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(12
Europaisches
Pat ent amt
European
Patent Office
Publication number:
0 1 9 4 4 8 3
Office
europeen
des brevets A1
EUROPEAN PATENT APPLI CATI ON

Application number: 86102208.5
Int. CI.4: B 01 D 53/ 22
^
B 01 D 13/ 00
Date of filing: 20.02.86
Priority 01.03.85 US 707299 Applicant: AIRPRODUCTS ANDCHEMICALS, INC.
01.03.85 US 707298 P.O. Box 538
Allentown, Pennsylvania 18105(US)
Date of publication of application:
@ Inventor: Pez, Guido Peter
17.09.86 Bulletin 86/38 3705 Vale View Drive
Allentown, PA18103IUS)

Designated Contracting States:
BE DE FR GB NL Inventor: Carlin, Richard Trotter
Idylwood Apts, Apt No. 666 Slate Creek Drive
Cheektowaga New York 14227(US)
Representative: Kador 8t Partner
Corneliusstrasse 15
D-8000Miinchen5(DE)
(54) Method for
gas separation.
57 A
process
for separating a gas
from a mixture of
gases
comprises passing the
gas
mixture over a membrane,
selectively permeable by the
gas being separated, owing to
one or more reversible reactions between a continuous layer
of active molten material, immobilized in a thin, rigid,
porous, inert support therefor, and the
gas being separated.
Techni cal F i e l d
This i n v e n t i o n r e l a t e s to an i mproved method of
s e p a r a t i o n of a
g a s
from
a
mi xt ur e of
gases
and to i mproved membranes f or the s e p a r a t i o n
p r o c e s s .
Background A r t
Numerous
appr oaches to the s e p a r a t i o n of
a
gas
from a mi xt ur e o f
gases by d i f f e r e n t i a l
per meat i on have been
i n v e s t i g a t e d . Robb et a l . , i n
U.S. Pat ent 3, 335, 545, have pr oposed use of
a l i qui d, e nt r a ppe d in
a
porous or pe r me a bl e s uppor t , to s e p a r a t e
mi xt ur es of
gas es .
The
use of a
s o - c a l l e d " q u a s i - l i q u i d f i l m, " f or exampl e, di e t hyl e ne g l y c o l ,
in
a
s uppor t
has p e r mi t t e d s e p a r a t i o n of car bon di oxi de from n i t r o g e n ,
hydrogen or
oxygen,
the s e l e c t i v i t y bei ng somewhat hi gher t han would be
p r e d i c t e d on the bas i s of the mol ecul ar wei ght s
of the
gases as the s o l e
f a c t o r , i n f l u e n c i n g s e p a r a t i o n . Ward, I I I , has pr opos ed, in U.S. P a t e n t
3, 503, 186, a s i mi l a r p r o c e d u r e for s e p a r a t i n g s ul f ur di oxi de from o t h e r
g a s e s .
The
use
of f a c i l i t a t e d
t r a n s p o r t l i qui d membranes has been r e vi e we d
by Way et a l . , J. Membrane Sci ence, vol . 12 (1982),
pages
239- 259.
Anot her t y p i c a l d i s c l o s u r e of ga s s e p a r a t i o n usi ng a
f a c i l i t a t e d
t r a n s p o r t i mmobi l i zed membr ane is t ha t of Bas s et t et a l . , Bi ochi mi ca e t
Bi ophys i ca Act a, vol . 211 ( 1970) ,
pages
194-215. F a c i l i t a t e d
t r a n s p o r t
of
gases t hr ough l i q u i d membranes is al s o r e c i t e d , f or
exampl e,
in t h e
f ol l owi ng U.S. P a t e n t s :
Wa r d , I I I , et al . ' 510 r e c i t e us i ng an
i mmobi l i zed
l i q u i d
f i l m as a
per meabl e membrane, wher ei n t he l i q u i d f i l m c ont a i ns at l e a s t one
s o l u b l e , n o n - v o l a t i l e , di s s ol ve d c a r r i e r s pe c i e s , which is r e v e r s i b l y
c h e mi c a l l y r e a c t i v e wi t h
a
s e l e c t e d
component
of
a gaseous
mi x t u r e .
Ki mura, et al . (U.S. Pa t e nt 4, 318, 714) have r e c i t e d us i ng a n
i on- e xc ha nge
membrane to a c c o mg l i s h f a c i l i t a t e d s e p a r a t i o n of a gas
f r o m
a mi xt ur e of
g a s e s .
Yanamot o, et al . (U.S. Pat ent 3, 155, 467) have d i s c l o s e d s e p a r a t i o n
and p u r i f i c a t i o n of
hydr ogen, usi ng a pal l adi um a l l oy as a per meabl e wa l l
s t r u c t u r e .
Sol i d and mol t en s a l t e l e c t r o l y t e s have. been d i s c l o s e d , in t he f u e l
c e l l or e l e c t r o c h e mi c a l a r t s , in t he f ol l owi ng r e p r e s e n t a t i v e p a t e n t s :
Yo s h i s a t o , et a l . , in U.S. Pa t e nt 4, 330, 633, r e c i t e us i ng a s o l i d
e l e c t r o l y t e compr i s i ng a s i n t e r e d
body
of mixed i nor ga ni c met al oxi des a s
a membrane for the r e g e n e r a t i o n of
oxygen
at r e l a t i v e l y hi gh t e mp e r a t u r e s
( about 800 C) .
Oxygen is known to
per meat e s e l e c t i v e l y t hr ough me t a l l i c s i l v e r .
However,
oxygen
f l uxe s at r eas onabl e
t e mpe r a t ur e s ( about 400C)
are l ow,
as r e p o r t e d by Gr yaznov, et a l . , Rus s i an. J. Phys. Chem., vol . 47 ( 1973) ,
pages
1517- 1519. At hi gher t e mp e r a t u r e s , me t a l l i c membranes f or t h e
s e p a r a t i o n of
oxygen
from ot her
gases are u n s t a b l e , s e e Mul ha upt , U. S.
Pat ent 3 , 3 5 9 , 7 0 5 .
A l i mi t i n g f e a t ur e in
many
of t hese d i s c l o s u r e s is t ha t
a gas
s h o u l d
not c ompl e t e l y per meat e the e l e c t r o l y t e or e l e c t r o d e , s i nce c ompl e t e
p e n e t r a t i o n coul d s hor t c i r c u i t the d e v i c e .
Bat l gne et a l . , U.S. Pat ent 4, 396, 572, r e c i t e
usi ng a por ous
c e r a mi c
b a r r i e r , havi ng a p l u r a l i t y of super i mposed l a ye r s of
pa s t e s
of
v a r y i n g
c ompos i t i on, to
s e pa r a t e
urani um h e x a f l u o r i d e i s ot opes by u l t r a f i l t r a t i o n .
I t is
a ppa r e nt
t hat p r e s e n t l y
a v a i l a b l e membranes for
s e p a r a t i o n o f
gases by d i f f u s i o n , per meat i on or
u l t r a f i l t r a t i o n
are for the most
p a r t
r e l a t i v e l y u n s e l e c t i v e or complex in s t r u c t u r e .
I t is t h e r e f o r e
an obj e c t o f t h i s i nve nt i on to pr ovi de met hods a nd
a r t i c l e s of t he s e p a r a t i o n of
gases
from mi xt ur e s , which are much
mor e
hi ghl y
s e l e c t i v e and have hi gher f l uxes of per meat i ng
gas
t han
p r e s e n t l y
a v a i l a b l e met hods and to pr ovi de membranes which
are si mpl e to c o n s t r u c t
and to u s e .
Di s c l os ur e of I n v e n t i o n
In
one a s p e c t ,
t hi s i nve nt i on r e l a t e s to a pr ocess
f or
s e p a r a t i n g a t
l eas t
one gas
from
a mi xt ur e of
gas es ,
compr i s i ng pas s i ng the
gas
mi x t u r e
over a membrane s e l e c t i v e l y per meabl e to the
gas
bei ng s e p a r a t e d as a
r e s ul t of
one or more r e v e r s i b l e r e a c t i o n s , i nc l udi ng o x i d a t i o n - r e d u c t i o n
r e a c t i o n s , bet ween the
gas bei ng s e pa r a t e d
and
an
a c t i ve ma t e r i a l in t h e
membrane; wher ei n the membrane compr i ses a t hi n,
por ous,
i ne r t
s uppor t
i n
which is i mmo b i l i z e d t h e a c t i v e ma t e r i a l and the act i ve ma t e r i a l is
a
mol t en s a l t , p r e f e r a b l y capabl e of one or more
r e v e r s i b l e r e a c t i o n s wi t h
the
gas bei ng s e p a r a t e d .
In a not he r
a s pe c t ,
t h i s i nve nt i on r e l a t e s to a
pr oces s
f o r
s e p a r a t i n g a gas
from at l e a s t
one ot her
gas
in
a
mi xt ur e
by
the
s t eps
o f
i nt r oduc i ng the mi xt ur e i nt o a module havi ng at l eas t
a feed
gas
i n l e t
and a per meat e gas
out l e t and c ont a i ni ng a membrane s e l e c t i v e l y pe r me a bl e
to the
gas
bei ng s e p a r a t e d ,
which membrane compr i ses a t hi n,
porous
i n e r t
suppor t
in which an a c t i ve ma t e r i a l is i mmobi l i zed wi t hi n the
p o r e s ,
whi ch membrane has
a
i n l e t si de and a per meat e
si de and which a c t i v e
ma t e r i a l i s a
mol t en s a l t capabl e of under goi ng one or more r e v e r s i b l e
r e a c t i o n s , wi t h
t he gas bei ng s e p a r a t e d ; pas s i ng the mi xt ur e
t hr ough t h e
f eed i n l e t and i nt o c o n t a c t wi t h t he i n l e t si de of the membrane; r emovi ng
from t he i n l e t si de of t he membrane a
gas
st ream r e j e c t e d by the membrane
and
r emovi ng
from the
per meat e gas
o u t l e t the
gas pas s i ng by
r e a c t i o n
t hr ough the membr ane.
In s t i l l a not he r a s p e c t , t h i s i n v e n t i o n r e l a t e s to a me mb r a n e f o r
gas s e p a r a t i o n p r o c e s s e s ,
c ompr i s i ng a t hi n,
por ous,
i n e r t
s uppor t
i n
whi ch is i mmobi l i zed
a
mol t en a c t i v e s a l t , capabl e of
under goi ng one o r
more
r e v e r s i b l e r e a c t i o n s , ot he r t han o x i d a t i o n - r e d u c t i o n r e a c t i o n s , wi t h
t he
gas
bei ng s e p a r a t e d .
" S a l t , " as used in t he s p e c i f i c a t i o n and cl ai ms , means a s u b s t a n c e
which i s compr i s ed of c a t i ons and ani ons and which is c h a r a c t e r i z e d
by
o v e r a l l e l e c t r i c a l n e u t r a l i t y . The c a t i ons and ani ons
may
be i n o r g a n i c ,
or ga ni c or a combi nat i on of bot h. I t wi l l be under s t ood t ha t s a l t s ha ve
a wide
range
of
mel t i ng poi nt s and t h a t , for the
pur poses
of t h i s
i n v e n t i o n , t he me l t i ng poi nt of t he s a l t used as a c t i ve ma t e r i a l is t h e
minimum
t e mp e r a t u r e , at which the membranes of t hi s i nve nt i on can be u s e d
f or s e p a r a t i o n of a
gas
from
a mi xt ur e of
g a s e s .
" I mmobi l i z e d, " as used in the s p e c i f i c a t i o n and cl ai ms , r e f e r s t o
mol t en a c t i ve ma t e r i a l , c a pt ur e d wi t hi n the
por es
or i n t e r s t i c e s of t h e
cer ami c or ot he r
s uppor t , as
wel l
as
any
ma t e r i a l in the form of
a t h i n
f i l m of s a l t mel t on t he s ur f a c e of t he s uppor t . Al t hough t he mo l t e n
s a l t need not n e c e s s a r i l y f i l l t he e n t i r e v o i d volume o f t h e
p o r o u s
s uppor t ,
i t is be l i e ve d
t ha t a t hi n cont i nuous l ayer
of mol t en s a l t in
o r
on t he
s uppor t i s n e c e s s a r y
f or the s u c c e s s f u l ope r a t i on of the membr anes.
" Re v e r s i b l e r e a c t i o n , " as used in the s p e c i f i c a t i o n and c l a i ms
e s s e n t i a l l y means a chemi cal r e a c t i o n which
can go
f or war d to the
r i g h t
or backwar ds to the l e f t , dependi ng upon
the r e l a t i v e c o n c e n t r a t i o n s o f
r e a c t a n t s and pr oduct s at a n y t i me . One
type
of r e v e r s i b l e r e a c t i o n
wi t hi n the meaning
of the i nve nt i on is f or mat i on of
a
c o o r d i n a t i o n
compl ex. A c o o r d i n a t i o n
complex or
c o o r d i n a t i o n compound c o n s i s t s of a
c e n t r a l atom or i on, s ur r ounde d by a s et of ot her at oms, i ons or s ma l l
mol e c ul e s . The at oms, ions or mol ecul es s ur r oundi ng t he c e n t r a l atom
a r e
c o n v e n t i o n a l l y c a l l e d l i ga nds . The r e s u l t i n g e n t i t y is
g e n e r a l l y a
complex and, s p e c i f i c a l l y ,
in the p r a c t i c e of t hi s i n v e n t i o n is a compl ex
i on. The
gas
bei ng s e p a r a t e d
from the mi xt ur e wi l l
a c c o r d i n g l y be a
l i ga nd in t hi s compl ex i o n .
Typi cal exampl es
of c o o r d i n a t i o n compounds
i nc l ude e n t i t i e s such a s
- +3 +3 ++
PF6. Cr(CO6), Cr(NH3)6+3, CO(NH3)6+3, CoCl4
and Zn(NH3)2++. The
compl exes
us ef ul in accor dance with t hi s i nve nt i on wi l l be t hose f or med
by an
ion of a s a l t , whet her a
cat i on or an a n i o n .
In a r e p r e s e n t a t i v e cas e,
the s e p a r a t i o n of ammonia from
ni t r oge n i n
c ont a c t wi t h a membrane compr i s i ng mol t en zinc c h l o r i d e , i t is p r o p o s e d
t hat the zi nc c h l o r i d e in t hi s ammoni a- r i ch envi r onment r e a c t s r e v e r s i b l y
to form
a
zi nc ammoni at e c o o r d i n a t i o n compound, Zn(NH3)++. The
i n i t i a l c o n d i t i o n o f a c r o s s - s e c t i o n of the membrane is
t hought to be
t hat de pi c t e d be l ow:
The zi nc ammoniate i ons t hus formed at the f eed si de wi l l d i f f u s e
t owa r d t he
per meat e s i de , where t her e is a lower c o n c e n t r a t i o n of s uc h
i ons. At the
per meat e
si de
membrane-gas i n t e r f a c e , where t her e is
a much
l ower p a r t i a l
p r e s s u r e
of ammonia, the zinc ammoniate i ons w i l l
r e v e r s i b l y d i s s o c i a t e back i nt o zi nc ions and f r ee ammonia, which i s
removed as the
per meat e s t r e a m.
The
s t eady s t a t e c o n d i t i o n of the membrane is shown in the di agr am
bel ow, wher ei n the zi nc i ons thus formed at the
per meat e
si de d i f f u s e
back to a r e g i o n o f l ower c o n c e n t r a t i o n at the feed s i de, t hus c o mp l e t i n g
the o v e r a l l cycl e, whi ch amounts to net t r a n s p o r t
of ammonia
t hr ough t he
membrane. This net t r a n s p o r t
of ammonia t hrough the membrane a r i s e s f r om
the r e v e r s i b l e r e a c t i v i t y of ammonia with zinc ions and the
mobi l i t y o f
t he z i n c i o n s and zi nc ammoni at e i ons in t he mol t en s a l t . Chl or i de a c t s ,
i n t h i s exampl e, to pr ovi de e l e c t r i c a l
n e u t r a l i t y .
The ot her f eed
gas, n i t r o g e n , does not r e a c t wi t h the mol t en s a l t .
Si nce t her e is
no mechani sm
by wh i c h n i t r o g e n can be
t r a n s p o r t e d a c t i v e l y
t h r o u g h t he membr ane, i t r emai ns l a r g e l y on t he f eed si de and a n
e x c e l l e n t o v e r a l l s e p a r a t i o n of ammonia n i t r o g e n is t hus a c h i e v e d .
Al t hough t he f o r e g o i n g gi ves a pr oposed t h e o r e t i c a l e x p l a n a t i o n o f
t he mechani sm
by
which t he
pr oc e s s
of t he p r e s e n t
i nve nt i on
o p e r a t e s , i t
wi l l b e unde r s t ood t ha t t he i n v e n t o r s do not . wi s h to be bound by s u c h
e x p l a n a t i o n
and
r e l y on t he appended
cl ai ms to def i ne the i n v e n t i o n .
In p r a c t i c e , p r e f e r r e d s e p a r a t i o n s empl oyi ng c o o r d i n a t i o n c ompl e xe s
ar e t hos e wh e r e i n :
(a) f us ed mol t en l i t h i u m n i t r a t e is used f or the s e p a r a t i o n
o f
ammonia from n i t r o g e n or hydr ogen or a mi xt ur e t h e r e o f , p r e f e r a b l y f r om
n i t r o g e n , b y t he r e v e r s i b l e f or ma t i on of
a l i t hi um ammoniate in t he me l t ;
(b) ammonia is
s e p a r a t e d
from
hydr ogen or n i t r o g e n usi ng mol t en z i n c
c h l o r i d e as
t h e a c t i v e ma t e r i a l in t he membrane and the complex
formed i n
t he mel t is
a mono or di ammoni at e; a n d
(c) wat er i s
s e p a r a t e d from
oxygen,
n i t r o g e n or ai r
by
f or ma t i on o f
one or more d i s s o l v e d
hydr a t e compl exes in a mel t of l i t hi um and s odi um
n i t r a t e s .
Anot her t ype of r e v e r s i b l e r e a c t i o n , a p p r o p r i a t e for t he p r a c t i c e o f
t h i s i n v e n t i o n is an a c i d - b a s e r e a c t i o n . This
t ype
of r e a c t i on i n c l u d e s
t h o s e of Ar r heni us a c i d s , Lowr y- Br ons t ed aci ds and Lewis aci ds a n d
b a s e s .
A
r e p r e s e n t a t i v e embodi ment of
a s e p a r a t i o n i nvol vi ng an
a c i d - b a s e
r e a c t i o n is the s e p a r a t i o n
of car bon di oxi de from
a
mi xt ur e of
g a s e s ,
usi ng as the a c t i ve membrane i n g r e d i e n t a mol t en
t e t r a a l k y l a mmo n i u m
c a r b o x y l a t e s a l t .
Al kyl can be the same or d i f f e r e n t
a l kyl
of 1 - 24
car bon atoms and is
p r e f e r a b l y of 1 - 10 car bon at oms. The c a r b o x y l a t e
can have
any
ani on r a d i c a l whi c h wi l l
give a
s a l t of t he mel t i ng p o i n t
r ange,
d e s i r e d f or o p e r a t i o n of the membrane. Tet r ahexyl ammoni um
benzoat e (THAB) is
p a r t i c u l a r l y p r e f e r r e d .
These
t e t r a a l kyl a mmoni um c a r b o x y l a t e s can
al s o be used for t h e
s e p a r a t i o n of
hydr ogen s u l f i d e from ot her
g a s e s .
A f u r t h e r r e v e r s i b l e r e a c t i o n , u t i l i z e d in the p r a c t i c e of t h i s
i n v e n t i o n , is f or ma t i on of
an or gani c chemi cal
compound, which is
c a p a b l e
of
s pont aneous f or ma t i on and d i s s o c i a t i o n at the
t e mp e r a t u r e
of
o p e r a t i o n
of the membrane. For exampl e, t et r aal kyl ammoni um s a l t s o f amino a c i d s
can r eact r e v e r s i b l y wi t h car bon di oxi de to form c a r ba ma t e s . Th i s
r e a c t i o n
can be used f or t he
s e p a r a t i o n
of carbon di oxi de from o t h e r
gases. Alkyl can be the
same or
d i f f e r e n t
al kyl of 1-24 car bon atoms. A
p r e f e r r e d embodiment is t ha t in which the amino aci d is gl yc i ne o r
s a r c os i ne and the al kyl i s of 1-10 car bon atoms. In t he
case
o f
s a r c o s i n e , the r e l e v a n t r e a c t i o n i s :
' I t is
pr oposed t hat s e p a r a t i o n
of ammonia, based on f or ma t i on o f
c o o r d i n a t i o n
compl exes wi t h zi nc c h l o r i d e ,
may
be
gover ned accor di ng t o
chemi cal
p r o p e r t i e s set f o r t h
by
Krasnov et a l . , "Tabl es and Diagrams o f
Thermodymanic Pr o p e r t i e s of Zinc Chl or i de Ammoniates in
Vapor and Li q u i d
Phas es , " Moskov.
Vsesoyuznyy Topl o- Te khni c he s ki y I n s t i t u t e . I n v e s t i y a ,
Moscow, n o . l l ( 1 9 3 5 ) ,
pages
44-49; St ar okadomskaya,
" S a t u r a t i o n P r e s s u r e
of Ammonia
During the Thermal Decompos i t i on of the Diammonium Sal t o f
Zinc Ch l o r i d e , " Zhur nal Pr i k l a d n o y Khi mi i , vol . 9 (1935 or 1936),
pa ge s
599-602; Zubakhi na, " I n v e s t i g a t i o n of Complexing in the
ZnCl2-NH3
Syst em, " Trudy Na u c h n o - l s s l e d o v a t e k ' s k o g o I n s t i t u t e Osnovnoi Khi mi i , v o l .
19 ( 1969) ,
pages
105- 110.
S o l u b i l i t y
be ha vi or of ammonia in mel t s of a l k a l i n i t r a t e a nd
p e r c h l o r a t e
is d i s c u s s e d b y Al l u l l i , J. Phys. Chem. , vol 73( 1969) ,
p a g e s
1084- 1087.
-
P r o p e r t i e s of c h l o r o a l u mi n a t e s , which
might be
germane
to the
use o f
mol t e n
cupr ous
c h l o r i d e c o o r d i n a t i o n compl exes, e . g . ,
(C2H5)3NH+ CuCl2-
or (C2H5)3 NH+CuCl 2- as
a c t i ve ma t e r i a l s f or the c o o r d i n a t i o n
of car bon monoxi de, ar e r e por t e d by Wal ker, "Sol i d and Li qui d Pha s e s
Co n t a i n i n g
CuAICI4, "
Symposium on
Advances in
Se pa r a t i on Te c hnol ogy,
p r e s e n t e d bef or e t he Di v i s i o n of Pet r ol eum Chemi s t r y, I nc . , S e a t t l e
Meet i ng, March, 1983,
pages
746-755; Kendal l , et a l . , "A St udy
of t h e
Fa c t o r s I n f l u e n c i n g Compound
For mat i on and S o l u b i l i t y
in Fused S a l t
Mi x t u r e s , " J. Am. Chem. Soc. , vol . 45 (1923)
pages
963, f f ; Hus s e y,
"Room
Te mpe r a t ur e
Mol t en Sal t Syst ems, Mamantov et a l . , ed. , Advances i n
Mol t en Sa l t Chemi s t r y 5, El s e v i e r , New York ( 1983) ,
pages
185-219;
H u s s e y
et a l . , "The El e c t r o c h e mi s t r y " o f Copper
in
a Room
Temper at ur e
Ac i d i c
Ch l o r o - a l u mi n a t e Me l t , " J. El ect r ochem. Soc. : So l i d - St a t e Sci ence a nd
Te c hnol ogy, v o l . 1 2 6 1979),
pages
1029-1034; and
Hussey, Mamantov e d . ,
Advances in Mo l t e n Sa l t Chemi s t r y 5,
pages
219- 223.
The r e a c t i o n of s i l v e r (1) compounds havi ng har d c o u n t e r i o n s ;
e . g . ,
AgBF4, AgC104,
wi t h o l e f i n s is r e c i t e d by Cot t on et a l . , "Advanced
I n o r g a n i c Chemi s t r y A Compr ehensi ve Text , " John Wiley & Sons, New Yor k
( 1980) ,
pages
9 7 1 - 9 7 2 . I t is
expect ed t hat the r e por t e d complex f o r ma t i o n
of monoval ent s i l v e r compounds
wi t h o l e f i n s coul d be e xpl oi t e d f o r
s e p a r a t i n g o l e f i n s from
a gas
mi xt ur e c o n t a i n i n g t hem.
Anot her r e v e r s i b l e r e a c t i o n is a " Re ve r s i bl e o x i d a t i o n - r e d u c t i o n
r e a c t i o n , " whi ch
as used in the
s p e c i f i c a t i o n
and cl ai ms
e s s e n t i a l l y
means an o x i d a t i o n - r e d u c t i o n r e a c t i o n which
can go
f or war d to the r i g h t
or
in
r e v e r s e to t he l e f t , dependi ng
upon
the r e l a t i v e c o n c e n t r a t i o n s o f
r e a c t a n t s a n d pr oduc t s at
any
t i me. Re p r e s e n t a t i v e r e a c t i o n s i n c l u d e
i n t e r c o n v e r s i o n bet ween n i t r a t e and n i t r i t e i o n s :
It is pr opos ed
t hat oxi des
are pr oduced by
r e a c t i ons such
a s :
and t hat the oxi des in the mel t , i nc l udi ng one or more of
0=, 02=
and
02r
c a t a l y z e the r e a c t i o n .
Anot her
t ype of o x i d a t i o n - r e d u c t i o n r e a c t i o n which can be e x p l o i t e d
in the
p r a c t i c e
of t hi s i nve nt i on i nc l ude s i n t e r c o n v e r s i o n o f
oxygen- oxi de s p e c i e s :
A
f u r t h e r e x e mp l a r y o x i d a t i o n - r e d u c t i o n r e a c t i o n is t hat i n v o l v i n g
o x i d a t i o n of
hydr ogen by hydr oxi de i o n s :
In a r e p r e s e n t a t i v e case, an a l k a l i met al n i t r a t e mol t en s a l t
membrane is f i r s t a c t i v a t e d by a l l owi ng some
of the n i t r a t e
(NO3)
ions to l ose
oxygen
and to f o r m n i t r i t e
(NO2)
i ons in the me l t
s p ont a n e o us l y, as
r e s u l t of h e a t i n g .
The worki ng mol t en s a l t membrane wi l l t hus cont ai n both an a l k a l i
met al n i t r a t e and an
a l k a l i metal n i t r i t e . The ope r a t i on
of the membrane
can be f u r t h e r v i s u a l i z e d as f o l l o w s :
At the feed si de of the membrane, ni t r oge n and
oxygen
are
in c o n t a c t
wi t h the s ur f ace of t he a l k a l i metal n i t r a t e / n i t r i t e mel t . The i n i t i a l
c o n d i t i o n i s as d e p i c t e d in t he f ol l owi ng c r o s s - s e c t i o n a l di agr am of t h e
membr ane:
The exces s
c o n c e n t r a t i o n of n i t r a t e ions at t he feed si de of t h e
membrane wi l l
promot e
t h e i r d i f f u s i o n t owar ds the
per meat e
s i de. At t h i s
i n t e r f a c e , t he r e i s
a much l ower p a r t i a l pr e s s ur e
of
oxygen,
t han at t h e
f eed i n t e r f a c e ; t h e r e f o r e , n i t r a t e i ons wi l l
r e v e r s i b l y d i s s o c i a t e i n t o
n i t r i t e i ons and l i b e r a t e
oxygen,
which is removed in the
p e r me a t e
s t r e a m. The s t e a dy s t a t e c o n d i t i o n of t he membrane is shown in t h e
di agr am bel ow, in which n i t r i t e i ons t hus formed at the
per meat e
s i d e
d i f f u s e back to a r egi on of l ower c o n c e n t r a t i o n at the feed si de t o
c o mp l e t e t h e o v e r a l l
c yc l e ,
which amount s t o n e t t r a n s p o r t
of
oxyge n
t hr ough
t he membrane. The net
t r a n s p o r t
of
oxygen
a r i s e s from r e v e r s i b l e
r e a c t i v i t y
of
oxygen
wi t h n i t r i t e i ons and mo b i l i t y of the n i t r i t e a n d
n i t r a t e i ons in t he s a l t .
The ot her feed
gas, ni t r oge n, does not r eact wi t h the mol t en s a l t .
Because t her e is
no
mechanism
by
which
n i t r o g e n can be a c t i v e l y
t r a n s p o r t e d t hr ough the mel t , i t wi l l be l a r g e l y r e j e c t e d at the f e e d
si de of the membrane., In t hi s
way,
e x c e l l e n t
s e p a r a t i o n
of n i t r o g e n and
oxygen
is a c h i e v e d .
Al t hough t he f or e goi ng gi ves an at t empt t o p r o v i d e a t h e o r e t i c a l
e x p l a n a t i o n
of the mechanism of the
pr oc e s s
of t he pr es ent i nve nt i on, i t
wi l l be under s t ood t hat the i nve nt or s do not wi sh to be bound by s u c h
e x p l a n a t i o n and r el y on the appended cl ai ms to def i ne the i n v e n t i o n .
It is
pr oposed t hat the
use
of
an
a l k a l i met al n i t r a t e mel t membrane
for s e p a r a t i o n of
oxygen
from ai r r e l i e s on the n i t r a t e - n i t r i t e
i n t e r c o n v e r s i o n . However, the r e a c t i on bet ween
oxygen
and oxi de s p e c i e s
may
al s o be o c c u r r i n g , as di s c us s e d more f u l l y by Zambonin, et a l . , J .
Am. Chem. Soc. , vol . 91 (1969),
pages
2225- 2228; Zamboni n,
E l e c t r o a n a l y t i c a l Chemi st r y and I n t e r f a c i a l El e c t r o c h e mi s t r y , vol . 45
( 1973) ,
pages
451-458 and Fl i nn et a l . , J. El e c t r o a n a l . Chem., vol 63
( 1975) ,
pages
39- 57.
It is al s o known t hat ot her mol t en s a l t syst ems
r eact r e v e r s i b l y
wi t h
oxygen
by
pr oc e s s e s i nvol vi ng e q u i l i b r i a wi t h reduced
oxygen
s p e c i e s , p a r t i c u l a r l y oxide ( O )
per oxi de
L02)
and
s u p e r o x i d e
(02).
For exampl e,
i t has been
r e por t e d
t hat
Na2O-Na2SO4
mel t s t ake
up oxygen r e v e r s i b l y at 920C, pr es umabl y by the r e a c t i o n s :
St er n et a l . , J. Phys. Chem. vol . 83 ( 1979) ,
pages
2848-2854. It is a l s o
t hought
t hat redox e q u i l i b r i a , i n v o l v i n g the decompos i t i on of s u l f a t e t o
s u l f i t e and
gaseous
s ul f ur di oxi de, are
i n v o l v e d .
It is
expect ed t hat
hydr oge n- hydr i de i n t e r c o n v e r s i o n in mo l t e n
a l k a l i met al hydr oxi de membranes of the i nve nt i on would
oper at e
i n
accor dance wi t h the behavi or r e por t e d by Bai kov, et a l . , " Ac t i va t i on o f
Mol ecul ar
Hydrogen by
Sol i d and Fused Hydr oxi des . I I I . Ki net i cs and
Mechanism of I s ot ope Exchange Between Hydrogen and Sol ut i ons of Water i n
Al kal i Mel t s" and "IV. The Role of Cat i ons in the
Ca t a l ys i s
o f
Homomol ecul ar Exchange of Hydrogen on Sol i d Hydr oxi de s , "
K i n e t i k a i
Ka t a l i z , vol . 23 ( 1982) ,
pages
573-577 and vol . 24 ( 1983) ,
p a g e s
5 0 2 - 5 0 5 .
Re v e r s i b l e
oxygen upt ake
from
Na 0-NaCl
mel t s is al s o known,
St e r n , et a l . , J. El ect r ochem. Soc. , vol . 124 ( 1977) ,
pages
641- 649.
Cupr ous
c h l o r i d e - a l k a l i me t a l h a l i d e mel t s ,
e . g . , CuCl - CuCl 2- KCl ,
are
a l s o known to r e a c t r e v e r s i b l e wi t h
oxygen, pr oba bl y by t he r e a c t i o n :
Font ana, et a l . , Ind. Eng. Chem., vol . 44 ( 1952) ,
pages
369- 378.
Because of the compl exi t y of t he redox
pr oc e s s e s t hought to occur i n
s a l t me l t s , i t is unde r s t ood t hat t he
pr oc e s s e s
of t h i s i nve nt i on i n c l u d e
t r a n s f e r of
ga s e s , capabl e of under goi ng an o x i d a t i o n - r e d u c t i o n r e a c t i o n
wi t h a mol t en s a l t , i mmobi l i zed in
a s uppor t , r e g a r d l e s s of t he mechani sm
by
whi ch t he
pr oc e s s a c t u a l l y t akes p l a c e .
I t wi l l be unde r s t ood t ha t the r e v e r s i b l e r e a c t i o n s , a p p r o p r i a t e
f o r
use
in t he p r a c t i c e of t hi s i nve nt i on, are not l i mi t e d to t hose set f o r t h
a b o v e .
The membranes of the pr e s e nt
i n v e n t i o n are r e p r e s e n t e d
ma c r o s c o p i c a l l y in
Fi g. 1, f or the s e p a r a t i o n
of
a per meabl e
gas
(A) f r om
a
mi xt ur e of
gases
A and B. The
por ous
s ol i d s uppor t
is a r i gi d, o r
s l i g h t l y f l e x i b l e , i n e r t ma t e r i a l , s e l e c t e d from me t a l l i c , pol ymer i c o r
cer ami c s u b s t r a t e s . The
s uppor t
ma t e r i a l is f i l l e d
or coat ed wi t h a t
l e a s t a c ont i nuous
l ayer
of the s e l e c t e d mol t en s a l t , or mi xt ur e t h e r e o f .
The f eed
gas pas s es over t he feed si de of the membrane, as shown
by t h e
mi xt ur e A + B on the
upper
si de of Fi g. 1. The r e a c t i v e member of t h e
gas
mi xt ur e wi l l
undergo one or more r e v e r s i b l e r e a c t i o n s wi t h ions i n
t he mol t en s a l t , as
di s c us s e d above.
Eve nt ua l l y, at s t e a dy s t a t e
c o n d i t i o n s , the r e a c t i v e
gas
(A) per meat es the membrane. In a n
e xpe r i me nt a l c ont e xt , the
r e a c t i ve or per meat e gas
(A) is removed f r om
the syst em by an i ne r t
sweep gas
and a sample of the
sweep gas
st ream i s
t r a n s f e r r e d to a gas chr omat ogr aph
f or
a n a l y s i s . In a l ar ge
s c a l e
u t i l i z a t i o n of the i nve nt i on, i t wi l l be p r e f e r r e d to exhaus t
pe r me a t e
gas
from the
syst em
with
a compr es s or
and t r a n s f e r
r e l a t i v e l y pur e
per meat e gas
to a pr ocess
r e q u i r i n g
i t or to c o n t a i n e r s .
I t is
pr opos ed t hat the
gas pr e s s ur e ,
r e qui r e d to di s pl a c e l i q u i d
t hat is i mmobi l i zed by c a p i l l a r y
f or ces from the
pores
of a porous
we t t e d
membrane, conforms to the e qua t i on ( Por t e r , "Handbook of S e p a r a t i o n
Techni ques f or Chemi cal En g i n e e r s , " S c h we i t z e r , ed. , Mc Gr a w- Hi l l ( 1979) ,
Appendi x A,
page
2- 89) :
wher ei n Y is t he s ur f ace t e n s i o n of the g a s - l i q u i d i n t e r f a c e , 0 is t h e
c ont a c t angl e bet ween the l i q u i d and the
pore
wal l and d is the
pore
s i z e .
In q u a l i t a t i v e t erms, the s a l t or mi xt ur e of s a l t s s e l e c t e d f or t h e
membrane wi l l be f l u i d at the t e mpe r a t ur e
of
use,
but the melt wi l l n o t
have an
e xc e s s i ve r at e of flow
or t endency to dry out or mi gr at e
from t h e
i ne r t
s uppor t .
The s a l t wi l l be e s s e n t i a l l y n o n - v o l a t i l e under c o n d i t i o n s
of u s e .
Al t hough membranes, c ompr i s i ng a monomol ecul ar l ayer
of a c t i v e
mol t en s a l t in t he i ner t
s uppor t
wi l l f unc t i on in accor dance wi t h t h e
i nve nt i on, i t is p r e f e r r e d to use membranes, havi ng a cont i nuous f i l m o f
mol t en a c t i ve s a l t i mmobi l i zed in and l ayer ed on
the
s uppor t , or a
combi nat i on t h e r e o f . Membranes meet i ng t hi s c r i t e r i o n wi l l have a
r e l a t i v e l y low
p e r me a b i l i t y to a
n o n - r e a c t i v e
gas
at 760 t or r at t h e
t e mpe r a t ur e of
u s e , a s
measur ed a ga i ns t
the backgr ound cont ent of i n e r t ,
n o n - r e a c t i v e
sweep gas on the
per meat e
si de of the membrane. In a
p r e f e r r e d case,
the
p e r me a b i l i t y of ni t r oge n as the i ner t
gas
is s e l e c t e d
as a s t a nda r d and is below 20 Bar r er under t hes e c o n d i t i o n s .
The
s uppor t
is s e l e c t e d from cer ami c, g l a s s ,
me t a l l i c and
o r g a n i c
pol ymer i c ma t e r i a l s , s t a bl e at the t emper at ur e
of
use,
which
are e i t h e r
r i gi d or s l i g h t l y f l e x i b l e and which do not r e a c t wi t h the a c t i ve mo l t e n
s a l t or wi t h the
gas
mi xt ur e
bei ng t r e a t e d . A p r a c t i c a l lower l i mi t f o r
the t hi c kne s s of
s e l f - s u p p o r t i n g membranes is below 0.01 c e n t i me t e r s , b u t
some
t hi nne r ma t e r i a l s
may
l ack the r i g i d i t y r e qui r e d. However,
u l t r a f i n e
porous
cer ami c f i l ms , l ess than 20 mi cr omet er s in t hi c kne s s
a r e
known, Leemaars et a l . , J. Ma t e r i a l s Sci ence, vol . 19( 1984) ,
pa ge s
1077-1088. It wi l l be unde r s t ood t hat the
s uppor t can be coat ed o r
a d h e r e d t o a n o t h e r ma t e r i a l ,
u s u a l l y
of
g r e a t e r p o r o s i t y , which wi l l
pr ovi de t he s t r u c t u r a l r i g i d i t y r e q u i r e d .
For exampl e, a " c ompos i t e " or "asymmet r i c" membrane, as de s c r i be d i n
Sc h we i t z e r , "Handbook of Se p a r a t i o n Techni ques
f or Chemi cal
En g i n e e r s , "
McGraw Hi l l ( 1 9 7 9 ) , p a g e s 2-19 to 2- 26, c ont e mpl a t e d f or
use
in t h e
p r a c t i c e
of t h i s i n v e n t i o n woul d have a
t hi n f i n e l y
por ous l a y e r ,
c o n t a i n i n g t he a c t i v e mol t en s a l t , s uppor t ed
f u r t h e r on a ma c r opor ous
s uppor t c o mp r i s i n g pol yme r i c , cer ami c or
me t a l l i c ma t e r i a l .
I t i s f u r t h e r p r e f e r r e d t ha t t he s uppor t
have a por e
s i ze of 0 . 0 0 3 -
100 mi c r o me t e r s . It wi l l be a p p r e c i a t e d t hat l ar ge
e f f e c t i v e membrane
a r e a s c a n be a t t a i n e d by us i ng a p l u r a l i t y of s mal l er membr anes,
c onne c t e d
by a ma ni f ol d
or ot he r connect i ng means, or t ha t a l a r g e
membrane can be made me c h a n i c a l l y s t r ong by the use of s uppor t i ng means ,
wel l known to t hos e s k i l l e d in the a r t .
The membrane
may
be c o n t a i n e d wi t hi n a module in t he c o n f i g u r a t i o n
of hol l ow f i b e r s , a s p i r a l wi ndi ng or a
s e r i e s of f l a t
p l a t e s . A
d e s c r i p t i o n of hol l ow f i b e r and s pi r a l l y- wound
membrane c o n f i g u r a t i o n s i s
gi ven
in Sc h we i t z e r , i b i d . ,
pages
2-61 to 2-65 and 2- 21, r e s p e c t i v e l y .
In
any s e p a r a t i o n
p r o c e s s ,
c a r r i e d out under the p r i n c i p l e s of t h i s
i n v e n t i o n where the mol t en s a l t under goes
r e v e r s i b l e r e a c t i o n s wi t h t h e
gas
bei ng s e p a r a t e d , t he maximum a c hi e va bl e f l ux of
per meat e gas p e r
c r o s s - s e c t i o n a l
ar ea
of membrane is equal to the e f f e c t i v e d i f f u s i o n
c o e f f i c i e n t of t he c a r r i e r ( a c t i v e mol t en s a l t ) , mu l t i p l i e d by t h e
c o n c e n t r a t i o n g r a d i e n t of c a r r i e r ( dr i vi ng
f or ce) bet ween the t wo
i n t e r f a c e s of t he membrane. Thus ,
In g e n e r a l , the f l ux
t hr ough a
membrane may be e xpr e s s e d as t h e
pr oduc t
of
a s t a n d a r d p e r me a b i l i t y t i mes the c r o s s - s e c t i o n a l
ar ea
of t h e
membrane, t i me s (P/l. ), wher ei n l is the
pr e s s ur e
d i f f e r e n c e
a c r os s t he membrane and l is the t hi c kne s s of the membr ane.
As in
any f a c i l i t a t e d t r a n s p o r t syst em,
the a c t ua l f l ux wi l l a l s o
depend on t he k i n e t i c s of the r e v e r s i b l e r e a c t i ons of the per meat i ng
g a s
wi t h t he mol t e n s a l t .
Pe r me a b i l i t y (Po) is expr es s ed
in Bar r er u n i t s , t hat i s ,
3 2
1 Bar r er = ( c m . cm x
1 0 ) / ( s e c . c m . cmHg)
When pol ymer i c membranes are used to
s uppor t a melt and i t i s
de s i r e d to
e xpr e s s
the g a s f l u x t hr ough the membrane in
a manner whi c h
r e f l e c t s
onl y
the
s e p a r a t i o n per f or mance
of the mel t , a c o r r e c t i o n w i l l
be made for the
p o r o s i t y
and t o r t u o s i t y of t he membr ane, so t h a t :
Flux = Po . A. (P/l) ( p o r o s i t y / t o r t u o s i t y )
S e l e c t i v i t y ( S ) f or a mi xt ur e of
gas es ,
A and B, in which A is t h e
per meat e gas,
is expr es s ed by
the r a t i o of p e r me a b i l i t i e s :
Very hi gh s e l e c t i v i t i e s are obs er ved, usi ng t ypi c a l membranes o f
t hi s i nve nt i on. For exampl e,
s e l e c t i v i t i e s of 80-145 were measured f o r
s e p a r a t i o n of ammonia from ni t r oge n, usi ng a mol t en s al t membrane o f
l i t hi um c h l o r i d e . The
same s e p a r a t i o n , u t i l i z i n g molten zinc c h l o r i d e
a s
the a c t i ve mol t en s a l t in the membrane,
gave
s e l e c t i v i t i e s above 1000 : 1.
Si mi l a r l y , the s e p a r a t i o n
of car bon di oxi de from ni t r oge n, u s i n g
mol t en
t et r aal kyl ammoni um benzoat e or s a r c o s i n a t e s a l t s in the membr anes ,
exceeded a s e l e c t i v i t y of 10. In the case
of the t e t r a l kyl a mmoni um
benzoat e membrane, i t
was s u r p r i s i n g l y f o u n d t h a t the
pr esence
of wa t e r
in the
gas
st r eam improved the s e p a r a t i o n , r a t h e r than a f f e c t i n g i t
d e l e t e r i o u s l y .
The s e l e c t i v i t y for
s e pa r a t i on
of wat er
vapor
from ni t r oge n, us i ng a
mol t en l i t hi um n i t r a t e / s o d i u m n i t r a t e membrane, was
about 200 : 1.
It is t h e r e f o r e
appar ent
t hat the membranes of the pr es ent i n v e n t i o n
give i mpr es s i ve s e l e c t i v i t i e s , compared to s e l e c t i v i t i e s of known
membranes, t y p i c a l exampl es of which
are set f o r t h in Table 1 be l ow.
For the
r e g e n e r a t i o n of
oxygen
from a i r , p r e f e r r e d
mel t s
are l i t h i u m
n i t r a t e
or sodium n i t r a t e , i mmobi l i zed in
a porous
me t a l l i c
or c e r a mi c
s uppor t . Pr e f e r r e d
ope r a t i ng t e mpe r a t ur e s are above 400C, more
p r e f e r a b l y above 450C. Mi xt ur es of n i t r a t e s , p a r t i c u l a r l y
of two
o r
more of sodium, l i t hi um and pot assi um n i t r a t e s , c ont a i ni ng a maximum o f
99%
by wei ght of
any
of the n i t r a t e s , are p a r t i c u l a r l y p r e f e r r e d .
S e l e c t i v i t i e s a ppr oa c hi ng
200 f or
oxygen
in a i r have been
a c h i e v e d ,
us i ng t he t e a c h i n g s of t hi s i n v e n t i o n . I t wi l l be a p p r e c i a t e d t h a t s uc h
s e l e c t i v i t i e s ar e much hi ghe r t han t hose obs er ved f or s e p a r a t i o n o f
o x y g e n - n i t r o g e n
mi xt ur e s usi ng c o n v e n t i o n a l
pol ymer membranes, as shown
in Tabl e 2 .
Br i e f De s c r i p t i o n of the Dr awi ngs
In Fi g.
1 i s shown a s i de vi ew of
a membrane, us e f ul f or t h e
p r a c t i c e
of t he i n v e n t i o n .
In F i g s . 2 , 3 and 4
ar e shown a t e s t
a ppa r a t us
f or
de mons t r a t i ng t h e
p r i n c i p l e s
of t h i s i n v e n t i o n , i n c l u d i n g a membrane, membrane hol der a nd
t e s t c e l l .
Best Mode for Car r yi ng Out the I n v e n t i o n
In a most p r e f e r r e d as pect
of t hi s i nve nt i on, the membrane c o mp r i s e s
an
i ne r t cerami c s uppor t
at l e a s t 0.02 cm
in t h i c k n e s s , and which has
a
pore
s i ze of 0 . 0 0 3 - 200 mi cr omet er s , is f i l l e d wi t h
a
cont i nuous f i l m o f
molten a c t i ve ma t e r i a l and has a p e r me a b i l i t y to
n i t r o g e n below 20
Bar r er s at 760 t o r r at the t e mpe r a t ur e
of
u s e .
Wi t hout f u r t h e r e l a b o r a t i o n , i t is be l i e ve d t hat
one
s k i l l e d in t h e
art can,
u s i n g t h e pr e c e di ng d e s c r i p t i o n , u t i l i z e t he
p r e s e n t
i n v e n t i o n
to i t s f u l l e s t e xt e nt . The f o l l o wi n g p r e f e r r e d s p e c i f i c embodi ment s
a r e ,
t h e r e f o r e , to be c ons t r ue d as merel y i l l u s t r a t i v e and not l i mi t a t i v e o f
the r emai nder o f t h e d i s c l o s u r e in
any way
what s oever . In the f o l l o wi n g
Exampl es, t e mpe r a t ur e s are set f or t h unc or r e c t e d in
degr ees Ce l s i u s .
Unless ot her wi s e i n d i c a t e d , al l par t s and pe r c e nt a ge s are by we i g h t .
For exper i ment s at hi gh t e mpe r a t ur e s , a membrane compr i s i ng a
t h i n
fi l m (about 0.2 mm) of
a
mol t en
s a l t s uppor t ed
in
a por ous
me t a l l i c o r
cerami c ma t e r i a l , was used. In a t y p i c a l case,
the membrane
s uppor t was
a c i r c u l a r pi ece
of #304 s t a i n l e s s s t e e l woven
wi re mesh (about 0.02 cm
in t h i c k n e s s ,
pore
si ze from 4-13 mi cr omet er s , Pal l
Cor p. , Cor t l a nd, NY),
s uppor t ed r i g i d l y
bet ween two I nconel 600 r i ngs about 10
cm
in i n n e r
di amet er . The me s h wa s l o a d e d wi t h a s al t
by me l t i ng the
dry
s a l t i n t o
i t s
por es ,
unt i l at l e a s t enough s a l t was used to pr ovi de a v i s i b l y
cont i nuous mol t en f i l m on one s ur f a c e of the wire mesh. The t h u s - c o a t e d
mesh and
suppor t assembl y was s eal ed i nt o a sample c e l l . In Fi gs. 2 and 3
are
shown a top view and a si de view, r e s p e c t i v e l y , of hol der a s s e mb l y 4
for
a wire mesh membrane s uppor t .
In Fig.
4 is shown the
sample c e l l 5,
i ncl udi ng the gol d 0- r i ng wi t h which the
suppor t as s embl y
is s e a l e d i n t o
the sample c e l l .
The sample
c e l l
or
module 5, as shown in
Fi g. 4, was pr ovi ded wi t h
means
f or i nt r oduc i ng f eed
g a s t h r o u g h
feed i n l e t 7 on the feed si de o f
the membrane 1, and for removal of a
gas
st ream r e j e c t e d by the membrane
t hr ough r e j e c t o u t l e t 8 wi t h per meat e sweep gas
i n l e t 10 on the o p p o s i t e
side of the membrane, f or pas s i ng
sweep gas
in c ont a c t wi t h the membrane
1 and
permeat e
o u t l e t means
11 for conveyi ng per meat e gases
and c a r r i e r
gas es
to an a n a l y z e r means. The a ppa r a t us was housed in
a t h e r mo s t a t t e d ,
t u b u l a r , h i g h - t e mp e r a t u r e he a t i ng mant l e and coul d
ope r a t e a t
t e mp e r a t u r e s up
to about 550C. The e xpe r i me nt a l assembl y al so i n c l u d e d
a gas
mani f ol d and was f u r t h e r pr ovi ded
wi t h e l e c t r o n i c
mass
f l ow
c o n t r o l l e r s t o per mi t p r e c i s e bl e ndi ng
of f eed
gas
mi xt ur e s . A
ga s
c hr oma t ogr a ph was used f or a n a l y s i s of the per meat e
gases
in the
sweep
s t r e a m.
A t y p i c a l l o we r - t e mp e r a t u r e membrane was pr e pa r e d by pl aci ng s e v e r a l
d r o p s o f a l ow- me l t i ng s a l t ( t et r ahexyl ammoni um be nz oa t e , Eastman Kodak
Co. ) on a c i r c u l a r pi ece
of 3501 ( Cel anese
Cor p. ) por ous pol ymer.
The
pol ymer was 27 mi c r ome t e r s t hi c k and had
pore
di mens i ons of 0.4
x
0 . 0 4
mi c r ome t e r s . The s a l t was smeared
over the s uppor t
wi t h a mi c r os c ope
s l i d e , which was
used t o remove excess
s a l t from the membrane. The
f i l l e d / c o a t e d membrane was l oaded i nt o a c e l l , ot he r wi s e as above, b u t
t h e r mo s t a t t e d i n a b a t h of e t hyl e ne g l y c o l .
In a not he r embodi ment of t he i nve nt i on
a s p e c t ,
t he method of t h i s
i n v e n t i o n wi l l be s e p a r a t i o n of
oxygen
from ot he r
gas es , usi ng mo l t e n
sodi um or l i t hi um n i t r a t e , i mmobi l i zed in
a por ous
met al s uppor t , at a
t e mp e r a t u r e above 400C.
Example 1
Se p a r a t i o n of Ammonia from Ni t r ogen us i ng a Li t hi um Ni t r a t e
I mmobi l i zed Mol t en Sa l t Membrane
S t a i n l e s s s t e e l woven
wi re mesh (# 304, about 0. 02 cm t hi ck, 4- 13
mi c r ome t e r s
pore
s i z e , ar ea about 0.8
cm2)
was coat ed wi t h f u s e d
l i t h i u m n i t r a t e
t o p r o v i d e a v i s i b l y c ont i nuous mol t en f i l m on one
s u r f a c e of t he wi re mesh, whi ch
was
mount ed i nt o the h i g h - t e mp e r a t u r e
t e s t i n g a p p a r a t u s .
The sampl e was heat ed to a f ur nace
t emper at ur e
o f
279C, us i ng a f eed fl ow of 30
cm3/min
f or f eed
gas
and a
sweep
flow on
t he
per meat e
si de of t he membrane of 30
cm3/min
of hel i um, both a t
about 1 at mos pher e p r e s s u r e
and 25C. The t o t a l
pr e s s ur e
in the c e l l
dur i ng the e xpe r i me nt s was about 760 t o r r . The c o n c e n t r a t i o n of
gases
i n
t he per meat e s t r eam was
de t e r mi ne d
by gas chr omat ogr aphy, usi ng a
305
cm
mo l e c u l a r s i eve column f or n i t r o g e n
and a
183
cm Chromosorb column f o r
ammonia, bot h ope r a t e d i s o t h e r ma l l y at 60C. Af t er the syst em ha d
s t a b i l i z e d at the o p e r a t i n g t e mp e r a t u r e ,
t her e was no l eak of
n i t r o g e n
acr os s
t he membrane, as
i n d i c a t e d by
very
low n i t r o g e n p e r me a b i l i t y .
The u t i l i t y
of the membrane in
s e p a r a t i n g
ammonia from ni t r oge n was
t e s t e d in t hr ee one- day runs. Duri ng each
run,
the c o n c e n t r a t i o n o f
ammonia in t h e a mmo n i a / n i t r o g e n
f eed
was var i ed from 0-100%. The
c o n c e n t r a t i o n s of ammonia and n i t r o g e n in the
per meat e were moni t or ed by
gas
c h r o ma t o g r a p h y .
Re s ul t s for s p e c i f i c ammonia n i t r o g e n mi xt ur e s ,
r e p r e s e n t i n g a n
aver age
of the t hr ee one- days runs we r e :
These r e s u l t s show t hat good s e p a r a t i o n of ammonia and n i t r o g e n was
a c c ompl i s he d, usi ng the i mmobi l i zed l i t hi um n i t r a t e membrane. It is a l s o
a ppa r e nt t hat p e r me a b i l i t y is
a
f u n c t i o n of the p a r t i a l
p r e s s u r e s
at t h e
feed i n t e r f a c e of t he membr ane.
Example 2
(a) Se pa r a t i on of Ammonia from Ni t r ogen usi ng a Zinc Ch l o r i d e
I mmobi l i zed Mol t en Sal t Membrane
The membrane was pr epar ed by mel t i ng zinc c h l o r i d e i nt o the
pores
o f
s t a i n l e s s s t e e l mesh (about 0. 02 cm t hi c k, area 0.8
cm2).
The membrane
was pl a c e d i n t he hi gh t e mpe r a t ur e c e l l and checked f or
c o n t i n u i t y by
meas ur i ng p e r me a b i l i t y of
pure
n i t r o g e n at 310C.
The membrane was used f or
s e p a r a t i o n o f ammonia from
n i t r o g e n over a
21-day per i od
of cont i nuous o p e r a t i o n . Gas flow on
bot h the f eed and
per meat e
si de
was
20
cm3/min
at about 1 aim and 25C. P e r me a b i l i t i e s
were c a l c u l a t e d as
t he means
of 10-15 measurement s of ammonia a nd
n i t r o g e n f l uxe s over a t wo- hour pe r i od, a f t e r t he
syst em
had r e a c h e d
e q u i l i b r i u m under a gi ven set of c o n d i t i o n s . Re s ul t s
we r e :
Ni t r oge n
f l ux t hr ough the zi nc c h l o r i d e membrane was
very
low, c l o s e
to t he backgr ound
l evel of
n i t r o g e n
in the
sweep
s t r eam. The r e f or e , t h e
s e l e c t i v i t y c o u l d n o t be de t e r mi ne d q u a n t i t a t i v e l y , but wa s e s t i ma t e d t o
be at l e a s t 1000 : 1.
(b) Se p a r a t i o n of Ammonia from Hydr oge n
Expe r i me nt s were
done
as
in
Example 2( a) , us i ng as the f eed st r eam a
mi xt ur e of ammonia and hydr ogen. Argon was
used as t he
per meat e sweep
gas
to f a c i l i t a t e d e t e c t i o n of hydr ogen by the
gas c h r o ma t o g r a p h .
At 311C, us i ng f eed of
pure
hydr ogen (800 t o r r ) , t he s t a n d a r d
hydr ogen p e r me a b i l i t y was c a l c u l a t e d t o be 9 Ba r r e r . Under the same
c o n d i t i o n s , us i ng pure
ammonia as f eed, the p e r me a b i l i t y of ammonia
was
2.9 x
104
Ba r r e r s . Th e r e f o r e , t he ammoni a/ hydr ogen s e l e c t i v i t y was
about 3 2 0 0 : 1 .
Example 3
Se p a r a t i o n of Ammonia from Ni t r oge n usi ng Zi nc Chl or i de I mmobi l i z e d
Mol t en Sa l t Suppor t ed in
a Porous Cerami c Membrane
A c i r c u l a r
sampl e
of
woven zi r coni um di oxi de c l o t h (about 0.038 cm
in t h i c k n e s s , 87% p o r o s i t y , t ype ZYW-15, Zi r c a r Cer ami cs , Fl o r i d a , N. Y. )
was soaked in mol t en zi nc c h l o r i d e . The t h u s - i mp r e g n a t e d membrane
was
s andwi ched bet ween two a nnul a r I nconel r i ngs ( out er di amet er about 1
cm,
i nner di a me t e r about 0.6 cm). The r e s u l t i n g assembl y was s eal ed i nt o t h e
hi gh t e mp e r a t u r e t e s t c e l l us i ng gol d O- r i n g s .
Pe r me a b i l i t y
measurement s were
made
as in
Example
2 at
gas p r e s s u r e s
of about 1 atm, f eed r at es of a mmoni a / ni t r oge n
or hel i um
sweep gas
of 20
cm3/min
at about 1 ai m and 25C and an
i n t e r n a l membrane t e mp e r a t u r e o f
311C.
Owing to u n c e r t a i n t i e s about the t hi c kne s s of the membr ane,
p e r me a b i l i t i e s i n Ba r r e r ,
a s i n d i c a t e d below, are u n c e r t a i n . Membrane
pe r f or ma nc e ,
de f i ne d as
Po/l
( cm / cm .
sec. cmHg) was
obt a i ne d
by
di vi di ng
s t a n d a r d p e r me a b i l i t y by the assumed t h i c k n e s s of the membrane
(l = 0. 038 cm). The ni t r oge n f l ux was a c c o r d i n g l y v e r y low, compar ed
to the backgr ound
l evel of n i t r o g e n
in the hel i um
sweep.
The e s t i ma t e d
PoNH3/PoN2 was
at l eas t 1400: 1
Example 4
Se p a r a t i o n of Carbon Di oxi de from Ni t r ogen usi ng a
Tet r ahexyl ammoni um Benzoat e I mmobi l i zed Mol t en Sal t Membrane
The membrane was pr epar ed by pl a c i ng s e ve r a l drops
o f
t e t r a he xyl a mmoni um be nz oa t e (THAB, Eastman Kodak Corp. ) on a
c i r c u l a r
pi ece
of 3501
Cel gar d" ( Cel anese Co r p . , t h i c k n e s s 0.0027
cm, ar ea 2 . 5 6
cm2,
pore
di mens i ons 0.4 x 0 . 0 4 mi c r o me t e r s , t o r t u o s i t y 1. 25, p o r o s i t y
0. 5) . The s a l t
was smeared over the pol ymer f i l m and al l owed to ent er t h e
porous
pol ymer. Excess s a l t was removed. The membrane was l oaded i n t o
the l o we r - t e mp e r a t u r e c e l l , t h e r mo s t a t t e d wi t h an et hyl ene gl ycol b a t h .
The i n i t i a l f eed flow was 11.7
cm3/min
of car bon di oxi de and 16. 9
cm3/min
of n i t r o g e n
and the per meat e
flow
was 10
cm3/min
of h e l i u m,
bot h at 1 atm. The per meat e was a na l yz e d
f or car bon di oxi de and n i t r o g e n
by gas chr omat ogr aphy, us i ng an
183 cm Por opak P col umn, run i s o t h e r ma l l y
at 60 C.
Carbon di oxi de and n i t r o g e n p e r me a b i l i t i e s were measured as a
f u n c t i o n of
t e mpe r a t ur e , t a ki ng i nt o account t he t o r t u o s i t y and
p o r o s i t y
of t he
s u p p o r t .
Re s u l t s wer e:
These r e s u l t s show t ha t car bon di oxi de p e r me a b i l i t y i nc r e a s e s wi t h
i n c r e a s i n g t e mpe r a t ur e ,
but s e l e c t i v i t y d e c r e a s e s .
Example 5
Se p a r a t i o n of Carbon Di oxi de from Ni t r oge n us i ng a
Tet r ahexyl ammoni um Sa r c o s i n a t e (THAS) I mmobi l i zed Molten S a l t
Membrane
Tet r ahexyl ammoni um hydr oxi de was pr e pa r e d by s t i r r i n g t o g e t h e r
t et r ahexyl ammoni um bromi de (2. 2
g,
East man Kodak Cor p. ) and 6.5
g.
o f
s i l v e r (I) oxi de in 25 ml of 80% met hanol : 20% wat er by volume. The
hydr oxi de was
t i t r a t e d wi t h
aqueous
s a r c o s i n e s o l u t i o n . Removal o f
s o l v e n t , us i ng a r ot a r y e v a p o r a t o r , gi ve t et r ahexyl ammoni um s a r c o s i n a t e ,
N( n- C6H11) 4 + NH(CH3)-CH2COO,
in t he form of
a yel l ow l i qui d. The
s a r c o s i n a t e
was
used to
pr e pa r e a membrane, s uppor t e d in a porous p o l y me r
f i l m as
in
Example
4. The membrane
was 0. 0027
cm in t h i c k n e s s ,
2. 56
c m
in
ar ea,
and had
a t o r t u o s i t y
of 1. 25 and p o r o s i t y of 0 . 5 .
The
pe r me a t i on exper i ment s were done at
gas p r e s s u r e s
about 760 t o r r a t
f eed f l ows of 11.7
cm3/min
f or car bon di oxi de and 16.9
cm3/min
f o r
n i t r o g e n and
sweep gas
fl ow (hel i um) of 10
cm3/ mi n.
Res ul t s wer e:
The THAS membrane was ope r a t e d
f or about four days at or below 75C
wi t hout
any
obser ved a l t e r a t i o n in i t s
p r o p e r t i e s . Af t er the membrane
was
heat ed to 95C, the car bon d i o x i d e p e r me a b i l i t y at 60C
was 218
Ba r r e r s and
PoCO2/PoN2
was 1 2 . 8 .
Al t hough the THAS membrane had l ower carbon di oxi de
p e r me a b i l i t y
t ha t the THAB membrane
of
Exampl e 4, the THAS
membrane
had
h i g h e r
s e l e c t i v i t y at e l e va t e d t e mp e r a t u r e s t han the THAB
membr ane.
Example 6
Se pa r a t i on of Water Vapor from Ni t r oge n usi ng Li t hi um Ni t r a t e / S o d i u m
Ni t r a t e I mmo b i l i z e d Mol t en Sal t Membrane
A mol t en s a l t membrane of
a
mi xt ur e of l i t hi um n i t r a t e / s o d i u m
n i t r a t e ( 0. 75: 0. 25 mol %)
was
i mmobi l i zed in
a s t a i n l e s s s t e e l wire mesh
as
in
Example 1. The membrane was pl a c e d
in the high t e mpe r a t ur e c e l l
and used to s e pa r a t e wat er
vapor
from n i t r o g e n . The d e t e c t i o n
syst em was
s i mi l a r to t hat of Example 1, except
t ha t a set of
hygr omet er s was
a t t a c h e d to each of the f eed and
per meat e
st r eams to measure dew
or f r o s t
poi nt (wat er c o n c e n t r a t i o n ) . The n i t r o g e n / wa t e r
feed mi xt ur e s
wer e
pr e pa r e d by pas s i ng n i t r o g e n t hr ough a bubbl e r , immersed in
a
wa t e r / e t h y l e n e gl ycol c ons t a nt t e mpe r a t ur e bat h. Feed mi xt ur e s of 1-3%
(by volume) of wat er were t hus o b t a i n e d .
Gas flows
were
20
CM /min
at about 1 atm. The membrane t h i c k n e s s
( s t e e l mesh) was
0.02
cm and the membrane area 0.8 cm. When t h e
membrane was heat ed to 230C,
very
low ni t r oge n p e r me a b i l i t y was
obs er ved. This i n d i c a t e s t hat the mol t en s a l t film
was c ont i nuous . The
membrane was
t e s t e d
over
f our
days
wi t h n i t r o g e n / wa t e r mi xt ur e s . Re s u l t s
we r e :
Owing to t he low l e ve l of n i t r o g e n pas s i ng t he f i l m, of t he or der o f
t he backgr ound l e ve l of n i t r o g e n , onl y a lower l i mi t f or
h y d r o g e n /
n i t r o g e n s e l e c t i v i t y
coul d be e s t i ma t e d. The t h u s - e s t i ma t e d
PoH2O/PoN2
is about 200: 1. I t is t h e r e f o r e
a ppa r e nt
t ha t t h e
s o d i u m/ l i t h i u m n i t r a t e i mmobi l i zed s a l t
membr ane per mi t s e x c e l l e n t
s e p a r a t i o n
of
wat er
from n i t r o g e n at 200 - 300C.
E x a m p l e 7
Ef f e c t of Wat er on Se p a r a t i o n of Carbon Di oxi de Usi ng an I mmobi l i z e d
Sa l t Membrane of Tet r ahexyl ammoni um Be nz oa t e
A membrane of t et r ahexyl ammoni um benzoat e, under c o n d i t i o n s
o t h e r wi s e as
in
Example 4, was used to s t u d y t h e e f f e c t of added wat er on
t he e f f i c i e n c y of
s e p a r a t i n g
car bon di oxi de from
n i t r o g e n . The wet f e e d
was pr oduced by bubbl i ng f eed t hr ough wat er at ambi ent
t e mpe r a t ur e
b e f o r e
pas s age over t he membr ane.
The f ol l owi ng r e s u l t s were o b t a i n e d :
These r e s u l t s show t hat moi st f eed had
hi gher car bon d i o x i d e
p e r me a b i l i t y
and s e l e c t i v i t y at lower
t e mpe r a t ur e s t han dry f eed. As t h e
t e mpe r a t ur e was r a i s e d, the e f f e c t of added wat er de c r e a s e d. I n
exper i ment s at 90C and above, a ddi t i on of wat er to the feed had
no
meas ur abl e e f f e c t .
Example 8
Se p a r a t i o n of
Oxygen
from Air usi ng a Li t hi um Ni t r a t e I mmobi l i z e d
Molten Sa l t Membrane
S t a i n l e s s s t e e l woven wire mesh (#304, about 0. 02
cm t hi c k, 4- 13
mi cr omet er s
pore
s i z e , area about 0.8
cm2)
was coat ed wi t h mo l t e n
l i t hi um n i t r a t e b y g r i n d i n g dry
l i t hi um n i t r a t e and p l a c i n g i t on t h e
mesh under an at mospher e
of
dry argon.
The cel l was c l os e d, connect ed t o
a gas
mani f ol d and heat ed to 285C under a feed flow of 10
cm3/min
o f
n i t r o g e n and per meat e
flow of 10
cm3/min
of hel i um at 1 atm
p r e s s u r e
for about 20 hr. At the end of t hi s time the l i t hi um n i t r a t e had we t t e d
t he s t a i n l e s s s t e e l mesh and formed
a v i s i b l y c ont i nuous mol t en f i l m
o n
one
s ur f a c e of t he wi r e mesh, and t hus
s e p a r a t e d t he feed and
p e r me a t e
s i des of t he c e l l :
The c e l l was
t hen heat ed to a f ur nace t e mp e r a t u r e of 429C, usi ng a
f eed flow of 10
cm3/min
of
zero gr ade
a i r and a
sweep
flow on t h e
p e r me a t e s i d e
of the membrane of 10
cm3/min
of hel i um, bot h at a b o u t
1 at mos pher e p r e s s u r e
and 25C. The t o t a l
p r e s s u r e
in t he cel l d u r i n g
t he e xpe r i me nt s was
about 760 t o r r .
The c o n c e n t r a t i o n of
gases
in the
per meat e
s t r eam was det er mi ned
by
gas
c hr oma t ogr a phy, us i ng a 183 cm 5A mol e c ul a r s i e ve column f or n i t r o g e n
and
oxygen,
o p e r a t e d i s o t h e r ma l l y at 60C. Af t er
t h e s y s t e m ha d
s t a b i l i z e d at t he o p e r a t i n g t e mp e r a t u r e ,
t he r e
was no l eak of
n i t r o g e n
a c r os s
t he membrane, as i n d i c a t e d by very
low n i t r o g e n p e r me a b i l i t y .
I t was obs e r ve d t ha t
oxygen
p e r me a b i l i t y i n c r e a s e d gr a dua l l y over 42
hour s of h e a t i n g .
Thi s
was
a t t r i b u t e d to an i n c r e a s e in t h e
c o n c e n t r a t i o n of oxi des (O .
O2 O2)
in the mol t en s a l t . I t
is pr opos ed t h a t t he d i s s o l v e d oxi des in t he mol t en s a l t c a t a l yz e d t h e
r e a c t i o n :
Ni t r oge n p e r me a b i l i t y was c ons t a nt ( about 12 Ba r r e r s ) . The
f o l l o wi n g r e s u l t s were o b t a i n e d :
These r e s u l t s show t hat a l i t hi um n i t r a t e i mmobi l i zed s a l t membrane
f u n c t i o n e d wel l f or a r e a s ona bl e t i me, and had good p e r me a b i l i t y a nd
s e l e c t i v i t y f or
oxyge n.
Example 9
Se p a r a t i o n
of Oxygen from Air usi ng a Sodium Ni t r a t e I mmobi l i z e d
Mol t en Sal t Membrane
A mol t en s al t membrane of
a sodium n i t r a t e
was i mmobi l i zed in
a
s t a i n l e s s s t e e l wire mesh as
in
Example
1. The sodi um n i t r a t e
was l o a d e d
ont o the s t a i n l e s s s t e e l mesh under an argon
a t mos phe r e a nd the cel l
was
a t t a c h e d to the
gas
mani f ol d. The c e l l was heat ed to 323C under a f e e d
flow of 10
cm3/min
o f n i t r o g e n and a per meat e
flow of 10
cm3/min
o f
hel i um f or about 15 h at 760 Torr. The f eed
gas was t hen changed t o
10
cm3/
min of zero grade
ai r at 760 To r r .
The c e l l
was
heat ed g r a d u a l l y to 450C, but no
oxygen was d e t e c t e d
in the per meat e st r eam, usi ng the a n a l y t i c a l method of
Example 1. At
477C,
oxygen was
obser ved in the
per meat e.
An e s s e n t i a l l y c o n s t a n t
val ue was
r eached a f t e r 4 h. The c e l l was hel d
at 477C f or 18 h and
t hen t he t e mpe r a t ur e was
va r i e d bet ween 452C and S25C t o det er mi ne t h e
e f f e c t of t e mpe r a t ur e
on
oxygen p e r me a b i l i t y . Re s ul t s
we r e :
Ni t r oge n p e r me a b i l i t y remai ned r e l a t i v e l y c o n s t a n t , at 12- 15
Ba r r e r . Thi s example shows t hat sodium n i t r a t e i mmobi l i zed mol t en s a l t
can
be used f or the s e p a r a t i o n of
oxygen
from a i r .
1. A
pr oc e s s
f or s e p a r a t i n g a
gas
from at l e a s t one ot her
gas
in
a
mi x t u r e , c ompr i s i ng pa s s i ng t he
gas
mi xt ur e
over a membrane s e l e c t i v e l y
pe r me a bl e to t he
gas bei ng s e p a r a t e d ,
which membrane compr i s es a t h i n ,
por ous
i n e r t
s uppor t
in which an a c t i v e ma t e r i a l is i mmo b i l i z e d wi t h i n
t he
por e s
and t he a c t i v e ma t e r i a l i s a mol t en s a l t .
2. The
pr oc e s s
of Cl ai m 1 wher ei n t he mol t en s a l t is
capabl e o f
u n d e r g o i n g one or more r e v e r s i b l e r e a c t i o n s , wi t h t he
gas bei ng s e p a r a t e d .
3. The
pr oces s
of Claim 2, wher ei n t he r e v e r s i b l e r e a c t i o n i s
f o r ma t i o n of a
c o o r d i n a t i o n
c ompl e x.
4. The
pr oc e s s
of Cl ai m 2, wher ei n t he r e v e r s i b l e r e a c t i o n is
a n
a c i d b a s e r e a c t i o n .
5. The
pr oc e s s
of Claim 2, wher ei n t he r e v e r s i b l e r e a c t i o n i s
f o r ma t i o n of an or ga ni c chemi cal compound.
6. The
pr oc e s s
of Claim 2 wher ei n t he r e v e r s i b l e r e a c t i o n is a n
o x i d a t i o n - r e d u c t i o n r e a c t i o n .
7. The
pr oc e s s
of Claim 1, wher ei n t he membrane i s c o n t a i n e d
wi t h i n
a module of hol l ow f i b e r s , a s p i r a l wi ndi ng or a
s e r i e s of f l a t
p l a t e s .
8. The
pr oc e s s
of Claim 1, wher ei n the r e v e r s i b l e
o x i d a t i o n - r e d u c t i o n r e a c t i o n i s n i t r a t e - n i t r i t e i n t e r c o n v e r s i o n ,
oxyge n
i s t he
gas
bei ng s e pa r a t e d and the a c t i ve ma t e r i a l in t he membrane i s
mol t e n a l k a l i met al n i t r a t e .
9. The
pr oces s
of Claim 1, wher ei n the
porous
membrane
c o n t a i n i n g
the mol t en s a l t i s s u p p o r t e d on a macr opor ous suppor t composed o f
cer ami c, g l a s s ,
me t a l l i c or pol yme r i c
ma t e r i a l .
10. The
pr oces s
of Claim 1, i nc l udi ng removing
gas pa s s i ng t h r o u g h
the membrane by. a st r eam of s weep
g a s .
11. The
pr oces s
of Cl ai m 1, i nc l udi ng removing gas pa s s i ng t h r o u g h
the membrane usi ng a c o mp r e s s o r .