enhances the probability of the bubble coalescence and are obtained.

makes bubble larger. On the other hand, in the present Acknowledgment

study the dimention of the apparatus is far larger than
that of the distributor and the depth of the liquids is The authors are grateful Prof T. Sakurai, Tokyo Inst. Tech.,
shallow. Therefore, the probability of the bubble coales- for valuable advices.
cence over the distributor is less than that of the Houghton
et al.'s case, because the circulation of the liquid in the Nomenclature
apparatus makes bubbles easy to apart each other. This [cm]
fact is recognized when the porous plate distributor is used d = volume equivalent bubble diameter [cm]
d = average bubble diameter [cm/sec2]
for liquid of group A and C in the bubble column with g = gravitational acceleration [g/cm- sec2]
continuous liquid flow. z/Po = excess pressure required to generate bubble [cm/sec]
ug = gas flow rate per unit area of porous plate [-]
Fr = ug2/e2gd, Froude numer
Summary We = ug2dp/e2o, Weber number [-]
p -density of liquid [g/cm3]
8 = average pore diameter denned by Eq.(l) [cm]
Bubbles which have been just generated from the porous e =porosity of porous plate [-]
plate are small and have an equal size, but sometime [dyne/cm]
a - surface tension of liquid
coalescence of these small bubbles occurs at a location
slightly removed from the distributor, where the gas hold- Literature cited
up is very large. Therefore, large and wide size distri- 1) Foulk, C.G.: Kolloid. Z., 60,115 (1932)
bution of bubbles are observed. This occurs easily in
2) Gleim, V. G. and Shelomov, I. K.: J. Appl. Chem. USSR,
pure water and pure solvents. The surface active sub- 32, 799 (1959)
3) Gleim, V.G., Shelomov, I.K. and Shidlovski, B.R.: J. Appl.
stances in water and solvents obstruct this coalescence of Chem. USSR, 32, 1069 (1959)
bubbles. In concentrated inorganic salt solutions, this
4) Houghton, G., Mcleam, A.M. and Ritchie, P. D.: Chem.
obstruction is also recognized. For the extreme cases Eng. Sd.f 7, 40 (1957)
when no coalescence is observed and the coalescence occurs 5) Koide, K. Hirahara, T. and Kubota, H.: Kagaku Kogaku,
at the maximumrate, the correlations of the average 30, 712 (1966)

bubble diameter and the conditions of bubble generation 6) Vershoor, H. : Trans. Inst. Chem. Eng.(London), 28,52(1950)

MASS TRANSFER COEFFICIENTS BETWEEN GAS AND LIQUID

PHASES IN PACKED COLUMNS*
KAKUSABURO ONDA, HIROSHI TAKEUCHI** AND YOSHIO OKUMOTO
Dept. of Chem. Eng., University of Nagoya, Nagoya

x CFr)"0-05 (We)0'2 } (1)

It has been shown that Eq. (l) can be applicable
Introduction
within ±20%error to the column packed with Raschig
Mass transfer coefficients for gas absorption, desorption rings, Berl saddles, Spheres and rods made of ceramic,
and vaporization in packed columns have been studied by glass, and polyvinylchloride, and also coated with paraffine
many mvestigators3'5>11>22>26l30>31). Assuming that the wetted film.
surface on packing pieces is identical with the gas-liquid This paper presents the correlations on the masstrans-
interface, Onda et al. presented the empirical equations fer coefficients for gas absorption and desorption based on
of the gas and liquid-side mass transfer coefficients, kG Eq. (l) of aw and confirms the applicability of those to
and kL, for the gas absorption and desorption12~18). the vaporization of water and the gas absorption into
organic solvents. Furthermore, its applicability to the
Recently, a newequation for the wetted surface area, distillation in packed columns is also discussed.
aw, taking into account the liquid surface tension and the
surface energy of packing materials was derived as
follows150 : I. Liquid-side Mass Transfer Coefficient : kL
ajat = l-exp{-1.45U/(7)0-75 (L/WO0"1
x (LW^V)-0-05 (UIPLoaty-2 1 à" 1 Gas absorption and desorption with water
= l-exp{-1.45(W<7)0-75 Cfo)0'1 The &l a data for gas absorption into water and desorp-
ton from water reported in the Iiterature3'6ll2'16>18'2()>24l27'28)
* Received on July 10, 1967 are divided by aw of Eq. (1). The kL thus obtained are
** Dept. of Ind. Chem., Suzuka College of Technology, Suzuka correlated as well as that in our previous paper12>18) by
56 JOURNAL OF CHEMICAL ENGINEERl|NG OF JAPAN
 Fig. I Correlation of liquid-phase data for gas absorption and desorption by using water

Table I Experimental results of gas absorption into

tration of surfactant.
organic solvents The kL calculated from these data are compared with
Packings Size Absorbent Temp. a n those obtained by water in Fig,1 in which the datain for
a=47 dynes/cm, in this work and 42 dynes/cm, the
Raschig ring 10mm CC14 25°C 0.120 0.70
Berl
Sphere
saddle l/2-in
l/2-in
»
"
»
"
0.0862
0.0227
0.73
0.86
literature7) deviate pretty from Eq. (2).
1.2 Gas absorption by organic solvent
" " CH3OH 20°C 0.0735 0.76
Many investigation on the gas absorption in packed
" 1-in » " 0.0389 0.83
Rod 14mm CC14 25°C 0.093 0.70 column have been carried out by using water as an ab-
sorbent. However, there are so far only a few data5>13>28)
on the gas absorption by organic solvent.
replacing at in Reynolds number by aw. Fig. 1 shows In the present work, the gas absorption of pure CO2
the relation of kL {pL/^LgYn I <jiLl'pLDLyin {atDvYA
into methanol and carbon tetrachloride were carried out.
vs. modified Reynolds number, (L/<z«,/O, and a straight The columns used were 6-and 12cm I. D. and packed
line represents
kL (pL/fiLg) m = O.OO5l(L/aw^Lyn (jxj'pLDLYV2 with 10~25mmRaschig rings, Berl saddles, spheres and
x (atDp)0A ,. (2) rods for 20~30cm height.
The mass transfer results are given in Table 1 as a
The exponent of Rbl in Eq. (2) coincides with that derived relation of kLa-aLn. Applying Eq. (l) to kLa data ob-
on the wetted area basis
Fujita-Hayakawa3),
by Krevelen-Hoftijzer26)
and also is nearly
and
equal to 0.61 of tainded in this work and reported in the literature5>13>28)
for organic solvents, the same plottings are shown in
that derived by Norman11}in a model apparatus. Fig. 2 in which the agreement of the observed values
Furthermore, the gas absorption of CO2into water added and Eq. (2) is also satisfactory.
a surfactant in packed columnwas carried out to confirm Thus, the liquid-side mass transfer coefficients, kz, for
the applicability of Eq. (2) for various inter facial. area. gas absorption and desorption in packed columns, have
Such absorption data have been reported by Hikita7). been correlated by Eq. (2) within an error of ±20% for
In this work, a non-foaming surfactant, NewpolPE-61f, organic solvents as well as water.
were used and the surface tensions of solutions were
47 dynes/cm. The kLa data obtained give smaller values
than are obtained with water as well as in the litera- 2. Gas-side Mass Transfer Coefficient : kG
ture7>36). This effect of addition of surfactant may result 2.1 Absorption
from the two phenomena à"the reduction of liquid mixing The Izgci data for gas absorption reported in the lite-
at the junction of packing pieces as pointed out by Hikita7) rature1>8ll5>16'17'30'32) are divided by aw calculated from Eq.
and the inter facial resistance with increase in concen- (l). The ko thus obtained are shown in Fig. 3 as a
T Sanyo-Kasei Co., Ltd. plot of {kGRT/atDG)/{^G/pGDGyn UA,) "2 0 vs. modified

VOL.1 NO.1 1968 57

 Fig. 2 Correlation of ab-
sorption "data by using organic
solvent with Eq. (2)

Fig. 3 Correlation of
phase data for absorption
gas-

(3) into 2.00. This difference comes from the fact that
Reynolds number. The equation for the best line passing
through the points in the higher group in Fig.3 is as
follows à"
kaa data for packing smaller than 15mmtend to decrease
koRT/atDo = 5.23(G/WG)0-7 (^g/PgDg)U3 feD,)"2'°
monotonously with the increase of at as reported in the
(3) literatures1 16). However,this cause is not clear at present.
The jD-factor for mass transfer can be obtained by
In Fig. 3, data for Raschig rings and Berl saddles smaller rearranging Eq. (3). For example, since atDp is 6(1-e) =
than 15mmare situated on the lower group and are best 3.4 for spheres, Eq. (3) becomes
correlated by merely changing the constant, 5.23, in Eq. > = 0.771[GDP7Ml-s)r°:30 (4)

58 JOURNAL OF CHEMICAL ENGINEERING OFJAPAN

 Fig. 4 Comparison of /cgO data for vaporization by various Fig. 5 Schematic diagram of experimental apparatus
investigators at L=78OOkg/m2 hr for vaporization in water-air system

Fig. 6-a 15mm Raschig rings Fig. 6-b 25mm Raschig rings

Fig. 6 Vaporization data in this work

(Operational temperature of water was
about 25°C and the differ ence of the
temperature between top and bottom
of the column was within 0.1°C.)

Fig. 6-c I in Berl saddles Fig. 6-d I in Spheres

Shulman et al.22) reported the following equation for data10'21>23'30) for vaporization because of the difficulties in
sublimation of dry naphthalene packings the experimental techniques, as shown in Fig.4, in which
jD = 1.195[GDPV^(l-s)]"0-36 (5) kGa for air-water system are plotted against the gas
The agreement between Eqs. (4) and (5) is fairly good massvelocity, G, for 1-in. Raschig rings.
within the region of 100<GD3,7j"fl(l-e) <10, 000. To ascertain their results, the rates of vaporization were
2 à"2 Vaporization measured for air-water system under the condition of
There are considerable differences among the published adiabatic process-i. e, constant temperature of water.

VOL. 1 NO. 1 1968 5?

 Fig. 7
Correlation of vaporization data with
Eq. (3) .

The schematic diagram of the apparatus is shown in through the column. From this point of view, Sawistowski19)
Fig. 5. The column consisted of 15cm I.D. acryle-resin reported the relation of Hog vs. x.
pipe with water jacket and was packed with ceramic Raschig In the present work, using the point values of ka and
rings, Berl saddles and spheres. Packed heights of 10-, hh calculated :from Eqs. (3) and (2) for gas absorption and
15- and 20-cm were used to make the end effect clear. gas-liquid inter facial area from Eq. (l), the height of pack-
The water contents in gas phase were analyzed by the ings was calculated by the following equation.
psychrometric method and the adsorption on calcium Z=Gm\ [-1 h-i )-* C6)
chloride. ; Jy.Kkaa kLa-Cav1y' ~ y
The typical experimental results are shown as kGa vs. in which the gas molar flow rate, Gm, is assumed to be
G in Figs.6-a, 6-b, 6-c, 6-d. To compare the kGa for constant. Thus, the heights of packings calculated from
vaporization with that for absorption, kGa data have been Eq. (6) has been compared with the actual height used to
divided by aw of Eq. (l) and (kGRT/atDG)/(ptG/PGDG)uz
(atDp)~2'Q axe plotted against the modified Reynolds
obtain the published data because the estimation of Kg<z
or Hog used in the previous literature is insignificant,
number, (G/at[tG), in Fig. 7. especially for non-ideal mixtures.
As shown in Fig.7, Eq.(3) correlates almost all of the The published data used for this calculation include
data for vaporization as well as gas absorption, but for the system of benzene-toluene29), methanol-water9'255 and
1/2-in. sphere the constant of Eq.(3) might be changed ethanol-water4) at total and finite reflux ratios. Com-
into 2.00 as described in the section of absorption. parisons of the calculated value, Zcai, with the actual,
Zact, are shown in Fig". 8 against Gm. Their agreements
are within ±30% except columns higher than 1.0m in
3. Applicability for Distillation
which the maldistribution of liquid might have occured.
Distillations in the packed column have been studied The relative magnitude of individual phase resistances
by many investigators. Most of them, however, have depends on the group m G/L, but the variable range in
reported the H. E. T. P. which is theoretically unfavorable, L/G is more restricted in distillation than in gas ab-
or H. T. U., assuming that the slope of the equilibrium sorption. Furthermore mand physical properties of liquid
line and the physical properties of mixture is constant mixtures mayvary widely from top to bottom throughout
through out the packed column. Yoshida-Koyanagi30) have the column, and hence the relative magnitude of individu-
discussed the applicability of HG and HL derived for gas al phase contributions depends on the liquid composition.
absorption to the distillation in a packed column. Fig". 9 shows the dependencies of the ratio of gas phase
Actually, the distillation process is equimolar counter resistance to total one upon the liquid composition for
diffusion, while the gas absorption or vaporization is ethanol-water and benzene-toluene systems.
unidirectional, but this difference in this case may have
little effect on the individual mass transfer coefficients.
In gas absorption, it is reasonable to obtain the average Conclusion
film coefficient in a packed column, but in the distillation Assuming that the wetted surface area evaluated by
column it is meaningless, because the temperature and Eq. (l) is identical with the gas-liquid inter facial area, the
concentration of mixture differ greatly at each point mass transfer^coefficients in packed columns on the gas

60 JOURNAL OF CHEMICAL ENGINEERING OFJAPAN

 Fig. 8 Comparison of calcu-
lated and actual packed heights
for distillation columns

absorption and desorption were correlated within a reason-

able error with Eq. (2) for kL and Eq. (3) for ka except
Raschig rings smaller than l|mm and Berl saddles smaller;
than 1/2".
It was found that the difference between the mass
transfer data for absorption and that for vaporization is
quite small and practically could be neglected. Thus,
Eq. (3) for gas absorption is also applicable to the vapori-
zation process within ±30%error. For the liquid-side mass
transfer coefficient, Eq. (2) is applicable within ±20%
error to the columns packed with Raschig rings, Berl
saddles, spheres and rods, and irrigated with organic
solvents as well as water systems of higher surface tension
than about 50 dynes/cm.
For the distillation in packed columns, it was ascertained
that the resistance in both phases should be taken into
account, and the height of packing could be evaluated by
Eq.(6) with Eq.(3) for kG, Eq.(2) for kL and Eq. (l) for
a within reasonable error.
JU

Fig. 9 Ratio of gas phase resistance to total one against

Nomenclature liquid concentration, x, for distillation

a = inter facial area in packing [m2/m3]

at = total surface area of packing [m2/m3] m= slope of equilibrium line [-]
aw = wetted surface area of packing [m2/m3] R = gas constant [m3-atm/kg-mole- °K]
Cav = average molar density [kg-moles/m3] Re = Reynolds number defined by {GlatPo) or (L/atPz) or
D = diffusivity [m2/hr] (L/ovPl) [-]
Dp = nominal size of packing , [m] Sc = Schmidt number defined by (p/pD) [-3
Dp = diameter of sphere possessing the same surface area Sh = Sherwood number defined by (kaRT/atDo) [-1
as a piece of packing [m] T = absolute temperature [°K]
Fr å = Froude number denned by (atL2/gpL2) [-] We - Weber number defined by (L2/'pLoat) [-3
G = superficial mass velocity of gas [kg/m2-hr] ^c = mole fraction of more volatile component in liquid [-]
Gm= superficial molar velocity of gas [kg-moles/m2-hr] y = mole fraction of solute or vapor in gas phase [-]
g = gravitational constant [m/hr2] 3^* = mole fraction of vapor in equilibrium with liquid
H =å height of a transfer unit [m] composition, x [-3
jD å = mass transfer factor defined by Eq.(4) [-] Z - height of packings [m3
Kg - overall coefficient [kg-moles/m2 -hr-atm] Greek letters
kG = gas-phase mass transfer coefficient [kg-moles/m2-hr-atm] s = void fraction [m3/ni33
kL = liquid-phase mass transfer coefficient ' [m/hr] P- - viscosity [kg/m-hr3
L = superficial mass velocity of liquid [kg/m2<hr] p =.density [kg/m3]

VOL.1 NO.1 1968. . 61

 Oc - critical surface tension of packing material [dynes/cm] 16)(1963)Onda, K., E. Sada, C. Kido and A. Tanaka: ibid., 27, 140
a = surface tension [dynes/cm] or [kg/hr2]
Subscrip ts 17)(1966)
Onda, K., E. Sada, C. Kido and S. Kawatake: ibid., 30, 226
1, 2 = bottom and top of column, respectively 18) Onda, K., H. Takeuchi and Y. Koyama: ibid., 31, 126(1967)
G, L = gas and liquid phase, respectively
19)(1959)
Sawistowski, H. and W. Smith: Ind. Eng. Chem., 51, 915
Literature cited 20) Sherwood, T. K. and F.A.L. Holloway: Trans. Am. Inst.
Chem. Engrs., 36, 21 (1940)
1) Fellinger, L.: Sc. D. thesis, M.L.T., Cambridge (1941) 21) Sherwood, T.K. andC.F.F.A.L. Holloway: ibid., 36, 39 (1940)
2) Fujita, S. and S. Sakuma: Chem. Eng.(Japan), 18, 64 (1954) 22) Shulman, H.L., Ullrich, A.Z. Proulx and J.O. Zim-
3) Fujita, S. and T. Hayakawa: ibid., 20, 113 (1956) merman: A. I. A.E.
Ch. E. Journal, 1, 253Ind.(1955)
4) Furnas, C. C. and M. L. Taylor: Trans. Am. Inst. Chem. 23) Surosky, and B.F. Dodge: Eng. Chem., 42,1112
Engrs., 36, 135 (1940) (1950)
24) Ueyama, K., H. Hikita, S. Nishigami and S. Funahashi:
5) 24,Hikita,
2 (1960)
H., T. Kataoka and K. Nakanishi: Kagaku Kogaku,
Kagaku Kogaku, 18, 68 (1954)
25) Uchida, S., et al.: ibid., ll, 53 (1947)
6)
7)
Hikita,
Hikita,
H.,
H.:
M.ibid.,Sugata24, and K. Kamo: ibid.,
9 (1960)
18, 454 (1954)
26)44, Van529Krevelen,
(1948)
D. W. and P. J. Hoftijzer : Chem. Eng. Progrs.,
8) (1950)
Houston, R.W. and C.A. Walker: Ind. Eng. Chem., 42, 1105 27) Vivian, J.E. and C.J. King: A. I. Ch. E.Journal, 10, 221
(1964)
9) 22,Katayama,
764 (1958)
S., T. Koyanagi and F. Yoshida: Kagaku Kogaku, 28) Yoshida, F. and T. Koyanagi: Ind. Eng. Chem., 50, 365
10) Lynch, E.J. and C.R. Wilke: ibid., 1, 9(1955 (1958)
ll) Engrs.,
Norman,41, W.109 S. (1963)and F. Y. Y. Sammak: Trans. Inst. Chem. 29) Yoshida, F. and T. Koyanagi: ibid., 46, 1756 (1954)
30) (1962)
Yoshida, F. and T. Koyanagi: A. I. Ch. E. Journal, 8, 309
12)235 Onda,
(1959)
K., E. Sada and Y. Murase: A. I. Ch. E. Journal, 5, 31) Weisman, J. and C.F. Bonilla: Ind. Eng. Chem., 42, 1099
(1950)
13) Onda, K. and E. Sada: Kagaku Kogaku, 23,220 (1959)
14) Onda, K., T. Okamoto and H. Honda: ibid., 24, 490(1960) 32) Wen, C.Y., H.D. Simons and M. Leva: West Virg. Univ.
15) Onda, K., E. Sada and M. Saito: ibid., 25, 820 (1961) Bull. Eng. Expt. Sta., 26 (1953)

GAS ABSORPTION WITH CHEMICAL REACTION IN PACKED

COLUMNS"

KAKUSABURO ONDA, EIZO SADA AND HIROSHI TAKEUCHI**

Dept. of Chem. Eng., University of Nagoya, Nagoya

Introduction CO2into aqueous solutions of NaOHin a packed column

is confirmed by using these correlations. Furthermore,
Theoretical analyses for gas absorption with chemical
reaction have been made by many investigators3>4>6'18): the assumption of a-aw is ascertained by comparing with
However, it is difficult to apply these theories to the the data for the gas absorption with pseudo fist-order re-
action.
processes in a packed column, because the individual
mass transfer coefficients and the inter facial area can not I. Experimental Work
be estimated strictly at present.
The assumption that the wetted surface in packings is 1 à"1 Apparatus and procedure
identical with the gas-liquid interface is not only con- The packed column consisted of a 12.0-cm I.D. jacketed
venient for estimation of the area but also reasonable for acryl-resin tube packed to the heights of 0.2m or 0.3m
mass transfer between gas and liquid phases. In our with 15mm ceramic Raschig ring and 1/2- and 1-in.
previous papers11>12\ the correlations for aw, ko and kL ceramic spheres. The liquid distributor was made of
were derived as follows :
acryl-resin and had sixty one 3.5mm I. D. glass nipples
ajat = 1 - exp{- 1.45UWU5aW arranged in a ll.6mm triangular pitch.
(Vat/pL2g) ~Q^ (L2/pLaaty-2} The aqueous solutions of 0.05, 0.1, 0.25, 0.5 and 1.0iV-
koR T/atDo NaOHwere irrigated over the packings after atheating in
= 5.23 (GWff) °"7 (fiG/PODG)m (atDp) "2-° the thermostat tank which was controlled 30±l°C.
kL {pL/[JtLgy n Air from a blower and carbon dioxide from a cylinder
= 0. 005l (L/aw^Ly/' (fiL/PLDL) -1/2 (atDpy-i (3)
were fed to the bottom of the packed column after the
In this paper, the applicability of the film theory18) of gas gas mixture waswell mixed and saturated with water
absorption with second order reaction to the absorption of vapor. The CO2content in the air was controlled by a
* Received on July 10, 1967
reducing valve at the CO2cylinder. The partial pressure
*å * Dept. of Ind. Chem., Suzuka College of Technology, Suzuka of the solute gas, p, was maintained constant in each run
62 JOURNAL OF CHEMICAL ENGINEERING OF JAPAN