ULTPAPUPE WATEP

SEPTEMBEP 1996--UP130653 53
D
DEAERATION
DEGASIFICATION OF WATER USING NOVEL MEMBRANE TECHNOLOGY
naturally prosont in wator. Dissolvod
gasos snould bo oaroully monitorod
and oontrollod, as tnoy oan aoot tno
produots and prooossos in wnion tno
wator is usod. For oxamplo, dissolvod
oxygon oan roaot witn motals, orming
an oxido layor on tno suraoo o inisnod
produots or piping matorial. Also, as tno
wator tomporaturo is inoroasod, dis-
solvod gasos oan orm bubblos tnat
may load to inoomploto wotting o sur-
aoos. Tno romoval o dissolvod gasos
is an important prooossing stop and is
routinoly aooomplisnod witn a vaouum
dogasiioation oolumn or witn onomi-
oals. Pomoval o spooiio gasos, suon
as oxygon, oan also bo aooomplisnod
by stripping tno gasos rom tno wator
using a vaouum and/or an inort gas suon
as nitrogon.
Mombranos navo boon usod to
dogasiy wator or moro tnan 20 yoars in
laboratory onvironmonts. Ono ma|or
drawbaok o tno mombranos nas boon
tnoir inability to nandlo industrial-sizo
lowratos oioiontly. Booauso o tnis low
oapaoity, mombranos navo boon viowod
as small-soalo dovioos. Ovor tno last
sovoral yoars, now dosigns navo ro-
oontly boon dovolopod to ovoroomo tno
oapaoity limitations. Dogasiioation
mombrano modulos, also oallod mem-
brane contactors, and dosignod to
nandlo industrial-sizo lowratos, aro now
oommoroially availablo. Tnis papor dis-
oussos tno tnoory bonind mombrano
dogasiioation and its ovolution ovor tno
last ow yoars.
Background
n ordor to bost oxplain tno oporation o
mombrano-basod dogasiioation sys-
toms, it is important to roviow tno laws
govorning idoal gasos. Tnoso rolation-
snips govorn tno oporation o tno mom-
brano oontaotors as woll as tnat o oon-
vontional dogasiioation oolumns.
Dalton's law statos tnat tno total pros-
suro o a gas mixturo is oqual to tno sum
o tno partial prossuros o tno individual
gasos in tno gas mixturo (Equation 1):
P
total
= P
1
+ P
2
+ P
3
+ ... Eq. 1
Tno partial prossuro oomponont o oaon
gas oan bo rowritton as in Equation 2:
P
total
= P
total
y
1
+ P
total
y
2
+ P
total
y
3
+... Eq. 2
wnoro y
n
= tno molo raotion o tno oom-
ponont.
Tnoso rolationsnips toll us tnat tno
prossuro tnat a gas will oxort in a ixod
volumo is dopondont on tno total pros-
suro o tno gas mixturo and on tno indi-
vidual oonoontration o tno gas in tno
mixturo (1). Tnis is an important rolation-
snip tnat is usod to oroato tno driving
oroo to romovo or dissolvo gasos into
wator.
Honry's law statos tnat tno solubility o a
gas in wator is dirootly proportional to
tno partial prossuro o tnat gas. Tnis
rolationsnip is gonorally valid at low dis-
solvod-gas oonoontrations (2).
P
1
= H
x
Eq. 3
wnoro P
1
= partial prossuro o tno gas;
H = tno Honry oooioiont or tnat gas
(tnis valuo oan bo ound in onginooring
tablos); and
x = oonoontration o dissolvod gas.
Tnis law tolls us tnat tno amount o gas
tnat will dissolvo in wator is proportional
to its partial prossuro. Wo know rom
issolvod oxygon,
nitrogon, and oar-
bon dioxido aro
SSN:0747-8291. COPYPGHT (C) Tall Oaks
Publisning, no. Poproduotion in wnolo, or in part,
inoluding by olootronio moans, witnout pormission
o publisnor is pronibitod. Tnoso rogistorod witn tno
Copyrignt Cloaranoo Contor (CCC) may pnotooopy
tnis artiolo or a lat oo o $1.50 por oopy.
By Fred Wiesler
and Rick Sodaro
Hooonst Colanoso Corp.
Dalton's law tnat tno partial prossuro o
a gas is dirootly proportional to its oon-
oontration in tno gas pnaso. From tnoso
two rolationsnips wo oan dotormino a
partioular gas oquilibrium oonoontration
in tno aquoous gas pnaso i wo know tno
total gas prossuro and tno oonoontra-
tion o tnat oomponont in tno gas pnaso.
Mass Transfer
n ordor to transor a dissolvod gas rom
an aquoous pnaso into tno gasoous
pnaso, tnoro must bo a driving oroo.
Tno driving oroo utilizod witn a mom-
brano oontaotor is a oonoontration (or
partial prossuro) dioronoo. From
Honry's law, wo noto tnat i wo roduoo
tno partial prossuro o a gas wo oan
roduoo tno amount o tnat gas tnat will
romain dissolvod in wator. So, i wo
roduoo tno partial prossuro o tno gas,
somo quantity o dissolvod gas will oomo
out o solution until tno systom roaonos
oquilibrium. From Equation 3, wo oan
soo tnat tno partial prossuro o a gas is
oqual to tno produot o tno total gas-
pnaso prossuro and tno oonoontration
o tno gas in tno gas pnaso. Tno partial
prossuro o tno gas oan bo roduood by
loworing tno total prossuro o tno gas
pnaso and/or by loworing tno oonoon-
tration o tno individual gas in tno gas
pnaso. Tnoso samo prinoiplos govorn
t no oporati on o a oonvont i onal
dogasiioation oolumn.
For oxamplo, wator tnat nas boon in
oontaot witn air and nas boon allowod to
roaon oquilibrium oontains a oortain
quantity o dissolvod nitrogon and dis-
solvod oxygon gas. Tno amount o oaon
gas tnat dissolvos into tno wator is pro-
portional to tno partial prossuro o tno
gas in air. tnis wator is oxposod to a
nitrogon onvironmont, suon as a nitro-
gon blankot, dissolvod oxygon will bo
romovod and nitrogon will bo dissolvod
into tno wator. Tno oxygon tonds to
loavo tno aquoous pnaso booauso o
tno onango in oonoontration and oorro-
sponding partial prossuro o tno oxygon
in tno gasoous pnaso. Tno nitrogon
tonds to dissolvo into tno wator booauso
o an inoroaso in oonoontration and par-
tial prossuro in tno gasoous pnaso. Simi-
larly, i tno wator is oxposod to a vaouum,
ULTPAPUPE WATEP

SEPTEMBEP 1996--UP130653 54
tno total gas-pnaso prossuro and oorro-
sponding partial prossuro o tno gasos
will bo roduood and botn gasos will bo
romovod rom tno wator.
Membrane Contactor Theory
Mombrano oontaotors aro typioally snoll-
and-tubo dovioos oontaining mioropo-
rous nydropnobio nollow ibors. Sinoo
wator will not pass tnrougn tno poros,
tno mombrano suraoo aots as an inort
support tnat allows wator to oomo into
diroot oontaot witn a gas pnaso witnout
disporsion. Tno partial prossuro o a
gas oan bo ad|ustod to oontrol tno
amount o tnat gas tnat will dissolvo into
wator.
Sinoo a mombrano oontaotor oontains
many small-diamotor ibors, tno intor-
aoo botwoon tno gas and liquid pnaso
booomos vory nign. n aot, tno oontaot
aroa por unit volumo ratio is typioally an
ordor o magnitudo groator tnan tnat or
a oonvontional paokod oolumn. Tnis
oonoopt oan groatly roduoo tno sizo o a
dogasiioation systom.
Tno rato at wnion tno gas will loavo tno
wator and ontor tno gas pnaso is limitod
by tnroo rosistanoos:
1. Tno rosistanoo tnat tno molooulos o
dissolvod gas will onoountor wnon
travoling tnrougn tno wator;
2. Tno rosistanoo tnat tno molooulos o
dissolvod gas will onoountor wnon
tnoy travol tnrougn tno mombrano;
and
3. Tno rosistanoo tnat tno molooulos o
dissolvod gas will onoountor wnon
tnoy travol tnrougn tno gas away rom
tno mombrano.
For typioal inort gasos suon as nitro-
gon and oxygon, tno liquid-sido mom-
brano rosistanoo will bo tno dominant
rosistanoo, and tno otnor rosistanoos
oan bo assumod to bo nogligiblo (3).
Evolution
Tno irst -gonorat ion mombrano
Figure 1. Oxygen remova| evices.
Figure 3. Oxygen remova| performance of a 10-inch-iameter
membrane contactor (135 m
2
area).
Figure 4. Pressure rop through a 4-inch-iameter membrane
contactor.
Figure 2. Oxygen remova| performance of a 4-inch-iameter
membrane contactor (19 m
2
area).
ULTPAPUPE WATEP

SEPTEMBEP 1996--UP130653 55
diamotor oontaotor nas allowod tno mombrano oontaotors to
bo utilizod in systoms witn largor lowratos. Tnis nign-oapaoity
oontaotor nas providod systom dosign onginoors an option to
roplaoo oonvontional dogasiioation toonnologios or low
lowratos as woll as or lowratos oxoooding 1,000 gpm.
Figuros 4 and 5 snow tno prossuro drop o tno samo two
mombrano oontaotors as a unotion o lowrato. Figuro 4 snows
two ourvos, ono dosoribing tno prossuro drop assooiatod witn
low insido tno nollow ibor (tubo sido), and tno otnor dosorib-
ing tno prossuro drop assooiatod witn low on tno outsido (snoll
sido) o tno nollow ibors. As oan bo soon rom tno grapn, tno
prossuro drop o tno oontaotor witn low insido tno nollow ibors
is muon groator tnan tno prossuro drop o tno samo oontaotor
witn low outsido tno ibors. Tnis oan bo attributod to tno largor
and moro opon low aroa availablo in tno snoll-sido dosign.
As oan bo soon rom tno prossuro-drop ourvos (Figuros 4
and 5), tno maximum oapaoity o tno 4-inon-diamotor oontaotor
is about 30 gpm (114 litors por minuto |L/min]), and tno 10-
inon-diamotor oontaotor nas a maximum oapaoity o 200 gpm
(760 L/min). Tno prossuro drop or oaon o tnoso dovioos at
tnoir maximum oapaoity is loss tnan 10 pounds por squaro inon
gaugo (psig). Tnis low prossuro drop allows tnoso dovioos to
bo plaood in sorios. Tno ability to plaoo tnoso oontaotors in
sorios allows tno ovorall oioionoy to bo inoroasod. For
oxamplo, i tnroo 10-inon oontaotors aro plaood in sorios in a
150-gpm stroam, tno irst oontaotor will romovo approximatoly
95% o tno dissolvod oxygon, tno sooond will romovo 95% o
tno romaining dissolvod oxygon, and tno tnird will romovo an
additional 95% o tno romaining dissolvod oxygon. Tnis allows
tno oontaotors to romovo 99.99% o tno dissolvod oxygon rom
tno 150-gpm wator stroam witn loss tnan a 15-psig prossuro
drop.
Carbon Dioxide Removal Performance
Tno mombrano oontaotors oan bo usod to romovo a varioty o
gasos rom wator. Wnon romoving a roaotivo gas suon as
oarbon dioxido, it is important to oxamino roaotion kinotios and
its ooot on mass-transor ratos. Tno mombrano oan romovo
only dissolvod spooios tnat oxort a partial prossuro and aro
volatilo. Tnorooro, only tno roo oarbon dioxido oan romovod,
not tno oarbonato or bioarbonato orms. Tno mombrano
Figure 5. Pressure rop through a 10-inch-iameter membrane
contactor.
Figure 6. Pemova| efficiency of nitrogen uner vacuum
conitions.
oontaotors woro simply bundlos o nydropnobio ibors plaood
into a snoll. Wator was pumpod tnrougn tno insido o tno nollow
ibor and gasos woro passod aoross tno outsido. Tno lowrato
tnrougn tno dovioo was limitod by tno prossuro drop assooi-
atod witn tno liquid low tnrougn tno nollow ibors, and mass
transor was innibitod by tno laminar low limitations o tno
liquid low (4). Tno dovioos woro limitod to low lowratos, and
systoms woro ovorsizod to mako up or tno low mass-transor
ratos.
Ovor tno last sovoral yoars, a novol mombrano oontaotor
dosign was dovolopod tnat nas dramatioally inoroasod tno
low oapaoity o tnoso dovioos up to 200 gallons por minuto
(gpm). Tnis patontod now dosign inoorporatos a nollow-ibor
abrio array tnat is wound around a oontral distribution tubo
witn a oontral rosin balo. Tnis patontod dosign allows or
turbulont low on tno outsido o tno nollow ibor (5). Tno ibor
is arrangod in a uniorm opon paoking tnat allows or a groator
low oapaoity and utilization o all o tno mombrano aroa. Wator
lows radially aoross tno mombrano, wnion induoos looal
turbulonoo tnat inoroasos tno mass transor in tno wator pnaso,
tno dominant mass-transor rosistanoo in a mombrano
oontaotor. Pnotograpns o tnoso dovioos aro snown in Figuro
1.
A typioal mombrano oontaotor oontains tnousands o
mioroporous polypropylono nollow ibors wovon into a abrio
array. By ad|usting tno oonoontration o tno gasos on tno insido
o tno ibor, tno oonoontration o dissolvod gasos in tno aquo-
ous pnaso, outsido o tno ibor, oan bo oontrollod.
Oxygen Removal Performance
Figuros 2 and 3 snow tno oxygon romoval porormanoo as a
unotion o wator lowrato o two oommoroially availablo mom-
brano oontaotors. Figuro 2 snows tno low vorsus poroontago
o oxygon romoval o a 4-inon-diamotor mombrano oontaotor.
Figuro 3 snows tno samo ourvo or a 10-inon-diamotor oontaotor.
Botn grapns woro gonoratod using a nitrogon swoop insido tno
nollow ibor.
As oan bo soon rom tnoso two grapns, tno 4-inon oontaotor
oan romovo approximatoly 90% o tno dissolvod oxygon at 20
gpm, and tno 10-inon will navo approximatoly tno samo ro-
moval oioionoy at 200 gpm. Tno nign oapaoity o tno 10-inon-
ULTPAPUPE WATEP

SEPTEMBEP 1996--UP130653 56
oannot romovo tno ionio spooios. Tno
amount o oarbon dioxido tnat will bo
romovod is typioally roportod as a por-
oontago o tno dissolvod-gas oompo-
nont.
Nitrogen Removal Performance
Nitrogon oxists as a dissolvod gas and
doos not dissooiato in wator. Undor
ambiont oonditions undor 1 atmospnoro
o air, wator will oontain approximatoly
14 parts por million (ppm) o dissolvod
nitrogon and 8.5 ppm o dissolvod oxy-
gon. Tost rosults indioato tnat oxygon
and nitrogon aro romovod at approxi-
matoly tno samo rato. Tnis oan bo attrib-
utod to tno similarity in sizos and woignts
o tno oxygon and nitrogon molooulos.
Sinoo tnoy aro similar in sizo and woignt,
tno liquid-pnaso rosistanoos aro similar.
Figuro 6 snows tno romoval oioionoy o
nitrogon undor vaouum oonditions.
System Design
Ovor tno last ow yoars, mombrano
oontaotors navo booomo viablo altorna-
tivos or dissolvod-gas romoval rom
wator. Tno mombrano dosign nas boon
improvod to ovoroomo nydrodynamio
prossuro-drop rosistanoos, allowing in-
dividual oontaotors to nandlo an oxooss
o 200 gpm. Booauso o tno oontaotors'
low prossuro drop, tnoy oan bo plaood
in sorios to inoroaso tnoir oxygon ro-
moval oioionoy.
Tno mombrano oontaotor allows or
somo uniquo dosign oonsidorations.
Booauso o tnoir nondisporsod immobi-
lizod gas liquid intoraoo, mombranos
oan bo oporatod ovor a wido rango o
lowratos witnout aooting tno oootivo
oontaot aroa or mass transor. Tno
intoraoo is unaootod ovon wnon tno
oontaotor is oxposod to suddon onangos
in low. Booauso o tno uniorm mom-
brano paoking struoturo o tno dovioo,
tno swoop gas oonsumption or vaouum
pump sizo oan bo minimizod. Tno modu-
lar dosign allows or systoms to bo built
witn a low proilo, and oan bo tailorod or
oaon applioation.
Conclusions
Mombrano oontaotors utilizo tno samo
basio gas laws tnat govorn tno oporation
o oonvontional dogasiioation oolumns.
Tno mombrano oontaotors simply bring
tno gas and liquid pnaso into oontaot
witn ono anotnor at a nydropnobio poro
ratnor tnan by disporsing tno liquid pnaso
into tno gasoous pnaso.
Mombrano oontaotors navo boon avail-
ablo or laboratory-soalo applioations
or many yoars. Tno rooont oapaoity
and porormanoo ovolution nas brougnt
tnom out o tno laboratory and into tno
ull-soalo manuaoturing aoilitios. Somo
o tnoso aoilitios uso mombranos to
proooss ovor 1,000 gpm o dooxygon-
atod wator.
Tno toonnology is still now to many
dosign onginoors and ondusors. Ovor
tno last sovoral yoars, tnoso nign-oa-
paoity mombrano dovioos navo provon
tnoir intogrity and navo rapidly grown
markot aoooptanoo. Tnoir uso in wator
systoms is mado attraotivo by many
uniquo onaraotoristios:
1. Tno modular dosign, liko tnat o
iltration, rovorso osmosis, and ion
oxonango, allows tno ontiro wator
systom to bo dosignod witn loxibility.
2. Tno nondisporsivo dosign oliminatos
systom upsots tnat ooour during start-
up and onangos in lowrato.
3. Tno mombrano dovioo and nousing
mako it possiblo to dosign an ooo-
nomioal "olosod" systom or gas
romoval.I
References
1. Donbign, K. The Princip|es of Chemica|
Equi|ibrium, 3rd od., pp. 114-118, Cam-
bridgo Univorsity Pross, London, England
(1978).
2. Edwards, W.M. Perry's Chemica| Engi-
neering Hanbook, Porry, P.H., Groon,
D.W.; Malonoy, J.O., Eds., 6tn od., sootion
14, MoGraw-Hill Book Co., Now York, N.Y.
(1984).
3. Yang, M.; Cusslor, E.L. "Dosigning Hol-
low-Fibor Contaotors", AChE Journa|
32(11), pp. 1-5 (Novombor 1986).
4. Pood, B.W.; Sommons, M.J.; Cusslor, E.L.
Membrane Separations Techno|ogy, Prin-
cip|es an App|ications, Noblo, P.D.; Storn,
S.A., Eds., Cnaptor 10, Elsovior Soionoo,
Amstordam, Tno Notnorlands (1995).
5. Prasad, P; Punklo, C.J.; Snuoy, H.F. "Spi-
ral-Wound Hollow Fibor Mombrano Fab-
rio Cartridgos and Modulos Having Flow
Dirooting Balos", U.S. Patont Numbor
5,352,361 (1994).
Author Fred Wiesler is a senior technical
service engineer with Hoechst Celanese
Separations Products Division in Char-
lotte, N.C. He has more than eight years
of membrane-related experience, four of
which have been spent working with
membrane contactors. Coauthor Rick
Sodaro is the manufacturing team leader
for the membrane contactor product line
of Hoechst Celanese Separation Prod-
ucts. He has 17 years of technical poly-
mer experience, of which the last four
have been spent working in the area of
membrane contactors.
Key words: DEAEPATON, DEGASF-
CATON