t a b l e o r a c i d - r e s i s t a n t z e o l i t e a d s o r b e n t
is necessary for a l o n g service life. U n i o n C a r b i d e announced three new pro-
cesses f o r p o l l u t i o n c o n t r o l r e c e n t l y . T h e y a r e t h e P u r a S i v - H g process
for m e r c u r y v a p o r r e m o v a l , t h e P u r a S i v - N process for N O ^ r e m o v a l f r o m
n i t r i c a c i d p l a n t off-gas, a n d t h e P u r a S i v - S process for S 0 r e m o v a l f r o m
2

In Molecular Sieves; Meier, W., et al.;

Advances in Chemistry; American Chemical Society: Washington, DC, 1973.
 28. LEE Applied Zeolite Absorbents 317

sulfuric acid plant off-gas (58). A recent British patent (57) described a
process using a molecular sieve bed preadsorbed with 0.1-10 wt % of am­
monia before the gas stream containing acidic gases is introduced.

Nonregenerative Applications

Applications of zeolite adsorbents are not limited to the fixed-bed,

cyclic operation discussed above. Some applications involve no regenera­
tion and therefore no cyclic operation. Important nonregenerative ap­
plications are drying Freon-type refrigerants and manufacture of dual-
pane windows. Every refrigerator and air conditioner using halogenated
hydrocarbon refrigerants require a desiccant cartridge to keep the refriger­
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ants super dry. The 3A molecular sieve can effectively dry refrigerants,
but its catalytic activity to decompose refrigerant should be suppressed.
Publication Date: June 1, 1973 | doi: 10.1021/ba-1973-0121.ch028

In the dual-pane window application, zeolite adsorbents are often used to­
gether with other adsorbents such as silica gel to keep the vapor pressure of
gases inside the dual pane window sufficiently low. It is important to re­
move water vapor and organic solvent vapors from the sealing compound
to avoid fogging in winter months.

Literature Cited

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RECEIVED December 4, 1972.

In Molecular Sieves; Meier, W., et al.;

Advances in Chemistry; American Chemical Society: Washington, DC, 1973.