Pergamon

('ilt,mic,t~ Englim'errnq 5~iemt,. VoI. 52. Nos 21 22. p p 4119- 4126. 1997
199'7 El sevi er Science Lt d All r i ght s re~er' .ed
Pr i nt ed in Gr e a t Br i t ai n
PII: S0009- 2509(97)00254- 6 cx~ 25t~ 97 sit ~ o~
Absorption dynamics of CO2 bubbles in a
pressurized liquid flowing downward
and its simulation in seawater
Katsumi Tsuchiya,** Hiroaki Mikasa* and Takayuki Saito**
*Depar t ment of Chemi cal Science and Technol ogy, The Uni versi t y of Tokus hi ma,
Tokus hi ma 770, Japan
t Mi ni ng and Geot echnol ogy Depar t ment , Nat i onal I nst i t ut e for Resources and Envi r onment .
Ts ukuba 305, Japan
(Received 1 Jul y 1997)
Abstract--The a bs or pt i on process of car bon di oxi de from a single bubbl e to t he s ur r oundi ng
l i qui d at el evat ed pr essur e is st udi ed bot h exper i ment al l y and t heoret i cal l y. Exper i ment s ar e
conduct ed in a l abor at or y- s cal e col umn t hr ough which t he l i qui d flows downwar d t o hol d each
i nject ed bubbl e near l y st at i onar y. The system is pressuri zed up to 0.6 M Pa and sodi um chl or i de
is added t o wat er. A si mpl e t heor et i cal model is used t o si mul at e t he basi c feat ures of t he
a bs or pt i on dynami cs for bubbl es ascendi ng in shal l ow ocean. The bubbl e size is found to
i ni t i al l y decr ease al most l i near l y with time. Thc addi t i on of NaCI si gni fi cant l y reduces t he
a bs or pt i on rat e of CO2. An anal ysi s of shape or surface osci l l at i ons of t he bubbl e reveal s t hat
this effect ari ses from t he suppr essi on of wavy fl uct uat i ons al ong the gas - l i qui d interface. The
model pr edi ct s t hat t he r at e of bubbl e size r educt i on is al most i ndependent of t i me and pressure
for bubbl es l ar ger t han 1 mm, r epr oduci ng the exper i ment al results r easonabl y well. ~" 1997
El sevi er Science Lt d
Keywords: Gl oba l warmi ng; car bon di oxi de; oceani c upt ake: shal l ow-sea injection; gas abs or p-
t i on: mass t ransfer coefficient.
I N TR OI ) I . / C TI ON
The oceani c upt ake (or in a posi t i ve sense, st orage) of
car bon di oxi de is one of t he pr omi s i ng measur es
for r educi ng t he gl obal warmi ng. Besides t he t echni cal
opt i on cur r ent l y accept ed most widely, which consi st s
of deep- sea ( > 3 km) i nject i on and subsequent seques-
t r at i on as l i qui d and t he associ at ed hydr at es, respec-
tively (Mar chet t i , 1977), t here is anot her opt i on
which utilizes shal l ow (200--400 m) i nject i on fol l owed
by downwa r d t r a ns por t t hr ough a dense gr avi t y cur-
rent (Haugan and Dr ange, 1992). The l at t er has
an a dva nt a ge of savi ng ener gy; cost of gas liquefac-
tion. It s s e c o n d - - a n d t he most c r i t i c a l - - s t e p, i.e.
t r ans por t i ng t he di ssol ved gas downwar d, can in pri n-
ci pl e s pont aneous l y t ake pl ace due to t he difference in
densi t y bet ween t he CO2- enr i ched and ambi ent sea-
wat er (Haugan and Dr ange, 1992). If one coul d l ocat e
sui t abl e sites and real i ze t he oper at i on with sufficient
gr avi t y cur r ent s bei ng at t ai ned, this t echni cal opt i on
woul d be qui t e efficient as a s hor t - t er m sol ut i on.
Rel easi ng gaseous CO2 i nt o seawat er under moder -
at e de pt h' pr e s s ur e condi t i ons will unavoi dabl y result
' Corresponding author. Te l . : ~-81-886-56-7426: fax:
+ 81-886-55-7025: c-mail: kats@chem.tokushirna-u.ac.jp.
in the for mat i on of(ascendi ngl bubbl es which hamper
t he gr avi t y current . The bubbl es mot i on enhances t he
di sper si on of t he di ssol ved gas or t he di l ut i on of t he
COz- enr i ched ' cl oud' of seawat er, which is al so det r i -
ment al t o sust ai ni ng cal m gr avi t y current s. To over-
come these i nherent difficulties, Sai t o and Kaj i shi ma
119961 recent l y pr opos ed a syst em cal l ed t he gas lift
advanced di ssol ut i on ( GLAD) to be used specifically
for t he CO2 sequest r at i on in t he ocean by shal l ow
injection. The GL AD system utilizes a gas-lift pump.
The upwar d mot i on of t he l i qui d or t he buoyant
pl ume of t he bubbl y gas - l i qui d mi xt ur e i nduces
' suct i on' of fresh seawat er at t he riser bot t om or t he
pump ent rance. As t he buoyant pl ume is r eachi ng
t he ri ser t op, t he di ssol ut i on process i s - - i de a l l y
s p e a ki n g - - t o be compl et ed; t he dense sol ut i on flow-
ing downwar d in t he downc ome r and rel eased from
its bot t om or t he pump exit coul d by itself descend
before any si gni fi cant di l ut i on t akes pl ace to a deeper
l ocat i on.
The present st udy focuses on obt ai ni ng a funda-
ment al under s t andi ng of t he a bs or pt i on behavi or of
single CO2 bubbl es in pressuri zed wat er in t he ab-
sence and presence of sodi um chl ori de. To si mul at e
t he basi c feat ures pr evai l i ng in t he shal l ow injec-
t i on scheme or in t he GLAD riser, exper i ment s are
4119
4120
conduct ed in a laboratory-scale, pressurized col umn
t hrough which the liquid flows downward to hold
each injected bubbl e nearly st at i onary so that its
behavior can be observed over a prol onged period.
The si ngl e-bubbl e absor pt i on process is then modeled
and simulated numeri cal l y by i ncor por at i ng the ex-
perimental results.
EXPERIMENrAL
The fate of a CO2 bubbl e is observed via a CCD
camera (Sony XC-711 LC), recorded on a video system
at 30 frames/s over an exposure time of 1/1000 s, and
later analyzed frame by frame to estimate its size from
the projected bubbl e area. If the gas phase within the
bubbl e is assumed to be pure CO2, the absor pt i on
rate of CO2 i nt o the liquid can be det ermi ned from the
time vari at i on of the bubbl e size.
Figure 1 shows a schematic of the experimental
setup used in this study. The mai n appar at us is the
downward-l i qui d-fl ow (DLF) col umn which consists
of the tapered test section, topped with the liquid-flow
st rai ght eni ng section, and the bubbl e injecting section
below. The test section is a rot amet er (Ni ppon Flow
Cell, Model SGK- I - 20A) fixed in an inverted position
with all the i nt ernal s removed and machi ned to effect
smoot h expansi on as the liquid flows downward. It
ha s a n 18 mm mi ni mum ID, 26 mm maxi mum I Da n d
230 mm effective height. The st rai ght eni ng section
comprises a 390mm long PVC cylinder of 18 mm
ID, top of which has a conical ent rance to suppress
Brass
rod
Straw
CCD
career
Drain Pump
Fig. 1. Schematic diagram of the experimental setup.
K. Tsuchiya e t a l .
sudden expansi on of the liquid flow from the 12 mm
OD inlet t ubi ng, and the i nt ernal flow spoiler. The
bubbl e injecting section houses, al ong the central axis
of the col umn, a stainless-steel nozzle of 4.0 mm ID
with a conical diverging end, t hrough which a single
gas bubbl e is introduced. Almost the entire port i on of
the experimental setup is immersed in a rect angul ar
water t ank which serves: to reduce any optical distor-
t i on associated with the curved surface of the test
section, as a protective cont ai ner, and as a const ant -
t emperat ure bath. Dur i ng each run the t emperat ure is
mai nt ai ned at 20 1 C.
Tap water or its NaCI sol ut i on is used as the liquid
phase, which is pumped from the pressurized liquid
t ank made of stainless steel and of 5 10 -3 m 3 effec-
tive volume, t hrough 12 mm OD t ubi ng, to the DLF
col umn and is circulated back to the tank. The circu-
lating liquid flow rate is measured with a rotameter.
The system is pressurized by the ni t rogen supply to
the t ank at a desired level up to 0.6 MPa. The pressure
in the tank (or the equi l i brat ed pressure in the whole
closed system) is moni t ored with a pressure gauge and
cont rol l ed by the back-pressure valve fixed on the
pressurizing gas line. The lateral di st r i but i on of down-
ward liquid velocity in the test section is roughly
examined by tracing tiny bubbl es which start appear-
ing as the pressure is reduced below a certain level.
The flatness of the di st r i but i on is improved by the
internal-flow spoiler, which includes a brass rod of
4 mm di amet er and 300 mm length mount ed on the
center of a honeycomb disk and a bundl e (half
a dozen) of plastic dr i nki ng straws of the same
diameter. The bubbl e size is eval uat ed either by col-
lecting each bubbl e to measure its volume, which can
be applied onl y once for a given bubbl e, or by
cont i nuousl y moni t or i ng the bubbl e via the CCD
camera -which suits the present obj ect i ve- - t o
measure the projected bubbl e area or its dimensions.
The former met hod is used with N2 bubbl es to cali-
brate the latter in convert i ng the projected di mensi ons
to the pert i nent volume. The effect of salts cont ent is
examined over the Na C1 concent r at i on range
0- 3 wt%.
PHYSICAL MODELING
The out come of directly i nject i ng gaseous C02 i nt o
the ocean, i.e. whether this will result in the negative
buoyancy of CO2-rich seawater, depends critically on
the rate of upt ake of CO2 from the ascendi ng bubbles.
A CO2 bubbl e, while rising, shrinks its vol ume as the
mass is transferred across its surface to the sur-
roundi ngs:
d 2 C b = - ~ d ~ k , , ~ C, , - C , ) . ~ 1 )
The effect of bubbl e-shape def or mat i on on eval uat i ng
the t rue i nt erraci al area f or mass transfer is not
accounted f or due t o the compl exi t y i nvol ved i n the
shape fluctuations. The surface area is represented
by the vol ume-equi val ent spherical di amet er ( d , , ) .
Absorption dynamics of CO, bubbles
Re a r r a n g i n g eq. (1) for t he bubbl e di a me t e r yi el ds 10"
d, / , _ 2 ]
d t - ( ' h L 6 ~ + k z . ( C s - C , ) . (2)
The first term on the ri ght -hand side ( R H S) of
eq. (2) c o n t a i n s t he va r i a t i on wi t h t i me i n t he mol a r
c o n c e n t r a t i o n of CO2 gas i n t he bubbl e (Ch) whi ch,
even for near l y p ur e - c o mp o n e n t bubbl es , needs to be
t a ke n i nt o a c c ount si nce t he st at i c pr essur e (pt a nd
t e mpe r a t ur e ( T) in t he s ur r o un d i n g l i qui d phase s
change as t he bubbl e rises at its t er mi nal vel oci t y L'h. 2
Ch is de t e r mi ne d from t he e qua t i o n of st at e
100
C ~ - p ~ . , ( Z R T ) (3)
5
wher e Z is t he compr es s i bi l i t y fact or a nd Ph t he pres- 7"
sur e i nsi de t he bubbl e gi ven as
2
p ~ = p + 4 a t . , . d , . (4)
10-t
by i ncor por at i ng the erect of surface tension (at.),
whi ch is si gni fi cant especi al l y for smal l bubbl es. 5
Di ffer ent i at i ng eq. (3) wi t h respect t o t i me gives 10 2
d < , ,
dt - R ~ \ Z - T J d-7" (5)
Si nce t he ver t i cal c o o r d i n a t e of t he bubbl e pos i t i on is
specified by
dz.:dl = - L:, (6)
a nd t he st at i c pr essur e at t he dept h z bel ow t he sea
surface by
P = P o + p t . . q z . 17)
Equa t i o n (5) is e xpa nde d i nt o
<
p d
d d t h - L;bC'b -
The s econd t er m on t he RHS of e q. 12) c ont a i ns t he
l i qui d- phas e mass t r ansfer coeMci ent ( k L ) whi ch can wi t h
be expressed for si ngl e bubbl e s as (Cliff e t a l . , 1978)
= l t ' .... " )
based on t he bo un d a r y- l a ye r modi f i cat i on of Hi gbi e' s
surface r enewal t heor y. We have i nt r oduc e d i nt o eq.
(9) a n o t h e r cor r ect i on fact or to be cal l ed here a ' sur -
face-flow r e t a r d a t i o n ' fact or I JR). whi ch a c c ount s for
t he ext ent of t he i nt er faci al i mmobi l i t y d o mi n a t i n g
excl usi vel y for smal l bubbl es . Accor di ng t o Kawas e
e t a l . (1992), t hi s fact or is cxpressed as t he r at i o of t he
c ont a c t / e xpos ur e t i me for a free surface to t hat for
a rigid one,
. [ R ~ 0 f r e e . / 0 r i g i d . ( 10 )
Ut i l i zi ng t hc r el evant s i ngl e - bubbl e da t a s um-
mar i zed by Mot a r j e mi a n d J a me s on (1978), we here
. . . . . . . . i . . . . . . .
Da t a from Mo t a o e mi and J a me s o n ( 1978)
4121
Hi g b i e ' s . . - - ~ - . - . . - . ~ 2 . - - , ,
5
s ur f a c e - " / " ~ % . . . . .
r e n e wa l /
F , q . ( 9) ; 0 / 5 o
"-" 2 with 7 c
" ~ _ i
f R - I 5<>
-a ~_ . . . . . . . Ca l de r ba nk and
I 0 " 2 . . . . . . . . . ~ - - - [ . . . . . . . . M o o - Yo un g ( I 9 0 1 )
/ E q . (9) wi t h cor r el at ed ],~ (a)
I ~ I I I I I I [ ] . . . . I I I
. . . . . . i
Cur v e fi t t i ng ":,,
. .~ . . . . . ~. - , . . - - =~
O' - wa t e r ~ 2 5 C /
c,
(b)
i i i i i l l l l
2 5 10 "~ 2 5 10 0
d, (cm)
Fig. 2. Dependencies of (a) liquid-phase mass transfer coef-
ficient and (bl surface-flo~, retardation factor on bubble
diameter in water.
pr opose a c or r e l a t i on for.lR. A gr aphi cal r epr esent a-
t i on of t he cor r el at i on/ cur ve- f i t t i ng pr ocedur e is pre-
sent ed in Fig. 2. The pr opos ed cor r el at i on, s hown by
t he s moot he d cur ve in Fig. 2(bL can be expressed as
Iogt oJ~ = 0.5 [ t anh [ 3.9 l ogt 0(d,,:0. 87)] - I I ( I I )
wherc d,. is in mm a nd de > 0.4 mm. Fo r t he t e r mi na l
rise vel oci t y of s i ngl e/ i s ol at ed bubbl e s needed to be
specified in eq. (91, we have adopt ed t he Fa n a nd
Ts uc hi ya (1990) cor r el at i on
K~ , . ~ 3 - o . , 3 , 12: i f not Kh 12)
= 1 4 . 7 ( . q p t . , p t . a t . ) ( K h > =
[ I 2a)
for c o n t a mi n a t e d , a que ous s ol ut i ons . The unspeci fi ed
pa r a me t e r c t akes 1.2 a nd 1.4 for wat er a nd seawat er
(or NaC1 sol ut i on), respect i vel y Wa n a nd Ts uchi ya,
1990).
As de mons t r a t e d in Fig. 2(al, eq. (9) wi t h eq. (11), as
well as wi t h eq. (12), seems to be us abl e as l ong as its
e s t i ma t i on of kL for a gi ven d,. exceeds t hat by t hc
Ca l d e r ba n k a nd Mo o - Yo un g (1961) c or r e l a t i on in t he
"smal l - bubbl e regime"
k t . = 0 . 3 ( v t . : D t . ) - 2 ~ ( V L ~ t ) t 3. 113)
If not . eq. (13) s houl d be used for t he kt. e s t i ma t i on
i nst ead. Not e t hat t hi s regi me c or r e s ponds to s war ms
4122
of r at her uni f or ml y di sper sed smal l bubbl es wi t h weak
bubbl e - bubbl e i nt er act i on, t hus cover i ng t he as ymp-
t ot i c case of si ngl e bubbl es .
Whi l e t he ext ent of t he s ur r o un d i n g l i qui d is i nfi ni t e
for a si ngl e bubbl e i nject ed i nt o t hc ocean, t hat in t he
pr esent exper i ment is finite. I n such a case, t he fol l ow-
i ng mass ba l a nc e needs to be made:
Rat e = 7zd2~kt.(Cs - C , ) = d { V I . C , ),"dt (14)
whi ch gives a n es t i mat e of t he r at e of i ncr ease in t he
ba c kg r o un d c o n c e n t r a t i o n i n t he bul k l i qui d
d C , ,.,'dt = Rat e,' Vt . (15)
Equa t i o n s (2), (6), (8) a nd (15) are to be i nt egr at ed
s i mul t a ne ous l y for o bt a i n i n g t he axi al / ver t i cal di st ri -
but i o n of t he bubbl e size, i.e. t he rat e of di mi ni s hi ng of
a CO, bubbl e , wi t h all t he per t i nent par amet er s bei ng
expressed in ma t he ma t i c a l forms. Specifically, t hey
i ncl ude: t he Peng a n d Ro bi n s o n (1976) e qua t i o n for
e va l ua t i ng Z or CA: a n empi r i cal c or r e l a t i on for t he
s ol ubi l i t y of CO2 in s eawat er ( Cs ) , whi ch de pe nds
s t r ongl y on bot h t e mpe r a t ur e a n d pr essur e but mod-
er at el y on sal i ni t y (Hor ne, 1969; Ha ug a n a nd Dr ange,
1992); a c or r e l a t i on for t he di ffusi vi t y of CO2 in
a l i qui d ( DD, whi ch vari es ma i nl y as a f unct i on of t he
l i qui d vi scosi t y as well as t e mpe r a t ur e (Per r y a nd
Chi l t on, 1973).
K. Tsuchiya et al.
1 4
RESULTS AND DISCUSSION
E f f e c t o f p r e s s u r e o n d i s s o l u t i o n r a t e i n w a t e r
Fi gur e 3 shows t ypi cal t i me var i at i ons i n t he bubbl e
di a me t e r as t he di s s ol ut i on of CO2 pr oceeds in t he
c i r c ul a t i ng wat er pr essur i zed at {a) 0.2, (b) 0.3, (c) 0.4
a n d (d) 0.6 M Pa. de is eval uat ed at pr ope r t i me i nt er -
val s as s oon as each i nj ect ed bubbl e gets st abi l i zed i n
free s us pens i on (after on t he or der of several seconds)
a nd is r epeat ed for 4 - 5 bubbl e s un d e r t he i dent i cal
c ondi t i on; t he pl ot is ma de so t hat at t i me t = 10 s t he
bubbl e di a me t e r is a r o un d 12 mm. As can be seen,
especi al l y i n Fig. 3(b), t he i ni t i al bubbl e size ( mar ked
wi t h filled symbol s) has no appr eci abl e effect on t he
bubbl e - d i mi n i s h i n g rat e over t he i ni t i al r api d a bs or p-
t i on p e r i o d - - t o be cal l ed Per i od I ( < 10 s). Beyond
t hi s per i od, t he d i mi n i s h i n g rat e becomes very sl ow
a nd wi t hi n 30 s, s ubs t a nt i a l par t of t he CO2 di ssol u-
t i on process has r eached ne a r t e r mi na t i on, l eavi ng
de fi ni t e a n d a p p r o a c h i n g a s ympt ot i c val ues (Per i od
II). These a s ympt ot i c val ues c or r e s pond to t he vol ume
of gas whi ch has been des or bed from t he l i qui d phase
t o t he bubbl e , i.e. Nz used t o pr essur i ze t he syst em,
t hus pr es ent i n wat er i n s a t ur a t i on. Thi s c or r e s pond-
ence has been par t i al l y conf i r med by col l ect i ng bub-
bles after t he r un a nd a na l yzi ng t hei r c o mp o s i t i o n by
gas c hr oma t ogr a phy. The a s ympt ot i c bubbl e size de-
pends on t he a mo un t of CO2 a bs or be d d ur i n g Per i od
I, t hus on t he i ni t i al bubbl e size as evi nced in Fig. 3(b).
The sol i d l i nes i n Fig. 3 r epr esent t he pr es ent model
pr edi ct i on obt a i ne d unde r each pr essur e vi a n ume r -
12
10
E 8
E
v
.~ 6
0
1 4
12
10
E 8
E
. ~ 6
0.2 MPa
. . . . . i . i i i . . . . . .
I , f I , I ,
I I I
. . . . . . : 0.3 MPa
, t h I , I , I ,
10 20 30 40 50
t (s)
1 4 ! , , ,
0 . 4 MPa
12 . . . . . . i . . . . . . . .
10
8 ~o
.~ 6 ~
4
(c)
0 , I , 1 f I f I ,
1 4 I ' ' '
.. 0.6 MPa
12 . . . . . . . . . . . . .
10
.~ 6 ~
4
2 ( d ) ~ ~
, I , I i 1 i I ,
0 1 0 2 0 3 0 4 0 5 0
t (s)
Fig. 3. Variations in bubble diameter during CO2 dissolu-
tion process in water at (a) 0.2, (b) 0.3, (c) 0.4 and (d) 0.6 MPa.
ical i nt egr at i on, us i ng a f our t h- or de r Run g e - Kut t a
scheme, of t he four di fferent i al e qua t i ons , eqs (2), (6),
(8) a n d (15). I n t he model cal cul at i on, eq. (9) for t he
mass t r ansfer coeffi ci ent kL has been r epl aced by t he
Ca l d e r ba n k a nd Mo o - Yo un g (1961) c or r e l a t i on i n t he
' l a r ge - bubbl e regime"
kL = 0 . 4 2 ( VI . / DL) - I:2(VL,Q )I 3 (16)
once kt, es t i mat ed from eq. (16) exceeds t hat from eq.
(9), i.e. for d,, > 2.5 mm [ see Fig. 2(a)] . Thi s regi me
si gni fi es t he pr eval ence of s t r ong l i qui d- pha s e agi t a-
t i on due t o i nt er act i ve bubbl es . The r epl acement has
been ma de to a c c ount for t he t ur bul e nc e pr evai l i ng in
t he d o wn wa r d l i qui d flow s uper i mpos ed, i n t he pre-
sent a ppa r a t us , on t he a s c e ndi ng bubbl e in ot her wi se
cal m l i qui d. The wal l effect on t he bubbl e rise vel oci t y,
whi ch is i mp o r t a n t in qui es cent or cal ml y fl owi ng
l i qui ds, is not a c c ount e d for in t he pr esent st udy:
t ur bul e nc e is expect ed t o r educe t he wal l effect whi l e
its ext ent is difficult to est i mat e.
The model pr edi ct i on is excel l ent d ur i n g Per i od
I un d e r l ower pr essur es (~<0.3 MPa ) a n d i n t he very
be g i n n i n g of Per i od I at 0.4 a n d 0.6 MPa . Its devi -
a t i on from t he exper i ment al da t a as d,, decreases be-
l ow 4 or 3 mm st ems from t he negl i gence i n t he model
of possi bl e Nz de s or pt i on, whi ch however, is r at her
a un i que t r ansfer process associ at ed wi t h t he pr esent
pr es s ur i zi ng scheme. The sl i ght de vi a t i on not i ceabl e
in t he last hal f of Per i od I or f o r d , , <6 8 r a m [ see
Fi gs 3(c) a nd (d/] c a n n o t be expl ai ned at t hi s stage;
however , t her e mi ght be s ome ot her pr essur e effects
un a c c o un t e d for in t he pr esent model , whi ch can
e n h a n c e t he mass t r ansfer i n t he r el evant size range.
The pr essur e effect pr edi ct ed by t he pr esent model
is d e mo n s t r a t e d mor e expl i ci t l y in Fig. 4 from
E
"3"
14
12
10
8
6
4
2
50
10
E
0.1
,..,,
0.01
I I I
0.1 0.2 0.3 0.4 0.5 0.6 (MPa)
\
k
\
ta)
, I ~ I ,
10 2 0 30 40 50
t + 50p (s)
(b)
Absorption dynamics of CO2 bubbles 4123
0.1 MP a (at mospher i c) t o 0.6 MP a (the hi ghest pres-
sur e e xa mi ne d i n t he pr es ent exper i ment ). The t i me
va r i a t i on of d, , i.e. t he bubbl e - d i mi n i s h i n g rat e is
al mos t i nde pe nde nt of t he pr essur e p as depi ct ed in
a series of par al l el i ng cur ves pl ot t ed on t he absci ssa
a r r a nge d in Fig. 4(a). The exper i ment al resul t s s how
a si mi l ar t r end except for t he poi nt s al r eady di scussed
(Fig. 31. The ' a bs ol ut e ' rat e (in a sense, speci fyi ng t he
a mo un t in mol es i nst ead of t he per cent age of t he
i ni t i al a mo un t ) of CO2 di s s ol ut i on, on t he ot her ha nd,
is conf i r med qua nt i t a t i ve l y to de pe nd on t he pressure;
t he effect is mor e p r o n o un c e d as t he pr essur e i n-
creases ne a r a t mos phe r i c pressure.
0. 3
0. 2"
0. 1"
J I
15
( MP a )
0.6
0.5
0.4
0 . 0 0 2 , I , I
0 5 10 20
t (s)
Eff~'('t ~ [ N a C I c ( me e t z t r at i on ml d i s s o l u t i o n r a t e
l - i gur e 5 shows t he effect of salt c o n c e n t r a t i o n of
NaCI s ol ut i ons , var i ed from 0 t o 3 wt %, on t he
bubbl e - di mi ni s hi ng rat e at 0.6 M Pa. As in t he case of
wat er, at a fixed salt c o n c e n t r a t i o n t he pr essur e effect
is found to be mi ni ma l : however, t he pr esence of an
el ect rol yt e, NaCI , is s hown e xpe r i me nt a l l y t o have
a si gni fi cant i mpact on t he rate. It t akes s ubs t a nt i a l l y
l onger t i me to r educe t he bubbl e size as t he salt
c o n c e n t r a t i o n is i ncreased. The r e duc t i on of t he di -
mi ni s hi ng rat e a mo un t s to by as l arge as 23 at t he
mode r a t e 1. 5wt % NaCI c onc e nt r a t i on, whi ch is
a bo ut hal f t he equi val ent c o n c e n t r a t i o n of t ypi cal
seawat er; t he effect is fur t her e n h a n c e d as t he c onc e n-
t r a t i on is i ncr eased to 3 wt %.
The c o r r e s p o n d i n g s i mul a t i on resul t s obt a i ne d
based on t he pr esent model ar e al so s hown in Fig. 5.
Despi t e a n a c c ount of changes associ at ed wi t h t he
a ddi t i on of NaCI in t he t h e r mo d yn a mi c , t r a ns por t
a nd physi cal pr oper t i es, t he model - - - - wi t hout fur t her
modi f i cat i ons fails to predi ct t he NaC1 effect to
a satisfactor2, ext ent . A possi bl e r eas on be hi nd t hi s
di s cr epancy st ems from t he modi f i cat i on of surface
mobi l i t y a l ong t he gas l i qui d i nt erface caused by t he
salt addi t i on. The effect is to r et ar d t he mot i on. . osci l -
l at i ons of t he bubbl e surface, whi ch in t ur n mus t have
r educed t he effective kt, val ue.
14
12
10
4
2
0
! I I I I I I
NaC1 cone. (wt%)
~l , ~ . . . . o 0
~,~,, . . . . . * 1 . 5
: ~ 1 ~ / ~ - - - A 3.0
,', A
0.6 MPa ~ .
10 2 0 30 40 50 60 7 0 80
t (s)
Fig. 4. Time variations in (a) bubble diameter and Ib) ab- Fig. 5. Effect of salt concentration on bubble-diminishing
sorption rate predicted by the model at various pressures, rate at 0.6 Ml)a. Thick lines are based on model prediction.
4124 K. Tsuchiya e t al.
A careful anal ysi s of bubbl e surface roughness re-
veals t hat t he ext ent of bubbl e- s hape osci l l at i ons,
which is found t o decl i ne with i ncreasi ng sal t concen-
t r at i on, has a di r ect link t o t he obser ved trend. In this
st udy, t he bubbl e surface roughness is r epr esent ed by
ri ppl es or peaks on t he ot herwi se s moot h surface of
t he bubbl e due t o ext r eme difficulty in quant i fyi ng t he
mor e a ppr opr i a t e sur face- ar ea fl uct uat i ons. The , - ,
peaks appear i ng on t he t wo- di mensi onal pr oj ect i on of
t he bubbl e surface ar e di fferent i at ed based on t hei r . ~
i nst ant aneous, l ocal r adi i of cur vat ur e. Fi gur e 6 shows
t ypi cal sket ches of a series of i nst ant aneous bubbl e
shapes, obt ai ned from t he pr oj ect ed vi deo images, for A-
different NaCI sol ut i ons. By assi gni ng different (t ot al
of 10) classes of peaks which can be mat ched l ocal l y
wi t h one of circles of radi i r angi ng from 0.26 t o
2.60 mm with an i ncrement of 0.26 mm, t he number of : ~
each class of peaks is count ed every i nst ant . At l east
seven frames of vi deo i mages ar e anal yzed for each o
bubbl e. Fi gur e 7 shows t he pr obabi l i t y of occurrence
of peaks for a series of measur ement s in (a) 0, (b) 1.5
and (c) 3.0 wt % NaCI sol ut i ons. As can be seen in t he
figure, for these par t i cul ar da t a sets, bubbl es in wat er
ar e char act er i zed by high occur r ence of l ar ge- cur va-
t ure peaks, i ndi cat i ng t hat ext ensi ve r i ppl i ng prevai l s
al ong t he bubbl e surface. As t he NaCI concent r at i on
increases, t he domi na nt peaki ng shifts t owar d smal l er
cur vat ur e, signifying t he decr easi ng degree of surface
ri ppl i ng. Fo r furt her anal ysi s, t he peaks ar e classified
i nt o t hree gr oups dependi ng on t he cur vat ur e as in-
di cat ed in Fig. 7.
~ 10 mm
~ Z
I -
~U
O o L O 0
[
Fig. 6. Typical sketches of three series of instantaneous
bubble shapes for different aqueous solutions. Bubbles
are dislocated vertically between each instant to avoid
overlapping.
, , , , , , i , , , : , i . . . .
x '. ' Water
20 ~ curv.~. (a)
20 f t ~ % NaCI soln
10
O . . . . ' I ' ' ~ ' ' ~ ( b) 1
f ' ' ' ' ' i . . . . ' ' ' I I
20 _ i _ i 3.0 wt% NaCI soln
: ', %--0 (c)
00 . . . . . I , , , ' . , I i ~ ~
1 2 3
Peak radi us (ram)
Fig. 7. Probability of occurrence of peaks with different
sharpness along 2D projected bubble surface in (a) 0, (b) 1.5
and (c) 3.0 wt% NaCI solutions.
As shown in t he curve of de vs t [ Fi gs 3, 4(a) and 5] ,
t here exists a l i near l y decr easi ng por t i on, t he sl ope of
which is a measur e of t he CO2 a bs or pt i on r at e or t he
k val ue of each bubbl e. Thi s fi ndi ng can l ead t o
a si mpl i fi cat i on of t he model equat i on, eq. (2), in t he
present l abor at or y- s cal e exper i ment al system. That is,
t he mol ar concent r at i on of CO2 gas in t he bubbl e
Cb is i nvar i ant with t i me dur i ng Per i od l and t he
di ssol ved CO2 concent r at i on in t he l i qui d C~ is negli-
gi bl e in compar i s on t o t he s at ur at i on concent r at i on at
t he bubbl e surface C s . Equat i on (2) is t hen r educed to
d~- \ - At J 2k,. . (17)
In t he cal cul at i on t he concent r at i on r at i o C s / C b , be-
ing cons t ant for a given pressure, ranges from 0.93 t o
0.86 over t he pr essur e r ange from 0.1 t o 0.6 MPa.
Equat i on (17) is r eadi l y i nt egr at ed, under t he assump-
t i on of cons t ant k, t o yield a si mpl e anal yt i cal expres-
si on for t he var i at i on of bubbl e di amet er :
d~ = duo - 2 ( C s . . " C h ) k t t (18)
whi ch signifies t he cons t ant sl ope in Per i od I.
Fi gur e 8 shows t he abs ol ut e val ue of t he slope,
equal t o 2 ( C s / C b ) k t , , pl ot t ed agai nst t he pr obabi l i t y
of occur r ence of t he gr oup of peaks wi t h (a) large,
(b) i nt er medi at e and (c) smal l curvat ures. Whi l e
Fi gs 8(a) and (b) show defi ni t e cor r el at i ons bet ween
t he sl ope and t he pr obabi l i t y. Fig. 8(c) shows much
weaker r el at i onshi p. Thi s t r end i ndi cat es t hat t he
mass t ransfer coefficient is onl y affected by t he pres-
ence of s har p peaks on t he r i ppl i ng bubbl e surface.
The mass t ransfer r at e is enhanced by peaks / r i ppl es of
1.2 / ' ' ' I ' ,
~ Peaks w/large curvature
0 . 8[ - ,
I 0 I @ ~ I ~ , I , I
~ . I . 2 ' , , , ,
~" Peaks w / i n t e r m e d i a t e curvature
E 0 . 8 "
" ~ 0 . 4
( b)
I 0 , 1 , I
Absorption dynamics of CO, bubbles
(a)
" 1
o O
o o 0 o
, I 0 I
~ , 1 . 2 ~ , , , , I
Peaks w/small curvature
0 . 8 ~- 0 0 N aCI cone. ~wt'~
A 1 5
0 ~ 2 1 0 , I , 1 , I ,
40 60 80 100
Probabi l i ty ( %)
Fig. 8. Absolute value of initial slope of d.. vs t curve as
a function of probability of occurrence of peaks with
(a) large, (b) intermediate and [c) small curvatures.
l arge cur vat ur e: t he e n h a n c e me n t is si gni fi cant when
t he pr oba bi l i t y of occur r ence of s har p peaks exceeds
50% [ Fi g. 8(a)] . The pr esence of t he el ect r ol yt e t ends
t o r educe t hi s pr obabi l i t y, t hus decr eas i ng kL. How-
ever, it is not a necessar y c o n d i t i o n t o resul t in l ower
kL val ues. Ta p wat er, d e p e n d i n g on its c o n t a mi n a t i o n
level, c a n gi ve a wi de r ange of pr oba bi l i t y a n d t here-
fore kL val ue. Whi l e t hi s anal ys i s pr ovi des a mechani s -
tic basi s for i mp r o v i n g t he pr opos ed model , mor e
ext ensi ve i nves t i gat i ons r egar di ng t he bubbl e surface
c ha r a c t e r i za t i on i n c o n n e c t i o n wi t h t he l i qui d- phas e
t ur bul e nc e level as well as c o n t a mi n a t i o n level are
r equi r ed for pr oper pr edi ct i on of t he mass t r ansfer
coefficient.
Si mul at i on qf . si ngl e- hubhl e absorpt i on in s eawat er
Due t o s ome un c e r t a i n t y not ed above r egar di ng t he
s al t s - cont ent effects, t he a bs o r p t i o n dyna mi c s of
si ngl e CO, bubbl e s r i si ng i n seawat er is s i mul at ed less
ext ensi vel y in t hi s st udy. The pr esent s i mul a t i on re-
sui t s i ndi cat e t hat for bubbl e s i nt r oduc e d 200 m be-
neat h t he sea surface, it is r equi r ed for t he bubbl e to
s pend at least 20 a nd 42 s (or 4.7 a n d 11.4 m of ascend-
ing) for gi ven i ni t i al di amet er s of 10 a nd 20 ram.
respect i vel y, before t he bubbl e di a me t e r reaches ~ of
t he i ni t i al val ue. Si mi l ar resul t s were r epor t ed by
Ha ug a n a nd l ) r a n g e (1992).
CONCLUDING REMARKS
The a p p a r a t us desi gned t o 'freeze" a si ngl e (ot her-
wise ri si ng) bubbl e at a fixed vert i cal l ocat i on by Greek
a ppl yi ng a d o wn wa r d flow of l i qui d is successful l y 0
ut i l i zed t o c o n t i n uo us l y mo n i t o r t he bubbl e dyna mi c s lb.
and, mor e specifically, to o bt a i n qua nt i t a t i ve da t a on v~.
4125
t he d i mi n i s h i n g rat e of c a r bo n di oxi de bubbl e s in
pr essur i zed wat er i n bot h t he abs ence a nd pr esence of
s odi um chl ori de. It is f ound t hat whi l e t he effect of
pr essur e on t he rat e is smal l wi t h sl i ght e n h a n c e me n t
of t he a bs o r p t i o n at hi gher pr essur es ( >/ 0. 4 MPa),
t hat of salt c o n t e n t is si gni fi cant , i ncr eas i ng t he t i me
r equi r ed t o r educe t he bubbl e size to a pr escr i bed level
by several fold for 3 wt % NaCI s ol ut i on.
The a bs o r p t i o n process of CO, from a bubbl e to
t he s ur r o un d i n g l i qui d at el evat ed pressures, whi ch
mi mi cs t he basi c feat ures of t hat for bubbl e s ascend-
i ng i n shal l ow ocean, is model ed by i n c o r p o r a t i n g t he
var i at i ons in all t he phys i cochemi cal pr oper t i es of t he
gas a nd l i qui d phases associ at ed wi t h pressure, t em-
per at ur e a nd sal t s c o n c e n t r a t i o n changes. The model
is capabl e of pr edi ct i ng t he exper i ment al val ues of t he
bubbl e - di mi ni s hi ng rat e as well as its t r end bei ng
al mos t i nde pe nde nt of t he pressure, a l t hough t he pre-
di ct ed t r end shows sl i ght l y l ower sensi t i vi t y t ha n t he
exper i ment al one. The model can be i mpr ove d by
fur t her i n c o r p o r a t i n g t he effect of l i qui d- phas e con-
t a mi n a t i o n a nd t ur bul e nc e levels whi ch c ont r ol t he
ext ent of bubbl e- s ur f ace osci l l at i ons.
Ac knowl ed gement
The work was supported, in part, by the Nev, Sunshine
Program of the Agenc> of Industrial Science and Techno-
logy, MITI.
N OTA TI ON
c i nt erraci al pa r a me t e r defi ned i n eq. (12)
CA mol a r c o n c e n t r a t i o n of CO, gas in a bubbl e,
tool m - 3
(-'s s a t ur a t i on c o n c e n t r a t i o n of di ssol ved CO, at
bubbl e surface, tool m - 3
C , di ssol ved CO. , c o n c e n t r a t i o n in bul k l i qui d,
tool m 3
d,, equi val ent bubbl e di amet er : di a me t e r of a
spher e ha vi ng t he s ame vol ume as t he bubbl e ,
m
Dr, mol ecul ar di ffusi vi t y in l i qui d, m 2 s
./R surface-ri ow r e t a r da t i on fact or defi ned by eq.
(10)
~! gr a vi t a t i ona l accel er at i on, m s -"
kL l i qui d- phas e mass t r ansfer coefficient, m s
K~ vi scous pa r a me t e r defi ned in eq. {12)
p pr essur e in l i qui d. Pa
Ph pr essur e i nsi de a bubbl e, Pa
R gas c ons t a nt , J tool 1 K
Re bubbl e Reynol ds n umbe r ( = d, . Uhv~l
t time. s
T t emper at ur e, K
Uh t e r mi na l bubbl e rise vel oci t y, m s -
V~. vol ume of s ur r o un d i n g : c i r c ul a t i n g l i qui d, m ~
z di s t ance beneat h sea surface, m
Z compr es s i bi l i t y fact or
letter.~
cont act . : exposur e time, s
l i qui d vi scosi t y, Pa s
l i qui d ki ne ma t i c vi scosi t y, m- ' s
4126
Pt. l i qui d densi t y, kg m- 3
at. l i qui d surface t ensi on, N m-
REFERENCES
Cal der bank, P. H. and Moo- Young, M. B. (1961) The
cont i nuous phase heat and mass t ransfer pr oper t i es
of di spersi ons. Chem. Enqn,q Sei. 16, 39- 54.
Clift, R.. Gr ace, J. R. and Weber, M. E. (1978) Bubble.s,
Drops, and Particles. Academi c Press, New York,
U.S.A.
Fan, L.-S. and Tsuchi ya, K. (1990) Bubble Wake Dy-
namics in Liquids and Liquid-Solid Suspensions.
But t er wor t h- Hei nemann, St oneham, MA, U.S.A.
Haugan, P. M. and Dr ange, H. (1992) Sequest r at i on
of CO2 in t he deep ocean by shal l ow injection.
Nature 357, 318-320.
Hor ne, R. A. (1969) Marine Chemistry. Wiley, New
York, U.S.A.
K. Tsuchiya et al.
Kawase, Y., Hal ar d, B. and Moo- Young, M. (1992)
Li qui d- phase mass t ransfer coefficients in bi or eac-
tors. Bioteehnol. Bioenqng 39, 1133-1140.
Mar chet t i , C. (19771 On geoengi neeri ng and t he CO2
pr obl ems. Climatic Change 1, 59- 68.
Mot ar j emi , M. and Jameson, G. J. (1978) Mass
t ransfer from very smal l bubbl e s - - t h e opt i mum
bubbl e size for aer at i on. ('hem. En,qng Sci. 33,
1415 1423.
Peng, D.-Y. and Robi nson, D. B. (1976) A new t wo-
cons t ant equat i on of state. Ind. Enqn,q Chem.
Fundam. 15, 59 64.
Perry, R. H. and Chi l t on, C. H. (1973) Chemical Engin-
eers" Handbook, 5th Edn McGr aw- Hi l l , New York,
U.S.A.
Sai t o, T. and Kaj i shi ma, T. (1996) Met hod and a ppa r -
at us for di ssol vi ng and i sol at i ng car bon di oxi de gas
under t he sea. U.S. Pat ent 08/534802.