United S ta tes Pa tent [ 1 9 ]

N is h ida et a l .
[ 5 4 ] METHOD OF S EPARATIN G CARBON
MON OXIDE AN D CARBON MON OXIDE
ADS ORBEN T US ED IN THIS METHOD
[ 7 5 ] Inv ento r s : Ta is u k e N is h ida , To k y o ; K a z u o
Ta j im a , Hir a ts u k a ; Yo Os a da ; Os a m u
S h ig y o , b o th o f Yo k o h a m a ; Hir o a k i
Ta nig u c h i, K u k i, a l l o f J a p a n
N ip p o n K o k a n K a b u s h ik i K a is h a ,
To k y o , J a p a n
[ 2 1 ] Ap p l . N o . : 9 4 8 , 3 9 4
[ 2 2 ] Fil ed: Dec . 3 1 , 1 9 8 6
[ 7 3 ] As s ig nee:
Rel a ted U. S . Ap p l ic a tio n Da ta
[ 6 3 ] Co ntinu a tio n o f S er . N o . 7 5 1 , 0 3 8 , J u l . 1 , 1 9 8 5 , a b a n
do ned.
[ 3 0 ] Fo r eig n Ap p l ic a tio n Pr io r ity Da ta
J u l . 4 , 1 9 8 4 [ J P] J a p a n 5 9 - 1 3 8 7 7 1
J u l . 4 , 1 9 8 4 [ J P] J a p a n 5 9 - 1 3 8 7 7 2
Ap r . 8 , 1 9 8 5 [ J P] J a p a n . . . . . . . . . . . 6 0 - 7 2 6 9 6
Ap r . 8 , 1 9 8 5 [ J P] J a p a n . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6 0 - 7 2 6 9 7
[ 5 1 ] Int. Cl . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . B0 1 D 5 3 /0 4
[ 5 2 ] U. S . Cl . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 5 /6 8 ; 5 5 /7 5
[ 5 8 ] Fiel d o f S ea r c h . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 5 /6 8 , 7 5 , 3 8 9 ;
4 2 3 /2 4 6 , 2 4 7 , 4 1 5 A; 5 0 2 /7 5 , 7 7 - 7 9 , 4 0 6 , 4 0 7
[ 5 6 ] Ref er enc es Cited
U. S . PATEN T DOCUMEN TS
3 , 0 1 3 , 9 8 2 1 2 /1 9 6 1 Br ec k et a 1 . . . . . . . . . . . . . . . . . . . . . . . 5 0 2 /7 5 X
3 , 1 8 5 , 5 4 0 5 /1 9 6 5 Br ec k et a 1 . . . 4 2 3 /2 4 7
3 , 3 3 1 , 1 9 0 7 /1 9 6 7 Gl ew et a 1 . 5 5 /7 5 X
3 , 4 0 7 , 0 3 9 1 0 /1 9 6 8 Br y a nt . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 0 2 /7 8 X
4 , 7 4 3 , 2 7 6
Ma y 1 0 , 1 9 8 8
[ 1 1 ] Pa tent N u m b er :
[ 4 5 ] Da te o f Pa tent:
3 , 4 7 6 , 5 0 8 1 1 /1 9 6 9 K ea r b y et a l . . . . . . . . . . . . . . . . . . . 4 2 3 /2 4 7 X
3 , 4 9 7 , 4 6 2 2 /1 9 7 0 K r u er k e . . . . . . . . . . . . . . . . . . . . 5 0 2 /7 5
3 , 7 5 5 , 5 4 0 8 /1 9 7 3 Ra s b a c k 5 0 2 /7 5 X
3 , 7 8 9 , 1 0 6 l /l 9 7 4 Ha y . . . . . . . . . . . . . . . 5 5 /6 8 X
4 , 0 1 9 , 8 7 9 4 /1 9 7 7 Ra b o et a l . . . . . . . . 5 5 /6 8
4 , 0 1 9 , 8 8 0 4 /1 9 7 7 Ra b o et a 1 . 4 , 1 8 0 , 6 9 3 1 2 /1 9 7 9 Ma r c il l y . . . . . . . . . . . .
4 , 2 9 7 , 3 2 8 1 0 /1 9 8 1 Rits c h er et a 1 . . .
4 , 3 5 8 , 2 9 7 1 l /1 9 8 2 Eb er l y , J r . . . . . . . . . . . . . . . 5 5 /7 5 X
4 , 4 7 0 , 8 2 9 9 / 1 9 8 4 Hir a i et a 1 . . . . . . . . . . . . . . . 5 5 /6 8
4 , 5 3 9 , 0 2 0 9 /1 9 8 5 S a k u r a y a et a 1 . . . . . . . . . . . . . . . . . . . . 5 5 /6 8 X
FOREIGN PATEN T DOCUMEN TS
1 8 7 0 0 1 1 / 1 9 8 0 Eu r o p ea n Pa t. Of f . . . . . . . . . 4 2 3 /4 1 5 A
1 5 1 2 2 6 3 1 2 / 1 9 6 7 Fr a nc e .
2 3 3 5 2 5 8 7 / 1 9 7 7 Fr a nc e .
7 2 5 5 l /1 9 8 2 J a p a n . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 2 3 /4 1 5 A
5 8 - 1 5 6 5 1 7 9 /1 9 8 3 J a p a n .
5 9 - 2 2 6 2 5 2 /1 9 8 4 J a p a n .
5 9 - 2 6 1 2 1 2 /1 9 8 4 J a p a n .
6 6 2 4 6 0 1 2 / 1 9 5 1 United K ing do m . . . . . . . . . . . . . . . . 4 2 3 /2 4 7
Pr im a r y Ex a m iner - Ro b er t S p itz er
Atto r ney , Ag ent, o r Fir m Fr is h a u f , Ho l tz , Go o dm a n &
Wo o dwa r d
[ 5 7 ] ABS TRACT
In a m eth o d o f th e inv entio n f o r s el ec tiv el y a ds o r b ing
CO in a g a s m ix tu r e c o nta ining a t l ea s t CO a nd CO2
with a n a ds o r b ent a nd des o r b ing th e a ds o r b ed CO, th e
a ds o r b ent c a r r ies o ne m eta l o r a m ix tu r e o f m eta l s s e
l ec ted f r o m N i, Mn, Rh , Cu ( I) a nd Ag , a nd a n a ds o r p
tio n tem p er a tu r e is s et to b e 5 0 to 2 5 0 C. to a l l o w a
s ing l e- s tep tr ea tm ent.
1 1 Cl a im s , 7 Dr a wing S h eets
CO - PS A
US . Pa tent Ma y 1 0 , 1 9 8 8 S h eet 1 o f 7 4 , 7 4 3 , 2 7 6
TEMPERATURE ( C )
F|G. 2
1 OO -
ADS ORPTION AMOUN T ( N m Q /g )
TEMPERATURE ( C)
S h eet 3 0 f 7 4 , 7 4 3 , 2 7 6 US . Pa tent Ma y 1 0 , 1 9 8 8
1 4 0 C
C
- - - - - no
CO
3 2 9 2 5 2 8 2 8 m o o 8
1 2 3 4 5 6 7 8 9 1 0 1 ii2 i3 i4 1 5 0 0
TIME ( MIN )
9 0 C
- - - 4 o c
2 3 4 5 s 7 s 9 1 o
TIME( M|N )
3 2 9 2 5 5 0 2 8 N 8 . o 0
US . Pa tent
GAS TEMPERATURE
AFTER COMPRES S ION ( C) CO ADS ORPTION AMOUN T ( m il /g )
IOO
Ma y 1 0 , 1 9 8 8 S h eet 5 0 f 7
F I G. 9
5 0 - b
0 /
4 0 / '
0 /
3 0 - '
2 0 - /o -
1 0 $ '
OO 2 5 5 O 7 5
ION - EXCHAN GE RATE ( /< > )
F I G. I0
5 0 0
S UPPLY GAS
TEMPERATUREI 5 0 C
_ PRES S URE I AMBIEN T
PRES S URE
Al l I I | I l l | l I
O O I 2 3 4 5 6 7 8
PRES S URE ( K g /c m ~ 2 G)
4 , 7 4 3 , 2 7 6
US . Pa tent Ma y 1 0 , 1 9 8 8 S h eet 6 o f 7 4 , 7 4 3 , 2 7 6
0
O
' U
I
I
U
6 1 2 3 4 5 6 7 8 9 1 0
ADS ORPTION PRES S URE ( K g /Cm G)
r
1
O
_ _ _ _ _ .
O O O O O O
7 6 5 4 w 2 . 1
Il l G.
E
1 2 3 4 5 e 7 8 9 1 o
ABS ORPTION PRES S URE ( K g /c m z e)
O
m w w w m
@ L Z Q EQ K PZ MUZ OU 0 0
i
US . Pa tent Ma y 1 0 , 1 9 8 8 S h eet 7 o f 7 4 , 7 4 3 , 2 7 6
F I G. B
Z
2 3 EHZ O 5 ' v H2 O
@ CO- PS A
. 1 5
?wa
FIG. i6
S URGE MAS S
TAN K FLOWMETER
4 , 7 4 3 , 2 7 6
1
METHOD OF S EPARATIN G CARBON
MON OXIDE AN D CARBON MON OXIDE
ADS ORBEN T US ED IN THIS METHOD
Th is a p p l ic a tio n is a c o ntinu a tio n, o f a p p l ic a tio n S er .
N o . 7 5 1 , 0 3 8 , ?l ed J u l y 1 , 1 9 8 5 , no w a b a ndo ned.
BACK GROUN D OF THE IN VEN TION
1 . Fiel d o f th e Inv entio n
Th e p r es ent inv entio n r el a tes to a m eth o d o f s el ec
tiv el y a ds o r b ing CO in a g a s m ix tu r e c o nta ining a t l ea s t
CO a nd CO; with a n a ds o r b ent a nd s ep a r a ting th e a d
s o r b ed CO.
2 . Des c r ip tio n o f th e Pr io r Ar t
Th e g a s m ix tu r e a s m entio ned a b o v e inc l u des na tu r a l
g a s es , m o di?ed g a s es s u c h a s na p h th a , g a s i?ed g a s es o f
c o a l , c o k e o r h ea v y o il , g a s es b y p r o du c ed in ir o n a nd
s teel wo r k s , es p ec ia l l y s h a f t f u r na c e g a s a nd c o nv er ter
g a s , a nd g a s es b y p r o du c ed a t o il r e?ner ies o r p etr o
c h em ic a l p l a nts .
As a m eth o d f o r s ep a r a ting , c o nc entr a ting o r r em o v
ing CO f r o m s u c h a g a s m ix tu r e a nd f o r m a nu f a c tu r ing
a n indu s tr ia l l y u s a b l e g a s , th e p r es s u r e s wing a ds o r p tio n
m eth o d ( to b e r ef er r ed to a s th e PS A m eth o d h er eina f
ter ) u s ing a s o l id a ds o r b ent is k no wn. In th e PS A
m eth o d, a f ter a n a ds o r b ing c o m p o nent is a ds o r b ed in a n
a ds o r b ent u nder a p r es s u r e o f no r m a l l y 1 to 5
k g /c m z ?, th e a ds o r b ed c o m p o nent is des o r b ed f r o m
th e a ds o r b ent a t a r edu c ed p r es s u r e o f 2 0 to 1 0 0 To r r . A
g a s b o o s ter is a r r a ng ed a t a l o c a tio n u p s tr ea m f r o m th e
l o c a tio n f o r p er f o r m ing th is p r o c es s .
Cu r r entl y u s ed a ds o r b ents g ener a l l y h a v e a l a r g er
a f f inity f o r CO2 th a n f o r CO a nd r eq u ir e s o m e p r etr ea t
m ent in o r der to s ep a r a te CO f r o m a g a s m ix tu r e c o n
ta ining CO2 . Fo r ex a m p l e, in th e tec h niq u e dis c l o s ed in
J a p a nes e Pa tent Dis c l o s u r e N o . 5 9 - 2 2 6 2 5 , th e PS A
m eth o d c o ns is ts o f two s tep s o f a p r etr ea tm ent f o r r e
m o v ing wa ter a nd CO2 a nd a PS A s tep f o r a ds o r b ing
CO. In a tec h niq u e dis c l o s ed in J a p a nes e Pa tent Dis c l o
s u r e N o . 5 9 - 2 6 1 2 1 f o r s ep a r a ting CO f r o m a c o nv er ter
g a s , m o r denite is u s ed a s a n a ds o r b ent a nd th e PS A
m eth o d a l s o c o ns is ts o f a PS A s tep o f a ds o r b ing
/s ep a r a ting CO2 a nd a PS A s tep o f a ds o r b ing /s ep a r a t
ing CO.
Ho wev er , s u c h a two - s tep m eth o d r eq u ir es a b u l k y
a p p a r a tu s a nd c o m p l ex p r o c edu r es .
Th e u s e o f a c tiv a ted c a r b o n, s il ic a g el , a c tiv a ted a l u
m ina o r z eo l ite a s a n a ds o r b ent is b eing s tu died. Fo r
ex a m p l e, J a p a nes e Pa tent Dis c l o s u r e N o . 5 8 - 1 5 6 5 1 7
dis c l o s es a s o l id a ds o r b ent c o ns is ting o f h a l o g ena ted
Cu ( I) a nd a c tiv a ted c a r b o n a s a CO a ds o r b ent. Ho w
ev er , no r ep o r t is a v a il a b l e wh ic h dis c l o s es th a t th is
s o l id a ds o r b ent ex h ib its a s ta b l e, a c c ep ta b l e p er f o r
m a nc e o v er a l o ng p er io d o f tim e. US . Pa t. N o .
4 , 0 1 9 , 8 7 9 dis c l o s es a n a ds o r b ent c o ns is ting o f a z eo l ite
h a v ing a s il ic a to a l u m ina r a tio a s h ig h a s 2 0 to 2 0 0 a nd
c a r r y ing Cu ( I) th er eo n. Ho wev er , in a z eo l ite h a v ing
s u c h a h ig h s il ic a to a l u m ina r a tio , th e nu m b er o f io n
ex c h a ng ea b l e c a tio ns is g ener a l l y c o ns ider ed to de
c r ea s e. Th is m ea ns th a t th e CO a ds o r p tio n c a p a c ity p er
u nit weig h t o f th e a ds o r b ent is dec r ea s ed.
S UMMARY OF THE IN VEN TION
It is a ?r s t o b j ec t o f th e p r es ent inv entio n to p r o v ide
a m eth o d o f a ds o r b ing CO in a g a s m ix tu r e c o nta ining
CO2 a nd CO u s ing a n a ds o r b ent a nd th er ea f ter s ep a r a t
1 5
2 0
3 5
4 5
5 5
6 0
6 5
2
ing th e a ds o r b ed CO b y s ing l e- s tep a ds o r p tio n/ s ep a r a
tio n.
It is a s ec o nd o b j ec t o f th e p r es ent inv entio n to p r o
v ide a m eth o d o f r ec o v er ing h ig h l y p u r e CO with a
h ig h r ec o v er y r a te.
It is a th ir d o b j ec t o f th e p r es ent inv entio n to p r o v ide
a m eth o d o f p r o v iding a n a ds o r b ent h a v ing a c a r r ier
s u ita b l e f o r a c h iev ing th e ?r s t a nd s ec o nd o b j ec ts .
It is a f o u r th o b j ec t o f th e p r es ent inv entio n to p r o
v ide a m eth o d o f b o o s ting a n a ds o r p tio n tem p er a tu r e to
a p r edeter m ined tem p er a tu r e ef ?c ientl y a nd ec o no m i
c a l l y wh en CO in a g a s m ix tu r e is a ds o r b ed b y a n a ds o r
b ent.
In o r der to a c h iev e th e ?r s t o b j ec t o f th e p r es ent
inv entio n a c c o r ding to th e p r es ent inv entio n, a n a ds o r
b ent c a r r ies o ne m eta l o r a m ix tu r e o f m eta l s s el ec ted
f r o m N i, Mn, Rh , Cu ( I) a nd Ag , a nd th e a ds o r p tio n
tem p er a tu r e f o r a ds o r b ing CO in th e g a s m ix tu r e is s et
to b e 5 0 to 2 5 0 C. With th is m eth o d, th e CO a ds o r p
tio n a m o u nt is l a r g er th a n th e CO2 a ds o r p tio n a m o u nt,
a nd with a s ing l e- s tep PS A tr ea tm ent, CO c a n b e a d
s o r b ed a nd s ep a r a ted.
In o r der to a c h iev e th e s ec o nd o b j ec t o f th e p r es ent
inv entio n, th e a ds o r p tio n tem p er a tu r e f o r a ds o r b ing CO
is s et to f a l l with in a r a ng e o f 1 5 0 to 2 5 0 C. With th is
m eth o d, th e r a tio o f CO a ds o r p tio n a m o u nt to a ds o r p
tio n a m o u nts o f o th er c o m p o nents ( i. e. , CO/COZ ,
CO/N 2 ) is im p r o v ed, s o th a t h ig h l y p u r e CO c a n b e
r ec o v er ed with a h ig h r ec o v er y r a te.
In o r der to a c h iev e th e th ir d o b j ec t o f th e p r es ent
inv entio n, a n a ds o r b ent c o ns is ts o f a z eo l ite c a r r ier h a v
ing a s il ic a /a l u m ina r a tio o f 1 0 o r l es s a nd a n ef f ec tiv e
p o r e dia m eter o f 0 . 3 8 nm ( 3 . 8 A) o r m o r e c a p a b l e o f
a ds o r b ing CO, a nd o ne m eta l o r a m ix tu r e o f m eta l s
s el ec ted f r o m N i, Mn, Rh , Cu ( I) a nd Ag . Th e a ds o r b ent
h a s a h ig h CO/N z a ds o r p tio n r a tio ( v CO/v N 2 ) a nd h a s
a n ex c el l ent a ds o r p tio n p er f o r m a nc e.
In o r der to a c h iev e th e f o u r th o b j ec t o f th e p r es ent
inv entio n, th e g a s m ix tu r e is a dia b a tic a l l y c o m p r es s ed a t
a p r es s u r e o f 0 . 5 k g /c m 2 . G to 7 k g /c m 2 . G to inc r ea s e
th e g a s m ix tu r e tem p er a tu r e s o a s to s et th e g a s m ix tu r e
a t a n a ds o r p tio n tem p er a tu r e. With th is m eth o d, th e g a s
m ix tu r e c a n b e ef f ic ientl y a nd ec o no m ic a l l y h ea ted
with o u t r eq u ir ing a h ea ter o r th e l ik e.
BRIEF DES CRIPTION OF THE DRAWIN GS
FIG. 1 is a g r a p h s h o wing th e CO a nd CO2 a ds o r p
tio n a m o u nts a s a f u nc tio n o f a ds o r b ent tem p er a tu r e
wh en a Cu ( I) - Y a ds o r b ent is u s ed;
FIG. 2 is a g r a p h s h o wing th e CO a nd CO2 a ds o r p
tio n a m o u nts a s a f u nc tio n o f a ds o r b ent tem p er a tu r e
wh en a n N a Y a ds o r b ent is u s ed;
FIG. 3 is a g r a p h s h o wing th e C0 , C0 2 , a nd N 2
a ds o r p tio n a m o u nts a s a f u nc tio n o f a ds o r b ent tem p er a
tu r e wh en a n Ag Y a ds o r b ent is u s ed;
FIG. 4 is a g r a p h s h o wing th e CO, CO; a nd N 2 a d
s o r p tio n a m o u nts a s a f u nc tio n o f a ds o r b ent tem p er a
tu r e wh en a n Ag m o r denite a ds o r b ent is u s ed;
FIG. 5 is a g r a p h s h o wing b r ea k th r o u g h c u r v es o f
CO a nd CO2 in a Cu ( I) - Y a ds o r p tio n to wer ;
FIG. 6 is a g r a p h s h o wing p u r g e c u r v es o f CO a nd
CO2 in a Cu ( I) - Y a ds o r p tio n to wer ;
FIG. 7 is a g r a p h s h o wing th e C0 , C0 2 a nd N 2 a d
s o r p tio n a m o u nts a s a f u nc tio n o f a ds o r b ent tem p er a
tu r e wh en a Cu ( I) - Y a ds o r b ent is u s ed;
FIG. 8 is a g r a p h s h o wing th e CO p u r ity o f r ec o v
er ed g a s a s a f u nc tio n o f CO r ec o v er y r a te u s ing a ds o r
b ent tem p er a tu r e a s a p a r a m eter ;
4 , 7 4 3 , 2 7 6
3
FIG. 9 is a g r a p h s h o wing th e CO a ds o r p tio n a m o u nt
a s a f u nc tio n o f io n- ex c h a ng e r a te o f z eo l ite;
FIG. 1 0 is a g r a p h s h o wing th e g a s tem p er a tu r e a f ter
b o o s ting a s a f u nc tio n o f g a s tem p er a tu r e wh en a g a s is
a dia b a tic a l l y c o m p r es s ed;
FIG. 1 1 is a g r a p h s h o wing th e CO a nd N 2 a ds o r p tio n
eq u il ib r iu m a m o u nts o f a n a ds o r b ent a s a f u nc tio n o f
a ds o r p tio n p r es s u r e;
FIG. 1 2 is a g r a p h s h o wing th e r ec o v er ed CO c o n
c entr a tio n a s a f u nc tio n o f a ds o r p tio n p r es s u r e;
FIGS . 1 3 a nd 1 4 a r e dia g r a m s s h o wing dif f er ent a p
p a r a tu s es f o r p r a c tis ing th e m eth o d a c c o r ding to th e
p r es ent inv entio n;
FIG. 1 5 is a dia g r a m s h o wing a tes ting a p p a r a tu s f o r
tes ting th e r el a tio ns h ip b etween th e p r es s u r e a nd g a s
tem p er a tu r e wh en a g a s is a dia b a tic a l l y c o m p r es s ed;
a nd
FIG. 1 6 is a dia g r a m s h o wing a tes ting a p p a r a tu s f o r
- tes ting dy na m ic a ds o r p tio n c h a r a c ter is tic s o f a n a ds o r
b ent.
DETAILED DES CRIPTION OF THE
PREFERRED EMBODIMEN TS
Th e p r es ent inv ento r s s tu died o n a m eth o d o f s ep a r a t
ing , c o nc entr a ting a nd el im ina ting CO f r o m a g a s m ix
tu r e c o nta ining CO2 b y a s ing l e- s tep . As a r es u l t o f s u c h
s tu dies , th e p r es ent inv ento r s f o u nd th a t wh en a n a ds o r
b ent h a v ing a m eta l o r a m ix tu r e o f m eta l s s el ec ted f r o m
N i, Mn, Rh , Cu ( I) a nd Ag is c a r r ied o n a c a r r ier , a l
th o u g h th e CO2 a ds o r p tio n a m o u nt is s ev er a l tim es th a t
o f th e CO a ds o r p tio n a m o u nt a t a m b ient tem p er a tu r e,
th e a ds o r p tio n eq u il ib r iu m a m o u nts o f CO a nd C0 ; a r e
r ev er s ed wh en th e a ds o r p tio n tem p er a tu r e is inc r ea s ed.
Mo r e s p ec i?c a l l y , th e r a te o f dec r ea s e in th e a ds o r p tio n
eq u il ib r iu m a m o u nt o f CO s ec u r el y ?x ed to a n a ds o r
b ent a s a f u nc tio n o f tem p er a tu r e inc r ea s e is v er y s m a l l .
Ho wev er , in c o ntr a s t to th is , th e r a te o f dec r ea s e f o r
CO2 is l a r g e.
Th is ?nding is s u r p r is ing f r o m th e g ener a l th eo r y
a c c o r ding to wh ic h a CO a ds o r p tio n a m o u nt is de
c r ea s ed a t h ig h tem p er a tu r es a nd CO a ds o r p tio n/s ep a
r a tio n is th er ef o r e p r ef er a b l y to b e p er f o r m ed a t a m b i
ent tem p er a tu r e.
Th is m ec h a nis m wil l b e des c r ib ed in m o r e deta il .
FIG. 1 is a g r a p h s h o wing th e CO a nd CO2 a ds o r p tio n
a m o u nts wh en Cu ( I) - Y is u s ed a s a n a ds o r b ent. Th e
g r a p h r ev ea l s th a t a s th e tem p er a tu r e is inc r ea s ed, th e
CO2 a ds o r p tio n a m o u nt is a b r u p tl y dec r ea s ed wh il e th e
CO a ds o r p tio n a m o u nt is o nl y s l ig h tl y dec r ea s ed. Wh en
th e a ds o r p tio n tem p er a tu r e r ea c h es a b o u t 5 0 C. , th e
CO a nd CO2 a ds o r p tio n a m o u nts b ec o m e s u b s ta ntia l l y
eq u a l to ea c h o th er . Wh en th e a ds o r p tio n tem p er a tu r e
r ea c h es 1 0 0 C. , th e CO2 a ds o r p tio n a m o u nt is de
c r ea s ed to a b o u t i th e CO a ds o r p tio n a m o u nt. At 1 5 0
C. , th e CO2 a ds o r p tio n a m o u nt is nea r l y z er o . Th er e
f o r e, wh en th is a ds o r b ent is u s ed, wh en a g a s m ix tu r e
c o nta ining a t l ea s t CO, CO; a nd/ o r N 2 is tr ea ted b y th e
PS A m eth o d a t a n o p er a tio n tem p er a tu r e o f 5 0 C. o r
h ig h er , CO c a n b e s ep a r a ted, c o nc entr a ted a nd r e
m o v ed b y a s ing l e s tep .
Ho wev er , wh en th e a ds o r p tio n tem p er a tu r e is in
c r ea s ed a b o v e 2 5 0 C. , th e f o l l o wing p r o b l em s a r e en
c o u nter ed:
( l ) Th e CO a ds o r p tio n a m o u nt is a l s o dec r ea s ed, a nd
th e a m o u nt o f a ds o r b ent r eq u ir ed p er u nit a m o u nt o f g a s
to b e tr ea ted is inc r ea s ed.
( 2 ) Ener g y r eq u ir ed f o r h ea ting th e a ds o r p tio n to wer
a nd/o r g a s to b e tr ea ted is inc r ea s ed.
1 0
2 5
3 5
4 0
4 5
5 5
6 0
6 5
4
( 3 ) Th e m a ter ia l f o r a n el ec tr o m a g netic v a l v e o r th e
l ik e o f a PS A a p p a r a tu s is ex p ens iv e in v iew o f r eq u ir ed
h ea t r es is ta nc e a nd th e l ik e.
( 4 ) S u b r ea c tio ns s u c h a s Hg - CO a nd HZ O- CO o c c u r .
Fo r s u c h r ea s o ns , th e a ds o r p tio n tem p er a tu r e m u s t no t
ex c eed 2 5 0 C.
Fo r th e r ea s o ns des c r ib ed a b o v e, a c c o r ding to th e
p r es ent inv entio n, th e tem p er a tu r e r a ng e f o r p er f o r m ing
CO a ds o r p tio n is s et to b e 5 0 to 2 5 0 C. In th is c a s e, if
th e p u r ity a nd r ec o v er y r a te o f r ec o v er ed C0 a r e no t
p a r tic u l a r l y a t is s u e, th e a ds o r p tio n tem p er a tu r e c a n f a l l
with in th e r a ng e o f 5 0 to 1 5 0 C. Ho wev er , in o r der to
r ec o v er h ig h l y p u r e CO a t a h ig h r ec o v er y r a te, th e
a ds o r p tio n tem p er a tu r e r a ng e is p r ef er a b l y s et to b e
1 5 0 to 2 5 0 C.
With in th e tem p er a tu r e r a ng e p r es c r ib ed a b o v e, th e
CO a nd CO2 a ds o r p tio n eq u il ib r iu m c h a r a c ter is tic s a r e
a s f o l l o ws . As c o m p a r ed to th e c a s e wh er ein th e a ds o r p
tio n tem p er a tu r e f a l l s o u ts ide th is r a ng e, th e CO a ds o r p
tio n eq u il ib r iu m a m o u nt dec r ea s es a l th o u g h o nl y
s l ig h tl y . Th is m ea ns a n inc r ea s e in th e a m o u nt o f a ds o r
b ent r eq u ir ed f o r tr ea ting a u nit a m o u nt o f g a s a nd is no t
a des ir a b l e c o nditio n. 7
Ho wev er , th e CO2 a nd N 2 a ds o r p tio n eq u il ib r iu m
a m o u nts a r e q u ite dif f ic u l t to dec r ea s e a b r u p tl y a s c o m
p a r ed to th e CO a ds o r p tio n eq u il ib r iu m a m o u nt. Fo r
th is r ea s o n, th e CO/COZ a ds o r p tio n r a tio a nd th e
CO/N z a ds o r p tio n r a tio c a n b e s et to b e v er y l a r g e a nd
th e s el ec tiv e CO a ds o r p tio n p er f o r m a nc e o f a n a ds o r
b ent c a n b e inc r ea s ed c o ns ider a b l y .
In a dditio n, s inc e th e m eth o d o f th e p r es ent inv entio n
is p er f o r m ed a t a h ig h tem p er a tu r e, wh en a n im p u r ity
g a s b etween a ds o r b ent p a r tic l es in r ec o v er ed CO g a s o r
a n im p u r ity g a s wh ic h is c o - a ds o r b ed is p u r g ed, th e
p u r g e s tep c a n b e p er f o r m ed with in a s h o r t p er io d o f
tim e a nd with a h ig h ef ?c ienc y . Wh en th e r ec o v er ed
CO is v a c u u m - ex h a u s ted a nd des o r b ed, th e p r o c es s c a n
b e p er f o r m ed with in a s h o r t p er io d o f tim e.
As a c a r r ier f o r a n a ds o r b ent to b e u s ed in a CO
a ds o r p tio n m eth o d a c c o r ding to th e p r es ent inv entio n, a
z eo l ite h a v ing a s il ic a /a l u m ina r a tio o f 1 9 o r l es s a nd
ef f ec tiv e p o r e dia m eter o f 0 . 3 8 nm ( 3 . 8 A) c a p a b l e o f
a ds o r b ing CO is p r ef er a b l y u s ed. Ex a m p l es o f a z eo l ite
c a r r ier m a y inc l u de Y- ty p e z eo l ite ( N a 2 O. Al 2 O3 4 .
8 S iO2 , 8 . 9 1 1 2 0 ) , A- ty p e z eo l ite ( N a 2 O. Al 2 O3 . 2 S iO2 . 4 . 5
H2 O) , m o r denite ( N a 2 O. Al 2 O. Al 2 O3 . 9 - 1 0 S iO2 . 6 Hg O) ,
X- ty p e z eo l ite ( N a 2 O. Al 2 O3 . 2 . 5 S iO2 . 6 H2 O) , L- ty p e
c l ino p til o l ite, Q - ty p e c l ino p til o l ite, er io nite, f a u j a s ite,
Z K - 4 , Z S M- 2 , Z S M- 3 , Z S M- 4 a nd Z S M- l O. A z eo l ite
c a r r ier c a n b e a na tu r a l o r s y nth etic z eo l ite.
An a ds o r b ent u s ing s u c h a z eo l ite c a r r ier h a s a h ig h
CO/N z a ds o r p tio n r a tio ( VCO/VN Z ) . Fo r ex a m p l e, N iY,
MnY a nd Rh Y h a v e h ig h CO/N z a ds o r p tio n r a tio s
( v CO/v N g ) o f a b o u t 2 . 5 o r m o r e, a nd Cu ( I) - Y, Ag Y a nd
Ag X h a v e ex tr em el y h ig h CO/N z a ds o r p tio n r a tio s o f
a b o u t 6 o r m o r e. Th e r ea s o n f o r th is is s u r m is ed to b e a s
f o l l o ws . Wh en a s el ec ted c a r r ier c o nta ins N i, Mn o r Rh ,
th e c a r r ied c a tio ns c a u s e a c h a ng e in p o r e dia m eter o f
th e z eo l ite to a l l o w ea s ier a ds o r p tio n o f CO th a n N 2 .
Cu ( I) a nd Ag c a tio ns wh ic h a r e tr a ns itio n el em ent c o p
p er g r o u p el em ents a nd h a v e a v a l enc y o f l h a v e a g o o d
a f f inity f o r CO. A s y ner g etic ef f ec t o f th es e two ef f ec ts
is a l s o p l a u s ib l e.
An a ds o r b ent u s ing a m eta l h a v ing a s tr o ng r edu c ing
p r o p er ty , e. g . , Ag Y, is s u ita b l e f o r u s e in s ep a r a ting CO
f r o m a g a s m ix tu r e wh ic h do es no t c o nta in h y dr o g en,
a c c o r ding to ex p er im ents c o ndu c ted b y th e p r es ent
inv ento r s . Am o ng th e z eo l ites enu m er a ted a b o v e, Ag Y
4 , 7 4 3 , 2 7 6
5
( 7 5 % io n- ex c h a ng ed) wa s u s ed to p er f o r m 6 a ds o r p
tio n/ des o r p tio n c y c l es o f a s ta nda r d g a s h a v ing a c o m
p o s itio n ( 7 4 % CO, 9 % CO2 , 3 % Hz a nd th e b a l a nc e o f
N 2 ) s u b s ta ntia l l y th e s a m e a s th a t o f a c o nv er ter g a s .
Th e a m o u nt o f CO a ds o r b ed b y th is a ds o r b ent a t 2 0 C.
a nd th e a m b ient p r es s u r e wa s dec r ea s ed f r o m 5 2 . 3 m l / g
o f th e ?r s t c y c l e to 4 1 . 7 m l /g , i. e. , b y 2 0 %. Th is is
a ttr ib u ted to th e f a c t th a t s il v er io ns a r e r edu c ed to
m eta l s il v er b y h y dr o g en a l th o u g h a t a m b ient tem p er a
tu r e.
Th e m eta l c a r r y ing m eth o d need no t b e th e io n- ex
c h a ng e m eth o d b u t c a n b e th e im p r eg na tio n m eth o d.
Ac c o r ding to a n im p r eg na tio n m eth o d, a z eo l ite is im
m er s ed in a s o l u tio n o f a p r edeter m ined m eta l s a l t u nder
a g ita tio n, a nd th e s o l u tio n is ev a p o r a ted to p r o v ide a
s o l id m a ter ia l . ( Ta k a h o S h ir a z a k i & N a o y u k i To do , ed. ,
S h o k u b a i Ch o s ei ( Ca ta l y s t Adj u s tm ent) , K o da ns h a
S c ienti?c , p p . 3 3 0 to 3 3 7 , 1 9 7 4 )
Wh en a n a ds o r b ent o f th e p r es ent inv entio n is p r e
p a r ed b y r edu c ing a Cu ( II) z eo l ite into a Cu ( I) z eo l ite,
H2 , CO, N H3 , o r CH4 g a s c a n b e u s ed a s a r edu c ing g a s
a t p r edeter m ined tem p er a tu r e a nd p r es s u r e. In o r der to
c a r r y l - v a l enc y c o p p er o n N a z eo l ite, Cu ( I) is dis s o l v ed
in l iq u id a m m o nia a nd io n- ex c h a ng e is p er f o r m ed.
Ac c o r ding to th e p r es ent inv entio n, in o r der to
a c h iev e a p r es ent a ds o r p tio n tem p er a tu r e o f 5 0 to 2 5 0
C. , th e g a s m ix tu r e is a dia b a tic a l l y c o m p r es s ed b y a g a s
b o o s ter with in a p r es s u r e r a ng e o f 0 . 5 to 7 k g /c m 2 . G to
o b ta in a g o o d ef f ec t.
In a c o nv entio na l PS A tr ea tm ent a ta m b ient tem p er a
tu r e, th e b o o s ting o r c o m p r es s io n deg r ee is s et indep en
dentl y o f a n a ds o r p tio n tem p er a tu r e, a nd h ea t c o r r e
s p o nding to th e tem p er a tu r e inc r ea s e b y a dia b a tic c o m
p r es s io n is ex h a u s ted o u ts ide th e r ea c tio n s y s tem . In
c o ntr a s t to th is , a c c o r ding to th e p r es ent inv entio n, th e
b o o s ting deg r ee is s et in r el a tio n to a n a ds o r p tio n tr ea t
m ent tem p er a tu r e o f a g a s m ix tu r e with a n a ds o r b ent,
a nd th e r es u l ta nt tem p er a tu r e inc r ea s e u p o n b o o s ting is
u til iz ed.
Th is m eth o d wil l b e des c r ib ed with r ef er enc e to a
c a s e wh er ein a c o nv er ter g a s o f a n ir o n a nd s teel wo r k
is a g a s m ix tu r e to b e tr ea ted.
A c o nv er ter g a s g ener a l l y h a s th e f o l l o wing c o m p o s i
tio n:
CO 6 0 - 8 0 %
CO2 1 0 - 2 0 %
H; 0 . 5 - 2 %
N 2 5 - 2 0 %
Wa ter 4 0 - 8 0 C. s a tu r a tio n a m o u nt
Wh en th e s u p p l y g a s tem p er a tu r e is a s s u m ed to b e 5 0
C. , th e c o nv er ter g a s tem p er a tu r e is inc r ea s ed b y a
b o o s ter , a s s h o wn in FIG. 1 0 .
As s h o wn in FIG. 7 , th e CO a ds o r p tio n a m o u nt b y
th e a ds o r b ent o nl y s l ig h tl y dec r ea s es with a n inc r ea s e in
tem p er a tu r e. In c o ntr a s t to th is , th e CO2 a ds o r p tio n
a m o u nt a b r u p tl y dec r ea s es , th u s inc r ea s ing th e CO/
CO2 r a tio . Wh en o nl y th is f a c to r is c o ns ider ed, th e
s ep a r a tio n p er f o r m a nc e o f CO a nd CO2 is inc r ea s ed
with a n inc r ea s e in tem p er a tu r e. Ho wev er , wh en th e
tem p er a tu r e is inc r ea s ed, th e CO a ds o r p tio n a m o u nt
its el f is dec r ea s ed, r es u l ting in a b u l k y a ds o r p tio n to wer .
Mo r eo v er , ex c es s iv e h ea ting is no t des ir a b l e wh en c o n
s ider ed f r o m th e v iewp o int o f th e a p p a r a tu s s inc e th e
m a ter ia l o f a n el ec tr o m a g netic v a l v e o r th e l ik e is ex
1 0
3 0
3 5
5 0
5 5
6 5
6
p ens iv e a nd s u b ~ r ea c tio ns o f HZ - CO a nd Hz O- CO a r e
c a u s ed.
Wh en th e p r es s u r e is c o ns ider ed, a s s h o wn in FIG.
1 1 , a s th e p r es s u r e is inc r ea s ed, th e CO a ds o r p tio n eq u i
l ib r iu m a m o u nt is inc r ea s ed. Ho wev er , with a n inc r ea s e
in p r es s u r e, th e N 2 a ds o r p tio n eq u il ib r iu m a m o u nt is
a l s o inc r ea s ed. Th is m ea ns th a t th e a ds o r p tio n to wer is
r ender ed c o m p a c t if th e p r es s u r e is inc r ea s ed. Th e CO
a nd N 2 a ds o r p tio n eq u il ib r iu m a m o u nts wer e c a l c u
l a ted. In th is c a l c u l a tio n, a g a s m ix tu r e o f CO/N 2 =l is
intr o du c ed into a n a ds o r p tio n to wer . Af ter a n a ds o r p
tio n eq u il ib r iu m is es ta b l is h ed, CO is des o r b ed a nd th e
des o r b ed CO c o nc entr a tio n a t ea c h a ds o r p tio n p r es s u r e
is p l o tted. Th e o b ta ined r es u l ts a r e s h o wn in FIG. 1 2 .
Th e g r a p h o f FIG. 1 2 r ev ea l s th a t th e CO c o nc entr a tio n
dec r ea s es with a n inc r ea s e in p r es s u r e.
In p r a c tic e, h o wev er , th e CO p a r tia l p r es s u r e is m u c h
l a r g er th a n th a t o f th e N 2 p a r tia l p r es s u r e in th e g a s
m ix tu r e. Fo r th is r ea s o n, th e CO p u r ity is a s s u m ed to b e
m u c h b etter th a n th a t s h o wn in FIG. 1 2 . In a dditio n,
s inc e a p u r g e s tep is no r m a l l y p er f o r m ed, a des ir ed
p u r ity inc r ea s e c a n b e a c h iev ed. Ho wev er , if th e p r es
s u r e is inc r ea s ed to o m u c h , th e p u r g e g a s a m o u nt f o r
im p r o v ing th e g a s p u r ity is inc r ea s ed, a nd th e CO r e
c o v er y r a te is dec r ea s ed.
In c o ns ider a tio n o f th e a na l y s is r es u l ts o f tem p er a tu r e
a nd p r es s u r e in r el a tio n to th e a ds o r p tio n c h a r a c ter is tic s
a nd h ea t l o s s in a n a c tu a l a p p a r a tu s , th e c o m p r es s io n
p r es s u r e in th e p r es ent inv entio n is 0 . 5 to 7 k g /c m 2 . G
a nd p r ef er a b l y 0 . 5 to 5 k g /c m 2 . G.
Ac c o r ding to th e m eth o d o f th e p r es ent inv entio n,
ev en if th e s u p p l y g a s c o nta ins a s a tu r a tio n a m o u nt o f
wa ter a t th e s el ec ted a ds o r p tio n tem p er a tu r e, th e wa ter
c o ntent wil l no t c o ndens e s inc e th e g a s is h ea ted b y a
b o o s ter . Th er ef o r e, if a n a ds o r b ent no t s u b j ec t to a n
in?u enc e o f wa ter c o ntent is u s ed, a PS A tr ea tm ent o f
CO c a n b e p er f o r m ed b y a s im p l e p r o c es s u s ing o nl y a
g a s b o o s ter 1 a s s h o wn in FIG. 1 3 . In th is c a s e, th e
p r es s u r e o f th e b o o s ter c a n b e ?x ed a t a p r edeter m ined
v a l u e with in th e p r es c r ib ed r a ng e, o r th e a ds o r p tio n
tem p er a tu r e c a n b e k ep t c o ns ta nt.
Ho wev er , if a n a ds o r b ent is o f a ty p e ea s il y s u s c ep ti
b l e to a n inf l u enc e o f wa ter c o ntent, a s s h o wn in FIG.
1 4 , a h ea t ex c h a ng er 2 a nd a c o o l ing u nit 3 c a n b e in
c l u ded a f ter a b o o s ter 1 . In th is c a s e, th e s a tu r a tio n
wa ter c o ntent a t a m b ient tem p er a tu r e is c o o l ed b y th e
h ea t ex c h a ng er 2 u nder p r es s u r e to p r o v ide a n ex
tr em el y g o o d des o r p tio n ef f ec t, a nd th e p o wer r eq u ir ed
to dr iv e th e c o o l ing u nit 3 is r edu c ed to a m inim u m .
As s u m e a c a s e wh er ein th e s u p p l y g a s is s u p p l ied in
th e a m o u nt ( r a te) o f l k g /Hr , wa ter in a n a m o u nt to
s a tu r a te a t 5 0 C. is a dded to p r o v ide a h u m id g a s , a nd
th e g a s is b o o s ted to a p r es s u r e o f 3 k g /c m 2 . G. Wh en
th e m a ter ia l ex c h a ng es in th e f l o w s h o wn in FIG. 1 4 a r e
c a l c u l a ted, th e r es u l ts a s s h o wn in Ta b l e 1 b el o w a r e
o b ta ined. It c a n b e s een f r o m th es e r es u l ts th a t th e wa ter
r em o v a l ef f ec t o b ta ina b l e with a h ea t ex c h a ng er is s u b
s ta ntia l .
TABLE 1
Mea s u r ing p o int a b c d e
Ga s p r es s u r e 0 3 3 3 3
k g /c m 2 - G
Ga s tem p er a tu r e C. 5 0 2 7 0 4 0 1 0 1 9 6
Dr y b a s e g a s a m o u nt 1 1 1 1 l
k g /I- Ir
Ga s wa ter c o ntent 0 . 0 8 3 0 . 0 8 3 0 . 0 1 1 0 . 0 0 2 0 . 0 0 2
k g /Hr
Co ndens ed wa ter 0 . 0 7 2 0 . 0 0 9
4 , 7 4 3 , 2 7 6
7
TABLE l - c o ntinu ed
Mea s u r ing p o int a b c d e
a m o u nt k g /Hr
To ta l deh y dr a tio n 8 6 . 6 9 7 . 7
r a te %
In th is m a nner , a c c o r ding to th e m eth o d o f s etting th e
h ig h - tem p er a tu r e PS A tr ea tm ent a ds o r p tio n tem p er a
tu r e b y s etting a nd/o r c o ntr o l l ing th e p r es s u r e o f a
b o o s ter , o nl y a b o o s ter is b a s ic a l l y r eq u ir ed. Th u s , a
c o o l ing u nit a nd/o r a wa ter - c o o l ed c o o l er no r m a l l y
u s ed in a c o nv entio na l PS A p r o c es s p er f o r m ed a t a m b i
ent p r es s u r e is no t r eq u ir ed, r es u l ting in a v er y s im p l e
a nd ec o no m ic a l p r o c es s .
Th e p r es ent inv entio n wil l no w b e des c r ib ed b y wa y
o f its Ex a m p l es .
EXAMPLE 1
C0 , C0 2 a nd N 2 Ads o r p tio n Ch a r a c ter is tic s o f Cu ( I) - Y
Ads o r b ent o f Pr es ent Inv entio n a nd N a Y Ads o r b ent o f
Co m p a r a tiv e Ex a m p l e a s a Fu nc tio n o f Tem p er a tu r e
A 0 . 5 N s o l u tio n o f Cu Cl ; wa s p r ep a r ed. Ten g r a m s o f
N a Y z eo l ite a nd 5 0 m l o f th e 0 . 5 N s o l u tio n wer e
c h a r g ed into a 1 0 0 m l r o u nd ?a s k . Af ter m o u nting a
c o ndens er o n th e r o u nd ?a s k , h ea t r e?u x ing wa s p er
f o r m ed a t 1 0 0 C. b y a m a ntl e h ea ter f o r 2 h o u r s . Af ter
th e ?a s k wa s l ef t to s ta nd, th e s u p er na ta nt wa s r ec o v
er ed b y dec a nta tio n. Ano th er 5 0 m l o f th e 0 . 5 N s o l u tio n
wer e a dded a nd s im il a r r e?u x ing wa s p er f o r m ed. Th e
r e?u x ing wa s p er f o r m ed a to ta l o f th r ee tim es . Th e
z eo l ite wa s wa s h ed wel l with p u r e wa ter , dr ied a t 1 1 0
C. , p u l v er iz ed, a nd b a k ed in a n el ec tr ic f u r na c e a t 4 5 0
C. f o r 2 h o u r s to p r ep a r e a n a ds o r b ent. Th e r ec o v er ed
s u p er na ta nt a nd th e ?l tr a te wer e m ix ed a nd th e m ix tu r e
wa s s u b j ec ted to ?a m e a na l y s is to deter m ine th e a m o u nt
o f r el ea s ed N a a nd th e io n- ex c h a ng e r a te. Th e o b ta ined
Cu ( II) - Y z eo l ite wa s r edu c ed in a h y dr o g en a tm o s p h er e
a t 1 8 0 C. f o r 3 0 m inu tes to p r o v ide Cu ( I) - Y.
Two g r a m s o f th e a ds o r b ent p r ep a r ed in th is m a nner
wer e c h a r g ed into a 2 0 m l s a m p l e b o ttl e wh ic h wa s s et
o n a c o ns ta nt- p r es s u r e ty p e a ds o r p tio n a m o u nt m ea s u r
ing a p p a r a tu s . Deh y dr a tio n wa s p er f o r m ed b y h ea ting
a t 1 5 0 C. in a v a c u u m o f 1 0 - 3 m m Hg f o r 1 h o u r .
Th e s a m p l e b o ttl e wa s s et in a th er m o s ta t a nd wa s l ef t
to s ta nd f o r 2 0 to 3 0 m inu tes . Wh il e th e b o ttl e wa s k ep t
a t th e m ea s u r ing tem p er a tu r e, He g a s ( p u r ity o f 9 9 . 9 %
u p ) wa s f ed in o r der to m ea s u r e th e a ds o r p tio n a m o u nt
u p to a s a tu r a tio n a ds o r p tio n a m o u nt a nd to deter m ine
th e dea d v o l u m e. Th e m ea s u r ing tem p er a tu r e wa s s e
q u entia l l y inc r ea s ed with in a r a ng e o f a b o u t 0 to a b o u t
1 5 0 C. a f ter m ea s u r ing th e s a tu r a tio n a ds o r p tio n
a m o u nt a t ea c h s et tem p er a tu r e. Af ter th e m ea s u r em ent,
des o r p tio n b y h ea ting a t 1 5 0 C. a t a p r es s u r e o f 1 0 * 3
m m Hg wa s p er f o r m ed a nd th e a ds o r b ent wa s l ef t to
na tu r a l l y c o o l . Th e a ds o r p tio n a m o u nt wa s m ea s u r ed
u s ing th e m ea s u r em ent g a s a nd f o l l o wing th e s a m e p r o - '
c edu r es a s des c r ib ed a b o v e. Af ter c o m p l eting m ea s u r e
m ents a t a l l g a s tem p er a tu r es , th e a ds o r p tio n a m o u nt
wa s m ea s u r ed. Th e CO a nd CO2 s a tu r a tio n a ds o r p tio n
a m o u nts p er u nit weig h t o f th e a ds o r b ent wer e deter
m ined in a c c o r da nc e with th e o b ta ined m ea s u r em ent.
FIG. 1 s h o ws th e o b ta ined r es u l ts . It c a n b e s een f r o m
FIG. 1 th a t th e a ds o r p tio n eq u il ib r iu m a m o u nts o f CO2
a nd C0 a r e r ev er s ed a t 5 0 C.
Ba s ed o n th es e r es u l ts , wh en a g a s m ix tu r e c o nta ining
a t l ea s t CO, CO; a nd/o r N 2 is tr ea ted a t 5 0 to 1 5 0 C.
b y th e PS A m eth o d a nd u s ing th is a ds o r b ent, s ep a r a
l 0
1 5
2 0
2 5
3 0
3 5
4 5
5 0
5 5
6 5
8
tio n, c o nc entr a tio n a nd r em o v a l o f CO c a n b e p er
f o r m ed b y a s ing l e- s tep m eth o d.
As a Co m p a r a tiv e Ex a m p l e, N a Y wh ic h wa s no t
s u b j ec ted to io n- ex c h a ng e with a m eta l wa s u s ed a s a n
a ds o r b ent, a nd th e s a tu r a tio n a ds o r p tio n a m o u nts wa s
deter m ined in a c c o r da nc e with th e s a m e m eth o d a s
des c r ib ed a b o v e. Th e o b ta ined r es u l ts a r e s h o wn in
FIG. 2 . In th is c a s e, th e CO2 a nd CO a ds o r p tio n eq u il ib
r iu m a m o u nts wer e no t r ev er s ed. Th is m ea ns th a t th e
r ev er s a l o f th e a ds o r p tio n a m o u nts a s s h o wn in FIG. 1
is a p h eno m eno n o c c u r r ing u niq u el y in a n a ds o r b ent in
wh ic h a s p ec i?c tr a ns itio n el em ent is c a r r ied o n a z eo
l ite.
EXAMPLE 2
C0 , C0 2 a nd N 2 Ads o r p tio n Ch a r a c ter is tic s o f Ag Y
Ads o r b ent a s a Fu nc tio n o f Tem p er a tu r e
Ag wa s c a r r ied o n N a Y u s ing a n Ag N O3 s o l u tio n
f o l l o wing th e s a m e p r o c edu r es a s in Ex a m p l e 1 . Th e
o b ta ined io n- ex c h a ng e r a te wa s 7 4 . 9 %. Th e s a tu r a tio n
a ds o r p tio n a m o u nts o f th e r es u l ta nt Ag Y a ds o r b ent
wer e deter m ined b y th e s a m e m ea s u r ing m eth o d a s in
Ex a m p l e 1 . Th e o b ta ined r es u l ts a r e s h o wn in FIG. 3 .
Th e s a tu r a tio n a ds o r p tio n a m o u nts c h a ng e in a s u b s ta n
tia l l y s im il a r m a nner to th o s e o f Cu ( I) Y in FIG. 1 .
EXAMPLE 3
C0 , C0 2 a nd N 2 Ads o r p tio n Ch a r a c ter is itc s o f Ag
Mo r denite Ab s o r b ent a s a Fu nc tio n o f Tem p er a tu r e
Th e s a tu r a tio n a ds o r p tio n a m o u nt o f a n Ag m o r den
ite a ds o r b ent ( 1 0 0 % io n- ex c h a ng e r a te) o b ta ined b y
c a r r y ing Ag o n N a m o r denite in a s im il a r m a nner to
th a t in Ex a m p l e 1 wa s deter m ined b y th e s a m e m ea s u r
ing m eth o d a s th a t in Ex a m p l e 1 . Th e o b ta ined r es u l ts
a r e s h o wn in FIG. 4 . Al th o u g h th e dec r ea s e r a te o f th e
CO2 a ds o r p tio n a m o u nt is s m a l l , a t 1 0 0 C. , th e CO2
a ds o r p tio n a m o u nt is a b o u t g th e CO a ds o r p tio n
a m o u nt.
EXAMPLE 4
S ep a r a tio n o f CO b y S ing l e- S tep Tr ea tm ent
1 6 0 g o f 2 m m q b XZ m m Cu ( II) - Y o b ta ined b y a dding
2 0 % o f a p el l etiz er a nd p el l etiz ing wer e p a c k ed a t a
p a c k ing dens ity o f 0 . 4 5 in a p y r ex g l a s s tu b e h a v ing a
dia m eter ( inner dia m eter ) o f 3 0 m m a nd a l eng th o f 5 0 0
m m to p r o v ide a n a ds o r p tio n to wer . An a ds o r p tio n tes t
wa s p er f o r m ed u s ing th is a ds o r p tio n to wer . A g a s m ix
tu r e tr ea ted wa s a s ta nda r d g a s c o ns is ting o f 7 3 . 9 % o f
CO, 9 . 0 % o f CO2 , 3 . 0 % o f H2 a nd th e b a l a nc e o f N 2
a s s u m ing a n o f f - g a s o f a n ir o n a nd s teel wo r k .
In o r der to r edu c e th e Cu ( l I) - Y, p u r e CO g a s wa s
?l l ed in th e to wer a nd h ea ted a t 2 5 0 C. f o r 1 h o u r . Th e
a ds o r b ent c o l o r c h a ng ed f r o m da r k b l u e to wh ite. Af ter
r edu c ing , th e C0 wa s s u f f ic ientl y des o r b ed a nd p u r g ed
a t 2 0 0 C. a m d 1 0 - 3 m m Hg f o r 1 h o u r wh il e He wa s
intr o du c ed a nd th e r ea c tio n s y s tem wa s k ep t a t 2 0 0 C.
In o r der to c o ntinu o u s l y m ea s u r e CO a nd CO2 c o nc en
tr a tio ns , two no n- s c a tter ing inf r a r ed r a y a na l y s is a p p a
r a tu s es wer e m o u nted a t th e o u tl et p o r t o f th e a ds o r p
tio n to wer . Th e g a s m ix tu r e wa s p a s s ed th r o u g h th e
a ds o r p tio n to wer a t a r a te o f 2 N l /m in a nd th e CO a nd
CO2 c o nc entr a tio ns a t th e o u tl et p o r t wer e m ea s u r ed.
Th e b r ea k th r o u g h c u r v es wh en th e CO/COz a ds o r p
tio n wa s p er f o r m ed a t 1 1 0 C. a nd 1 4 0 C. a r e s h o wn in
FIG. 5 . At eith er tem p er a tu r e, CO2 c a u s ed a b r ea k
th r o u g h f a s ter th a n CO indic a ting th a t th e a ds o r b ent
4 , 7 4 3 , 2 7 6
9
h a s a h ig h er CO a ds o r p tio n c a p a c ity th a n a C0 2 a ds o r p
tio n c a p a c ity . It wa s a l s o r ev ea l ed th a t th e b r ea k
th r o u g h tim e is s h o r tened a t h ig h er tem p er a tu r es . In
th is m a nner , it wa s c o n?r m ed th a t CO c a n b e s ep a r a ted
f r o m a g a s m ix tu r e c o nta ining C0 , C0 2 , H2 a nd N ; b y
a s ing l e s tep .
EXAMPLE 5
Pu r g e Ch a r a c ter is tic s o f CO2
Af ter th e a b o v e- m entio ned g a s m ix tu r e c a u s ed a
b r ea k th r o u g h a t 4 0 C. a nd 9 0 C. u s ing th e a ds o r b ent
a nd th e a p p a r a tu s u s ed in Ex a m p l e 4 , th e p u r e CO g a s
wa s p a s s ed th r o u g h th e to wer a t a r a te o f 2 N l /m in to
p u r g e th e to wer inter io r a nd th e CO a nd CO2 c o nc en
tr a tio ns a t th e to wer o u tl et p o r t wer e m ea s u r ed. Th e
o b ta ined r es u l ts a r e s h o wn in FIG. 6 . At tem p er a tu r es
o f 5 0 C. o r l o wer ( 4 0 C. f o r th e do tted c u r v e) wh ic h
is th e r ev er s a l tem p er a tu r e o f th e CO a nd CO2 s a tu r a
tio n a ds o r p tio n a m o u nts , it ta k es 6 m inu tes to p u r g e
CO2 . Ho wev er , a t tem p er a tu r es h ig h er th a n th is r ev er
s a l tem p er a tu r e ( 9 0 " C. f o r th e s o l id c u r v e) , p u r g ing
ta k es o nl y 2 m inu tes . It c a n b e s een f r o m th is o b s er v a
tio n th a t p u r g ing c a n b e p er f o r m ed with in a s h o r ter
p er io d o f tim e a t h ig h er tem p er a tu r es .
EXAMPLE 6
CO, CO; a nd N 2 Ads o r p tio n Ch a r a c ter is tic s o f th e
Ads o r b ent a t 5 0 C. to 2 5 0 C.
5
1 5
2 0
2 5
A 0 . 5 N s o l u tio n o f Cu Cl g wa s p r ep a r ed. Ten g r a m s o f 3 0
N a Y z eo l ite a nd 5 0 m l o f th e 0 . 5 N Cu Cl z s o l u tio n wer e
c h a r g ed in a 1 0 0 m l r o u nd ?a s k . Af ter a c o ndens er wa s
m o u nted o n th e r o u nd ?a s k , h ea t r ef l u x ing wa s p er
f o r m ed a t 1 0 0 C. f o r 2 h o u r s . Af ter th e s o l u tio n wa s l ef t
to s ta nd, th e s u p er na ta nt wa s r ec o v er ed b y dec a nta tio n.
Af ter a dding a no th er 5 0 m l o f th e 0 . 5 N Cu Cl g s o l u tio n,
r e?u x ing wa s p er f o r m ed in a s im il a r m a nner . Th e r e
?u x ing wa s p er f o r m ed a to ta l o f th r ee tim es . Th e z eo l ite
wa s wa s h ed wel l with p u r e wa ter , dr ied a t 1 1 0 C. ,
p u l v er iz ed a nd b a k ed in a n el ec tr ic f u r na c e a t 4 5 0 C. to
p r o v ide a n a ds o r b ent. Th e r ec o v er ed s u p er na ta nt a nd
th e ?l tr a te wer e m ix ed a nd th e m ix tu r e wa s s u b j ec ted to
?a m e a na l y s is to deter m ine th e a m o u nt o f r el ea s ed N a
a nd th e io n- ex c h a ng e r a te. Th e io n- ex c h a ng e r a te wa s
deter m ined to b e 8 3 . 5 %. Th e o b ta ined Cu ( II) - Y z eo l ite
wa s r edu c ed in a CO a tm o s p h er e a t 3 0 0 C. f o r 6 0 m in
u tes to p r o v ide Cu ( I) - Y.
Two g r a m s o f th e a ds o r b ent p r ep a r ed in th is m a nner
wer e c h a r g ed into a 2 0 m l s a m p l e b o ttl e wh ic h wa s s et
in a c o ns ta nt- p r es s u r e ty p e a ds o r p tio n a m o u nt m ea s u r
ing a p p a r a tu s . Deh y dr a tio n wa s p er f o r m ed a t 3 0 0 C. in
a v a c u u m o f 1 0 ' - 3 m m Hg f o r 2 h o u r s .
Th e s a m p l e b o ttl e wa s p l a c ed in a s il ic o ne o il ta nk
a nd wa s l ef t to s ta nd f o r 2 0 to 3 0 m inu tes . Wh il e th e
b o ttl e wa s k ep t a t th e m ea s u r ing tem p er a tu r e, He g a s
( p u r ity : 9 9 . 9 % u p ) wa s f ed. Th e a ds o r p tio n a m o u nt wa s
m ea s u r ed u ntil it r ea c h ed th e s a tu r a tio n a ds o r p tio n
a m o u nt to deter m ine th e dea d v o l u m e. Th e m ea s u r ing
tem p er a tu r e wa s s eq u entia l l y inc r ea s ed with in a r a ng e
o f a b o u t 0 to 3 0 0 C. a f ter m ea s u r ing th e s a tu r a tio n
a ds o r p tio n a m o u nt a t ea c h s et tem p er a tu r e. Af ter m ea
s u r em ent, h ea ting /des o r p tio n wa s p er f o r m ed a t 3 0 0 C.
a nd 1 0 - 3 m m Hg f o r 1 h o u r . Af ter th e a ds o r b ent wa s l ef t
to na tu r a l l y c o o l , th e a ds o r p tio n a m o u nt wa s m ea s u r ed
u s ing th e m ea s u r ing g a s f o l l o wing th e s a m e p r o c edu r es
a s des c r ib ed a b o v e. Af ter m ea s u r ing th e C0 , C0 2 a nd
N 2 a ds o r p tio n a m o u nts , th e s a m p l e wa s m ea s u r ed. Th e
CO a nd CO2 a ds o r p tio n eq u il ib r iu m a m o u nts p er u nit
3 5
4 5
5 0
5 5
6 0
6 5
1 0
weig h t o f th e a ds o r b ent wer e deter m ined u s ing th is
v a l u e.
FIG. 7 s h o ws th e o b ta ined r es u l ts . Th e CO a nd CO2
a ds o r p tio n eq u il ib r iu m a m o u nts a r e r ev er s ed a t a tem
p er a tu r e o f a b o u t 5 0 C. a s in th e c a s e o f Ex a m p l e 1 .
Ho wev er , with in a tem p er a tu r e r a ng e o f 5 0 to 1 5 0 C. ,
th e r a tio CO/COz o f th e CO a ds o r p tio n eq u il ib r iu m
a m o u nt to th e CO2 a ds o r p tio n eq u il ib r iu m a m o u nt is
1 . 0 2 to 5 . 8 . Ho wev er , with in a tem p er a tu r e r a ng e o f
1 5 0 a nd 2 5 0 C. , th e r a tio CO/CO2 ex c eeds 5 . 8 a nd
b ec o m es 1 7 . 1 . It c a n b e s een th a t in s u c h a tem p er a tu r e
r a ng e th e CO s el ec tiv e a ds o r p tio n c a p a c ity o f th e a ds o r
b ent is im p r o v ed c o ns ider a b l y .
EXAMPLE 7
CO p u r ity a nd Rec o v er y Ra te o f CO g a s a t Ads o r p tio n
Tem p er a tu r e o f 1 6 5 C. il 0 C.
Th e r el a tio ns h ip b etween th e CO p u r ity a nd th e r e
c o v er y r a te o f th e r ec o v er y g a s a s a f u nc tio n o f a ds o r p
tio n tem p er a tu r e wa s ex a m ined u s ing a PS A tes ter h a v
ing 4 S US 3 0 4 a ds o r p tio n to wer s h a v ing a dia m eter o f 2
inc h es a nd a l eng th o f 8 0 0 m m . Ea c h to wer h a d a m a n
tl e h ea ter with a tem p er a tu r e c o ntr o l l er , s o th a t th e
to wer tem p er a tu r e c o u l d b e k ep t a t th e p r es ent tem p er
a tu r e il 0 C.
8 6 0 g o f l /l 6 inc h p el l ets ( c o nta ining 2 0 % o f a p el l et
iz er ) o f Cu ( II) - Y z eo l ite p r ep a r ed f o l l o wing th e s a m e
p r o c edu r es a s in Ex a m p l e 6 wer e ?l l ed in ea c h to wer ,
a nd h ea ting a t 3 0 0 C. in a v a c u u m o f 5 0 To r r wa s
p er f o r m ed f o r a b o u t 5 h o u r s . Af ter p u r e CO g a s wa s
?l l ed a t a r a te o f a b o u t 1 N l /m in f o r a b o u t 2 h o u r s , th e
Cu ( II) - Y r edu c ed into Cu ( I) - Y.
Th e f o u r - to wer PS A a p p a r a tu s wa s o f a ty p e c a p a b l e
o f a c y c l e o f a ds o r p tio n s tep , p u r g e s tep , des o r p tio n s tep
a nd c o m p r es s io n s tep a s a m eth o d o f r ec o v er ing th e
a ds o r b ed m a ter ia l .
S ep a r a tio n a nd p u r g e o f a g a s m ix tu r e a s s u m ing a
c o nv er ter g a s h a v ing th e f o l l o wing c o m p o s itio n wa s
p er f o r m ed u s ing th e a b o v e a p p a r a tu s .
Ga s Co m p o s itio n
CO 7 4 . 5 %
c o ; 1 4 . 0 %
Hz 1 . 0 %
N 2 1 0 . 5 %
Th e s etting c o nditio ns wer e: l 6 5 il 0 C. f o r th e a d
s o r p tio n tem p er a tu r e, 1 k g /c m 2 . G f o r th e a ds o r p tio n
p r es s u r e, a nd 5 0 To r r f o r th e des o r p tio n p r es s u r e. Th e
r el a tio ns h ip b etween th e CO p u r ity a nd th e CO r ec o v
er y r a te o f th e r ec o v er ed g a s wa s deter m ined b y c h a ng
ing th e r a tio o f th e p u r g e g a s s u p p l y to th e des o r b ed g a s
a m o u nt a nd th e s u p p l y g a s s u p p l y a m o u nt wh il e k eep
ing th e g a s ?o w r a te with in ea c h to wer c o ns ta nt.
Il l u s tr a ting a n ex a m p l e o f th e o b ta ined r es u l ts , wh en
th e s u p p l y g a s wa s s u p p l ied a t a r a te o f 0 . 7 6 N l / m in a nd
th e r a tio o f th e p u r g e a m o u nt to th e des o r b ed a m o u nt
wa s 0 . 7 3 , th e CO r ec o v er y r a te wa s 7 3 % a nd th e r ec o v
er ed g a s h a d a c o m p o s itio n o f :
CO 9 6 . 2 %
CO; 3 . 0 %
N 2 0 . 7 %
H2 0 . 1 %
4 , 7 4 3 , 2 7 6
1 1
Th e do tted c u r v e in FIG. 8 s h o ws th e r el a tio ns h ip b e
tween th e CO p u r ity a nd th e CO r ec o v er y r a te.
EXAMPLE 8
CO p u r ity a nd Rec o v er y Ra te a t Ads o r p tio n
Tem p er a tu r e o f 2 1 0 il 0 C.
Th e r el a tio ns h ip b etween th e CO p u r ity a nd th e CO
r ec o v er y r a te o f th e CO g a s wa s ex a m ined f o l l o wing
th e s a m e p r o c edu r es a nd u s ing th e s a m e a p p a r a tu s a s in
Ex a m p l e 7 ex c ep t th a t th e a ds o r p tio n tem p er a tu r e wa s
s et a t 2 l 0 - _ l - 1 0 C.
To il l u s tr a te a n ex a m p l e, wh en th e s u p p l y g a s wa s
s u p p l ied a t a r a te o f 0 . 7 0 N l /m in a nd th e r a tio o f th e
p u r g e a m o u nt to th e des o r b ed a m o u nt wa s 0 . 7 4 , th e CO
r ec o v er y r a te wa s 7 2 % a nd th e r ec o v er ed g a s h a d a
c o m p o s itio n o f :
CO 9 8 . 5 %
CO; 1 . 0 %
N 2 0 . 4 %
H) , 0 . 1 %
Th e s o l id c u r v e in FIG. 8 s h o ws th e r el a tio ns h ip b e
tween th e CO p u r ity a nd th e r ec o v er y r a te.
It c a n b e s een f r o m th e a b o v e r es u l ts th a t wh en th e
a ds o r p tio n tem p er a tu r e is inc r ea s ed a b o v e th a t in Ex
a m p l e 6 , th e CO p u r ity f o r th e s a m e CO r ec o v er y r a te
is im p r o v ed. If th e CO r ec o v er y r a te is dec r ea s ed to
a b o u t 5 0 %, a CO p u r ity o f 9 9 % o r m o r e is o b ta ined.
EXAMPLE 9
CO Pu r ity a nd Rec o v er y Ra te o f Rec o v er ed Ga s a t
Ab s o r p tio n Tem p er a tu r e o f 1 3 5 : 1 0 C.
Th e r el a tio ns h ip b etween th e CO p u r ity a nd r ec o v
er y r a te wa s deter m ined f o l l o wing th e s a m e p r o c edu r es
a nd u s ing th e s a m e a p p a r a tu s a s in Ex a m p l e 7 ex c ep t
th a t th e a ds o r p tio n tem p er a tu r e wa s s et a t 1 3 5 : 1 : 1 0 C.
To il l u s tr a te a n ex a m p l e, wh en th e s u p p l y g a s wa s
s u p p l ied a t a r a te o f 0 . 7 2 N l /m in a nd th e r a tio o f th e
p u r g e a m o u nt to th e des o r b ed a m o u nt wa s 0 . 7 3 , th e CO
r ec o v er y r a te wa s 7 2 % a nd th e r ec o v er ed g a s h a d a
c o m p o s itio n o f :
CO 9 3 . 1 %
CO2 5 . 2 %
N 1 1 . 4 %
Hz 0 . 3 %
Th e a l ter na te l o ng a nd s h o r t da s h ed c u r v e in FIG. 8
s h o ws th e r el a tio ns h ip b etween th e CO p u r ity a nd th e
r ec o v er y r a te.
It c a n b e s een f r o m th es e r es u l ts th a t wh en th e a d
s o r p tio n tem p er a tu r e f a l l s b el o w 1 5 0 C. , th e CO p u r ity
is dec r ea s ed to 9 5 % o r l es s f o r a r ec o v er y r a te o f a b o u t
7 0 %. In o r der to h o l d a CO p u r ity o f a b o u t 9 8 %, th e
r ec o v er y r a te m u s t b e dec r ea s ed to a b o u t 3 0 %.
EXAMPLE 1 0
Ga s Ads o r p tio n Ch a r a c ter is tic s o f Ads o r b ent o f
Pr es ent Inv entio n a nd Ads o r b ent o f Co m p a r a tiv e
Ex a m p l e
Th e Y- ty p e z eo l ite ( N a 2 O2 O3 . 4 . 8 S iO2 . 8 . 9 H2 O) wa s
io n- ex c h a ng ed b y th e f o l l o wing 9 ty p es o f m eta l s to
p r ep a r e 9 a ds o r b ents . Th u s , 0 . 5 N s o l u tio ns o f FeCl ; ,
N i( N O3 ) 2 , MI1 C1 2 , Co ( N O3 ) 2 , CdCl z , Rh ( N O3 ) 2 , Ru Cl 3 ,
Cu Cl 2 , a nd Ag N O3 wer e p r ep a r ed. Ten g r a m s o f th e
1 2
z eo l ite a nd 5 0 m l o f ea c h 0 . 5 N s o l u tio n wer e c h a r g ed in
ea c h 1 0 0 m l r o u nd ?a s k . Af ter a c o ndens er wa s
m o u nted o n th e r o u nd ?a s k , h ea t r e?u x ing a t 1 0 0 C.
wa s p er f o r m ed f o r 2 h o u r s u s ing a m a ntl e h ea ter . Af ter
th e s o l u tio n wa s l ef t to s ta nd, th e s u p er na ta nt wa s r e
c o v er ed b y dec a nta tio n. Af ter a dding a no th er 5 0 m l o f
ea c h 0 . 5 N s o l u tio n to th e c o r r es p o nding ?a s k , r e?u x ing
1 wa s p er f o r m ed in a s im il a r m a nner . Th e r e?u x ing wa s
2 0
2 5
3 0
4 5
5 0
6 0
6 5
p er f o r m ed a to ta l o f th r ee tim es . Th e z eo l ite f r o m ea c h
?a s k wa s wa s h ed with p u r e wa ter , dr ied a t 1 1 0 C. ,
p u l v er iz ed, a nd b a k ed in a n el ec tr ic f u r na c e a t 4 5 0 C.
f o r 2 h o u r s to p r ep a r e a n a ds o r b ent. Ea c h r ec o v er ed
s u p er na ta nt a nd th e c o r r es p o nding ?l tr a te wer e m ix ed
a nd th e m ix tu r e wa s s u b j ec ted to ?a m e a na l y s is to de
ter m ine th e a m o u nt o f N a r el ea s ed a nd th e io n- ex
c h a ng e r a te o f ea c h z eo l ite. Th e Cu ( II) - Y z eo l ite wa s
r edu c ed in a h y dr o g en a tm o s p h er e a t 1 8 0 C. f o r 3 0
m inu tes to p r ep a r e Cu ( I) - Y. Th e m ea s u r ed io n- ex
c h a ng e r a tes a r e s h o wn in Ta b l e 2 b el o w.
Af ter th e a ds o r b ents p r ep a r ed in th is m a nner wer e
c o m p l etel y deh y dr a ted a t 1 5 0 C. a nd 1 0 - 3 m m Hg f o r
1 h o u r , th e N 2 , C0 , CO2 , 0 2 a nd H2 a ds o r p tio n a m o u nts
wer e m ea s u r ed a t 2 0 C. a t a m b ient p r es s u r e. In ea c h
a ds o r b ent, th e io n- ex c h a ng e r a te a nd th e g a s a ds o r p tio n
a m o u nt h el d a s u b s ta ntia l l y l inea r r el a tio ns h ip a s c a n b e
s een f r o m th e c a s e o f Ag Y s h o wn in FIG. 9 . Th er ef o r e,
a l l g a s a ds o r p tio n a m o u nts a r e c a l c u l a ted to b e th o s e a t
a n io n- ex c h a ng e r a te o f 5 0 %.
Th e Y- ty p e z eo l ites h a v ing N i, Mn, Rh , Cu ( I) a nd Ag
th er eo n s h o wn in Ta b l e 2 h a v e h ig h er CO a nd N 2 a d
s o r p tio n a m o u nts a s c o m p a r ed to th o s e o f N a Y no t
c a r r y ing a tr a ns itio n m eta l in Ta b l e 3 a nd th o s e c a r r y ing
o th er m eta l s in Ta b l e 4 .
TABLE 2
Meta l Ga s a ds o r p tio n a m o u nt Io n ex
io n- ex c h a ng ed N m l /g c h a ng e
Y- ty p e z eo l ite N 2 CO CD2 0 2 H2 v CO/v N z r a te %
N iY 5 . 6 1 6 . 9 1 1 1 . 4 2 . 2 0 . 3 3 . 0 2 5 1 . 2
MnY 4 . 9 1 2 . 4 1 1 2 . 1 3 . 3 0 . 3 2 . 5 3 4 1 . 9
Rh Y 3 . 3 1 2 . 5 8 2 . 3 2 . 1 2 3 . 1 3 . 7 9 5 9 . 2
Cu ( II) Y 5 . 1 1 1 . 5 9 1 . 6 2 . 5 1 . 2 2 . 2 5 8 2 . 7
Cu ( I) Y 5 . 0 3 3 . 1 9 6 . 4 3 . 3 1 . 8 6 . 6 2 8 2 . 7
Ag Y 6 . 1 3 7 . 7 1 1 2 . 0 3 . 2 9 . 5 6 . 1 8 7 4 . 9
TABLE 3
Ga s a ds o r p tio n a m o u nt
N m l /g
Y- Ty p e z eo l ite N 2 C0 CO2 0 2 Hz v CO/v N z
N a Y 5 . 8 1 4 . 2 1 1 7 . 0 2 . 9 0 . 9 2 . 4 5
TABLE 4
Meta l Ga s a ds o r p tio n a m o u nt l o n ex
io n- ex c h a ng ed N m l /g c h a ng e
z eo l ite N 2 CO CO2 0 2 H2 v CO/v N z r a te %
FeY 3 . 9 8 . 2 8 2 . 7 1 . 1 O 2 . 1 0 4 2 . 0
Co Y 5 . 1 1 1 . 8 9 9 . 8 2 . 6 0 . 3 2 . 3 1 4 9 . 9
CdY 5 . 8 1 2 . 9 1 0 1 . 7 ' 3 . 5 0 . 6 2 . 1 9 3 9 . 2
Ru Y 3 . 3 7 . 2 7 1 . 6 2 . 0 4 . 8 2 . 1 8 7 1 . 0
EXAMPLE 1 1
Ga s Ads o r p tio n Ch a r a c ter is tic s o f Ads o r b ent o f
Pr es ent Inv entio n a nd Ads o r b ent o f Co m p a r a tiv e
Ex a m p l e
Th e a ds o r p tio n a m o u nts f o r th e th r ee a ds o r b ents
p r ep a r ed b y s il v er io n io n- ex c h a ng e o f th e r o l l o ing
4 , 7 4 3 , 2 7 6
1 3
th r ee z eo l ites wer e m ea s u r ed. Th e io n- ex c h a ng e a nd
m ea s u r e' m ent o f th e a ds o r p tio n a m o u nts wer e p er
f o r m ed f o l l o wing th e s a m e p r o c edu r es a s in Ex a m p l e
1 0 .
A- ty p e z eo l ite:
Mo r denite:
X- ty p e z eo l ite:
1 0
Th e z eo l ites c a r r y ing Ag in Ta b l e 5 h a v e h ig h er CO
a nd N 2 a b s o r p tio n a m o u nts th a n th e z eo l ites no t c a r r y
ing a ny tr a ns itio n m eta l in Ta b l e 6 .
TABLE 5
Meta l Ga s a ds o r p tio n a m o u nt
io n- ex c h a ng ed N m l /g v CO/
z eo l ite N 2 C0 CO2 0 1 H2 v N g
Ag A _ 7 . 1 3 4 . 1 7 5 . 6 4 . 3 7 . 6 4 . 8 0
Ag X 4 . 9 4 5 . 4 1 0 3 . 8 3 . 3 9 . 7 9 . 2 7
Ag m o r denite 1 7 . 7 4 1 . 4 6 3 . 0 6 . 8 7 . 9 2 . 3 4
1 5
Io n ex
c h a ng e
r a te %
3 6 . 8
3 9 . 8
1 0 0 . 0
TABLE 6
Ga s a ds o r p tio n a m o u nt N m l / g
N ; C0 C0 2 Oz H2
1 2 . 5 3 1 . 5 9 3 . 3 6 . 7 7 . 2
6 . 1 1 6 . 6 l l l . 3 5 . 9 2 . 4
5 . 8 1 4 . 2 1 1 7 . 0 2 . 9 0 . 9
2 . 5 2
2 . 7 2
1 . 7 6
Z eo l ite
4 A( N a A)
1 3 X( N a X)
N a m o r denite
3 0
EXAMPLE l 2
Co n?r m a tio n o f Tem p er a tu r e Inc r ea s e b y Co m p r es s io n
Pr es s u r e a nd tem p er a tu r e a f ter c o m p r es s io n b y a
dia p h r a g m c o m p r es s o r 1 1 wer e m ea s u r ed b y a tes ter
s h o wn in FIG. 1 5 . Th e s a m p l e g a s wa s a ir , a nd g a s
tem p er a tu r e b ef o r e c o m p r es s io n wa s th e a m b ient tem
p er a tu r e ( a b o u t 2 5 C. ) . Th e c o m p r es s o r 1 1 h a d a m a x i
m u m f l o w r a te o f 2 5 N l /m in a nd a m a x im u m b o o s ting
p r es s u r e o f 1 2 k g /c m Z G, a nd p r es s u r e a f ter b o o s ting
wa s a dj u s ted b y m ea ns o f a needl e v a l v e 1 3 . Pip ing
c o nnec ted to th e o u tl et p o r t o f th e c o m p r es s o r a nd a
s u r g e ta nk 1 2 wer e m o u nted with h ea t- ins u l a to r s , a nd a s
s ta b l e tem p er a tu r e o b ta ined with a th er m o m eter T2 wa s
o b ta ined a s a m ea s u r em ent. Th e o b ta ined r es u l ts a r e 4 5
s h o wn b el o w. Th e c a l c u l a ted v a l u e a t ea c h p r es s u r e is
a l s o s h o wn. Th e a c tu a l a p p a r a tu s wa s s m a l l a nd h ea t
l o s s wa s l a r g e. Wh en th e a c tu a l m ea s u r em ents a r e c o m
p a r ed with th e c a l c u l a ted v a l u es o b ta ined a s s u m ing
z er o h ea t l o s s , a l th o u g h th e a c tu a l m ea s u r em ents h a v e
s m a l l tem p er a tu r e inc r ea s e r a tes , th ey do ex h ib it tem
p er a tu r e inc r ea s e with a n inc r ea s e in p r es s u r e.
3 5
5 0
TABLE 7
Tes t Pr es s u r e Tem p er a tu r e Tem p er a tu r e Ca l c u l a ted 5 5
N o . k g /c m 2 - G 1 c . 2 c . v a l u e c .
l 1 2 3 6 8 8 8
2 2 2 5 1 0 2 1 3 5
3 3 2 3 1 2 1 1 6 7
4 5 2 4 1 5 3 2 2 3
5 7 2 4 1 7 3 2 6 5 6 0
6 9 2 5 1 9 5 3 0 3
EXAMPLE 1 3
6 5
Dy na m ic Ads o r p tio n Ch a r a c ter is tic s o f Ads o r b ent
S inc e th e tem p er a tu r e inc r ea s e b y c o m p r es s io n wa s
c o n?r m ed in Ex a m p l e 1 2 , th e dy na m ic a ds o r p tio n c h a r
1 4
a c ter is tic s a t th e tem p er a tu r e c o r r es p o nding to ea c h
p r es s u r e in FIG. 1 0 wer e m ea s u r ed.
As s u m ing a c o nv er ter g a s , th e s u p p l y g a s s u p p l ied
h a d th e f o l l o wing c o m p o s itio n a s a s ta nda r d g a s a nd
wa s s u p p l ied f r o m a s u p p l y s o u r c e 2 1 ( a b o u t 8 0
k g /c m Z G) .
c o 7 3 . 7 %
N ; 1 4 . 2 4 %
Hz 3 . 0 3 %
C0 2 9 . 0 3 %
In a tes ter s h o wn in FIG. 1 6 , in o r der to k eep th e
p r es s u r e in th e s u r g e ta nk 2 3 a t 3 k g /c m 2 . G with a
c l o s ed v a l v e 2 7 , th e s ta nda r d g a s wa s ev a c u a ted b y a
p r es s u r e c o ntr o l v a l v e 2 2 a nd s u p p l ied into a n a ds o r p
tio n to wer h a v ing a n inner dia m eter o f 2 0 m m a nd a
h eig h t o f 1 , 0 0 0 m m th r o u g h a m a s s f l o wm eter 2 5 . Th e
g a s f l o w r a te s u p p l ied to th e m a s s f l o wm eter wa s s et a t
1 . 5 N l /m in b y a needl e v a l v e 3 1 m o u nted a t th e o u tl et
p o r t o f th e a ds o r p tio n to wer . Th e a ds o r b ent u s ed c a r
r ied z eo l ite Cu ( I) h a v ing a s il ic a /a l u m ina r a tio o f 1 0 o r
l es s . Wh en th e CO c o nc entr a tio n a t th e o u tl et p o r t o f
th e a ds o r p tio n to wer m ea s u r ed b y a CO m eter 3 2
r ea c h ed th e o r ig ina l c o nc entr a tio n, th e v a l v es 2 6 a nd 3 1
wer e c l o s ed a nd th e v a l v e 2 7 wa s o p ened. Th e a ds o r b ed
g a s wa s des o r b ed b y a v a c u u m p u m p 2 8 a t a b o u t 3 0
To r r , a nd th e c o m p o s itio n o f th e r ec o v er ed g a s wa s
a na l y s ed b y g a s c h r o m a to g r a p h y .
In Ex a m p l es , it wa s dem o ns tr a ted th a t ev en if h ea t
ins u l a to r s wer e u s ed, h ea t l o s s wa s c o ns ider a b l e. Fo r
th is r ea s o n, th e tem p er a tu r e o f th e to wer inter io r wa s
k ep t b y a n ex ter na l h ea ter a t a b o u t 2 0 0 C. wh ic h c o r r e
s p o nds to a p r es s u r e o f 3 k g /c m 2 . G.
As a r es u l t, th e r ec o v er ed g a s h a d th e f o l l o wing c o m
p o s itio n:
c o 9 0 . 6 %
N ; 6 . 0 %
Hz 0 . 1 %
CO2 3 . 3 %
It c a n b e s een f r o m th es e r es u l ts th a t CO s ep a r a tio n
c a n b e p er f o r m ed with a s ing l e- s tep tr ea tm ent b y th e
m eth o d o f th e p r es ent inv entio n. In p r a c tic e, s inc e a
p u r g e s tep is p er f o r m ed, a CO p u r ity o f a b o u t 9 9 % c a n
b e o b ta ined.
Wh a t is c l a im ed is :
1 . A m eth o d o f r ec o v er ing c a r b o n m o no x ide in a g a s
m ix tu r e c o nta ining a t l ea s t c a r b o n m o no x ide a nd c a r b o n
dio x ide, c o m p r is ing :
s el ec tiv el y a ds o r b ing c a r b o n m o no x ide in th e g a s
m ix tu r e o n a Cu ( I) a ds o r b ent s u p p o r ted o n a z eo l ite
c a r r ier s el ec ted f r o m th e g r o u p c o ns is ting o f Y
ty p e z eo l ite a nd m o r denite- ty p e z eo l ite a nd h a v ing
a s il ic a /a l u m ina r a tio o f no t m o r e th a n 1 0 , a n ef f ec
tiv e p o r e dia m eter o f no t l es s th a n 0 . 3 8 nm ( 3 . 8 A)
a nd c a p a b l e o f a ds o r b ing c a r b o n m o no x ide, th e
a ds o r p tio n tem p er a tu r e b eing 8 0 C. to 2 5 0 C. ;
s ep a r a ting th e a ds o r b ed c a r b o n m o no x ide; a nd
r ec o v er ing th e s ep a r a ted c a r b o n m o no x ide.
2 . Th e m eth o d o f c l a im 1 , wh er ein th e a ds o r p tio n
tem p er a tu r e is f r o m 8 0 C. to 1 5 0 C.
3 . Th e m eth o d o f c l a im 1 , wh er ein th e a ds o r p tio n
tem p er a tu r e is f r o m 1 5 0 C. to 2 5 0 C.
4 . Th e m eth o d o f c l a im 3 , wh er ein th e z eo l ite c a r r ier
is a Y- ty p e z eo l ite.
4 , 7 4 3 , 2 7 6
1 5
5 . Th e m eth o d o f c l a im 4 , wh er ein th e g a s m ix tu r e
c o nta ins a t l ea s t 6 0 % o f c a r b o n m o no x ide.
6 . Th e m eth o d o f c l a im 1 , wh er ein th e z eo l ite c a r r ier
is a Y- ty p e z eo l ite.
7 . Th e m eth o d o f c l a im 1 , wh er ein th e g a s m ix tu r e
c o nta ins a t l ea s t 2 0 % o f c a r b o n m o no x ide.
8 . Th e m eth o d o f c l a im 1 , wh er ein th e g a s m ix tu r e is
c o nv er ter g a s .
1 5
2 5
3 5
4 5
5 5
6 0
6 5
1 6
9 . Th e m eth o d o f c l a im 1 , wh er ein th e g a s m ix tu r e
c o nta ins a t l ea s t 6 0 % o f c a r b o n m o no x ide.
1 0 . Th e m eth o d o f c l a im 1 wh er ein th e z eo l ite c a r r ier
is a m o r denite- ty p e z eo l ite.
1 1 . Th e m eth o d o f c l a im 1 , wh er ein th e g a s m ix tu r e is
a dia b a tic a l l y c o m p r es s ed a t a p r es s u r e o f 0 . 5 k g /c m 2 . G
to 7 k g /c m 2 . G b y a c o m p r es s o r to b o o s t a g a s tem p er a
tu r e to th e a ds o r p tio n tem p er a tu r e o f 8 0 C. to 2 5 0 C. ,
a nd c a r b o n m o no x ide in th e g a s m ix tu r e is a ds o r b ed
with th e a ds o r b ent a nd r em o v ed.
# it * * *