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Oc - critical surface tension of packing material [dynes/cm]

a = surface tension
[dynes/cm] or [kg/hr2]

Subscrip ts

1, 2 = bottom and top of column, respectively


G, L = gas and liquid phase, respectively

Literature
1)
2)
4)

S. and T. Hayakawa:

Furnas,
C. C. and
Engrs.,
36, 135 (1940)

ibid.,

M. L. Taylor:

Trans.

H.,
M.ibid.,Sugata24, and
K. Kamo: ibid.,
H.:
9 (1960)

Am. Inst.

Chem.

Kagaku Kogaku,

ibid.,

30, 226

9) 22,Katayama,
S., T. Koyanagi and F. Yoshida: Kagaku Kogaku,
764 (1958)
E.J.

and C.R. Wilke:

ibid.,

1, 9(1955

ll) Engrs.,
Norman,41, W.109 S. (1963)and F. Y. Y. Sammak: Trans. Inst.

Chem.

12)235 Onda,
K., E. Sada and Y. Murase: A. I. Ch. E. Journal,
(1959)

Sherwood,

T. K. and

5,

13) Onda, K. and E. Sada: Kagaku Kogaku, 23,220 (1959)


14) Onda, K., T. Okamoto and H. Honda: ibid., 24, 490(1960)
15) Onda, K., E. Sada and M. Saito: ibid., 25, 820 (1961)

F.A.L.

Holloway:

36, 21 (1940)
T.K.
andC.F.F.A.L.
Holloway:
H.L.,
Ullrich,
A.Z.

merman:
A. I. A.E.
Ch. E.
Journal,
Surosky,
and B.F.

23)

(1950)
24)
Ueyama,

K.,

Uchida,

S.,

al.:

S. Nishigami

ibid.,

ll,

D. W. and P. J. Hoftijzer

27)

and

Vivian,
(1964)
28)
Yoshida,
(1958)

J.E.

29) Yoshida,
30) (1962)
Yoshida,

F. and T. Koyanagi:
F. and T. Koyanagi:

31)

F. and

Weisman,
(1950)

J. and

King:

Bonilla:

Chem.,

and

42,1112

S. Funahashi:

: Chem. Eng. Progrs.,

A. I. Ch. E.Journal,

T. Koyanagi:

C.F.

36, 39
(1940)
J.O.
Zim-

and

53 (1947)

26)44, Van529Krevelen,
(1948)

C.J.

ibid.,

Proulx

1, 253Ind.(1955)
Eng.

H. Hikita,

et

Trans. Am. Inst.

Dodge:

Kagaku Kogaku, 18, 68 (1954)

25)

18, 454 (1954)

R.W. and C.A. Walker: Ind. Eng. Chem., 42, 1105

10) Lynch,

17)(1966)
Onda, K., E. Sada, C. Kido and S. Kawatake:

Chem. Engrs.,
21)
Sherwood,
22)
Shulman,

(1941)
18, 64 (1954)

20, 113 (1956)

5) 24,Hikita,
H., T. Kataoka and K. Nakanishi:
2 (1960)
8) (1950)
Houston,

27, 140

20)

Fellinger,
L.:
Sc. D. thesis,
M.L.T., Cambridge
Fujita,
S. and S. Sakuma:
Chem. Eng.(Japan),

6)
Hikita,
7)
Hikita,

ibid.,

18) Onda, K., H. Takeuchi and Y. Koyama: ibid., 31, 126(1967)


19)(1959)
Sawistowski,
H. and W. Smith: Ind. Eng. Chem., 51, 915

cited

3) Fujita,

16)(1963)Onda, K., E. Sada, C. Kido and A. Tanaka:

Ind.

Eng.

10,

221

Chem., 50,

365

ibid., 46, 1756 (1954)


A. I. Ch. E. Journal,
8, 309
Ind.

Eng.

Chem., 42,

1099

32) Wen, C.Y., H.D. Simons and M. Leva: West Virg. Univ.
Bull. Eng. Expt. Sta., 26 (1953)

GAS ABSORPTION WITH CHEMICAL REACTION IN PACKED


COLUMNS"
KAKUSABURO ONDA, EIZO SADA AND HIROSHI

Dept. of Chem. Eng., University

Introduction

CO2into aqueous solutions

Theoretical
analyses for gas absorption
with chemical
reaction have been made by many investigators3>4>6'18):

However, it is difficult to apply these theories to the


processes in a packed column, because the individual

mass transfer coefficients and the inter facial area can not
be estimated

strictly

at present.

The assumption that the wetted surface in packings is

identical

with

the

gas-liquid

interface

is not only con-

venient for estimation of the area but also reasonable for

mass transfer between gas and liquid phases.


In our
previous papers11>12\
the correlations
for aw, ko and kL
were derived as follows :
ajat
= 1 - exp{- 1.45UWU5aW

(Vat/pL2g)
koR T/atDo
= 5.23

(GWff)

~Q^ (L2/pLaaty-2}
"7 (fiG/PODG)m

kL {pL/[JtLgy n

(atDp)

"2-

(fiL/PLDL)

-1/2

(atDpy-i

(3)

10,

1967

* * Dept. of Ind. Chem., Suzuka College of Technology, Suzuka


62

these

of NaOHin a packed column


correlations.

Furthermore,

the assumption of a-aw is ascertained by comparing with


the data for the gas absorption with pseudo fist-order reaction.
I.

Experimental

1 "1 Apparatus

Work
and procedure

The packed column consisted of a 12.0-cm I.D. jacketed


acryl-resin tube packed to the heights of 0.2m or 0.3m

with 15mm ceramic Raschig


ceramic spheres.
The liquid

acryl-resin

ring and
distributor

1/2- and 1-in.


was made of

and had sixty one 3.5mm I. D. glass nipples

arranged in a ll.6mm triangular


pitch.
The aqueous solutions
of 0.05, 0.1, 0.25,

0.5 and 1.0iV-

NaOHwere
irrigated
over the packings after atheating
in
the thermostat
tank which was controlled
30lC.

In this paper, the applicability of the film theory18) of gas


absorption with second order reaction to the absorption of
on July

by using

of Nagoya, Nagoya

Air from a blower and carbon dioxide

= 0. 005l (L/aw^Ly/'

* Received

is confirmed

TAKEUCHI**

from a cylinder

were fed to the bottom of the packed column after the


gas mixture waswell mixed and saturated with water
vapor. The CO2content in the air was controlled by a
reducing valve at the CO2cylinder. The partial pressure
of the solute gas, p, was maintained constant in each run
JOURNAL OF CHEMICAL ENGINEERING

OF JAPAN

in

the

range

of 0.03~0.07aim.

Table

The gas and liquid samples for analysis were taken at


the inlet and outlet of the column. CO2 in a gasphase

was analyzed by a modified Orsat apparatus which had a


lOOcc gas burette with O.lcc. scales. The error of analy-

End

Normality(JV)

Equivalent

packing

height(w)

effect

of the

packed

column

0.91

0.51

0.27

0.14

0.07

0.073

0.062

0.059

0.058

0.055

sis for lOOcc of sampling gas was about 0.05%.


Liquid
samples were analyzed for the concentrations
of total

alkali and hydroxide by the Winkler method.

1 "2 Experimental
results
The overall capacity
coefficients, Kg<z, were calculated
by the following
equation.
Koa = GMi(Yi - Y2)P/ZJpim
(4)

where Apim= [(yi-3^2)/In(3^1/3^2)]P,


since the back pressure of CO2over the aqueous solutions of NaOHcan be
assumed to be zero. The material balances of the solute
in gas and liquid phases were obtained within the range
of 10010%
in all runs
NaOH solution in which

except in the case of 0.05iV


they were fairly
beyond the

range. End effects in the packed column were determined


by using two packed heights of 0.2 and 0.3m for 15mm
Raschig

ring and expressed

as the equivalent

height

of

packing, Ze, which were tabulated in Table 1 for various


concentrations of sodium hydroxide. The end effect for
0.05iV solution could not be determined due to the poor
accuracy of data.

Its value,

0.05m. by the extrapolation

however,

was estimated

as

Fig. I KgOdata for CO2absorption


solutions

at 3O C

into aqueous NaOH

of the end effects for various

normalities
higher than 0.05iV-NaOH.
of the end effect on liquid rate could
the range of these runs.

The dependency
not be observed in

The effect of liquid rate on KGa for 15mmRaschig


rings is shown in Fig. 1. Kgcl increases with the liquid
rate and the relationship may be shown by (Kaa)cLw,

and
Hoftijzer18) and Brian2 3) presented relations between
/3 and 7*, r and q for second order or pseudo first-order
irreversible
the fluid

reactions
based on the particular
dynamics of the process.

models

of

where n varies within an extent from about 1/3 for the

The rate constants for Reaction (5) have been reported


bykro=72001/mol-sec
many investigators. at 30C
In ourwhere
laboratory,
Miwa9) found
kro is kr at infinite

case of high concentration

dilution using the liquid jet. For the solution of a given

centration.

of NaOHto 1/2 for low con-

Most of the previous

data in the literature

on CO2absorption in NaOHsolution have been obtained


with solutions of concentration greater than 0.5iV except
those of Blumet al.n whofound the value of n tovary
from about

0.3

to 0.5.

It

may be expected

that

the

more physical the mechanismof gas absorption approaches,


the lower the concentration of NaOHbecomes.

concentration,
the following relation
is found
logfc
= 3.875
+?/.
where

the

value

of factor,

at 30C
(8)

q, is 0.1339>10).

To estimate the diffusivity


of the solute in*the electrolyte solution, DL, the modified Stokes-Einstein's
equation
was used,

DlVl71

= const.

(9)

Miwa9) found that n was 0.9 to fit the equation (9) to


2.

Interpretation

for Chemical

Absorption

The reaction between CO2 and sodium hydroxide in


the aqueous solution
is believed
to take place in the
following
two steps :
CO2 + OH' -> HCO3'
(5)
HCO3' + OH'
> CO3" + H2O
(6)
Reaction (5) may be considered
to be rate controlling
because Reaction (6) is a proton transfer
reaction
and
about 103 times as rapid as Reaction (5).
Thus, the absorption of CO2 in a NaOH solution is regarded
as gas
absorption accompanied by a relatively
slow second-order
reaction.

the experimental
data for the systems
gas and one-valency electrolyte
solution
ion. Hence this relation
was used for
The diffusivities
ratio,
r=Don'/D.ca*,

of various solute
containing sodium
NaOH solution.
in potassium or

sodium hydroxide solution were 1.67 at 20C according


to Nijsing et al.10) and this value was used by assuming
that r was independent of temperature in the range of
20~30C.

Saturated
concentration
of CO2 in an electrolyte
solution was estimated
by the van Krevelen's
method19).

Although a part of NaOHwould change into Na2CO3in


the packed column, only the initial concentration of NaOH

expressed by Eq. (7).

NA = pkL{CAi - Cao) = kL\CAi - Cao)


(7)
where /3 is the so-called
reaction factor and Cao becomes
zero for an irreversible
reaction.
The reaction factor

has been taken into account as the salting effect on this


saturated concentration, Caz, under the assumption that
the salting effects of these two solutions (that is NaOH
and Na2CO3 solutions)
are the same.
The liquid side mass transfer coefficient was calculated
by Eq.(3).

depends on the kinetics of the reaction and on the parameters y, r# and. q. Hatta6), Danckwerts4), van Krevelen

Estimated values of kr, DL and H calculated by the


above mentioned methods and liquid properties used in

The rate of absorption with chemical reaction can be

VOL.1

NO.1

1968

63

this work are tabulated in Table 2.


The theoretical reaction factor, /3, for each experimental
condition was calculated by Eq. (10) of van Krevelen18).
P

tanhrVl-E^-D/r?]

first-order
tion.

The observed values of /3 in the packed column for gas

absorption

UW

additive

for 0.91Ab

Cb. The maximum

amounted to 38%
and 64% for 0.07N.
This range of

solution

the concentration corresponds to the regemes of the pseudo

with

a chemical

reaction

can be determined

from Eq. (ll) assuming the resistances

In the calculation
of y-^JkrCjiDL /kL, the concentration
of NaOHwas calculated as the arithmetic mean value of

inlet
and outlet liquid concentrations,
conversion of hydroxide
to carbonate

reaction as well as the slow second-order reac-

,
1/Kaa

- 1/koa

in each phase are

+ l/HfikLa

(ll)

and evaluating each capacity coefficient, Tzgcl and k,La, for


physical absorption from the product of ka given by Eq.
(2) or kL by Eq. (3) and am by Eq. (l). The evaluated
value of kaa amounted to about 10%of the total resistance
for 1.ON solution, but in the dilute solution it was less
than
a few per cent.
The values of /3ObS obtained
by Eq. (ll)
are compared
with
/3theo calculated
by Eq.(10) in Fig. 2. The observed
and theoretical
values of (Z are in agreement within an
error of 30%.

3. Relationship between Wetted and Inter facial Areas


In this study, it was assumed that aw is identical

However, the validity


discussion.

of this

assumption

to a.

needs further

In the case of a pseudo first-order reaction, it is possible


to obtain the inter facial area in packed columns whenthe
value of T is greater

than

5, because the value of fl is

nearly
equal toby Ttheand Eq.from(12).the definition of T, a is directly
determined
kLa

kLa

a=lkT=~7m5T

>.

_ (12)

where Cb is approximately constant and krCB represents


the pseudo first-order reaction rate constant.
Fig. 2

Theoretical

and observed

values

of ft for CO2

Yoshida-Miura21)
reported that the inter
facial area calculated
by Eq. (12) was- identical
with aw of Hikita's
equation

absorption into aqueous NaOHsolutions

and this

is shown by a dotte_4 line

in Fig.

3.

Fig. 3 Inter facial areas for chemical


absorption
and wetted
packed columns

Table 2 Liquid properties


OH'

of NaOHsolution,

Kkg/m3)

Mkg/m-hr)

0..Q7
0

64

1,037
1,019
1,009
-1,004

1,001
996

area

in

diffusivities,

Henry's law constant of CO2in NaOHaqueous solutions at 3O C

(j(dyne/cm)

DLx106(m2/hr)

Hx102(-g^^)
\

0.91
0.51
0.27
0.14

surface

3.49
3.23
3.07
2.98

72.5
71.9
71.6
71.4

2.93
2.88

71.3
71.2

6.62
7.13
7.49
7.67

2.26
2.54
2.71
2.84

7.81
7.92

2.91
2.97

m "atm

krx10~7f1
/

^-r-)
\kg-mole"nr/
3.57
3.15
2.93
2.82

2.76
2.59

JOURNAL OF CHEMICAL ENGINEERING

OF JAPAN

these data seemto be in the region of the pseudo first-order

In this work, the reaction factor, /3, for a second order


reaction has been obtained from the experimental results by
assuming a=aw. Thus, /3ot>s calculated by Eq. (ll) coincides
with /3tneo calculated from Eq. (10) as shown in Fig. 2.
This agreement between /3theo and /3Obs within a reasonable
error substantiates the assumptionthat a=awmaybe ap-

the low partial pressure of CO2. The inter facial area in


the packed columns has also been reported by Danckwerts

There are obviously somedifferences between aw and a


in packed columns, because the wetted surface measured

between aw and a shows that the gas-liquid


interface
is
uniformly effective
and essentially
identical
with aw for
gas absorption
with a pseudo first-order
reaction under
these conditions.

well with the inter facial area.

The inter facial area for 1- and l/2-in Berl saddles was
calculated
from KGa data forKGa
CO2-NaOHsystem
of Leva8)
and are shown in Fig.4.
data for 1- and l/2-in:

i\. Effect of Alkali Concentration on KGCt

spheres were obtained by the absorption of CO2 into 12VNaOH solution in the same apparatus described in the

The rate of absorption of CO2 into an alkali solution


depends not only on the concentration of CO2 at the

section 1-1. The inter facial areas from these data are

interface,
Cai, Cb.but also on the concentration on hydroxide
ions in liquid,

a was calculated

and Leva8) on the


neglecting
the gas
of Vassilatos20)
on
cal solution
using

reaction

from Kaa data of Tepe and Dodge17)


absorption
of CO2 in NaOH solution
phase resistance,
and from kLa data
the absorption
of CO2 into ammoniakr given by Pinsent et al..13)
All of

because of the high

concentration

of alkali

and

et al.5) and Richard et al..14) These data are shown in


Fig. 3 with a line of aw from Eq. (l). The agreement

shown in Fig. 5 in which the agreement between a and


aw is also fairly good.
As shown in Figs. 3, 4 and 5, the agreement between
a and aw for Raschig rings, Berl saddles and spheres substantiates
the use of Eq. (l) for estimation
facial area in packed columns.

of the

inter-

Fig. A Inter facial areas for gas absorption with pseudo firstorder reaction

and wetted

surface

areas for Berl

Fig. 6
Effect of alkali concentration
rate of absorption of CO2

OL.1

1968

NO.1

saddles

plicable

for the chemical

absorption

in packed

columns.

is the solid-liquid
interface
and it does not include the
area on column's wall. On the other hand, the change
of liquid path and the isolated droplets on the packing
pieces make aw larger. It seems, however, that these
matters compensate each other and hence Eq. (l) agrees

Fig. 6 shows the effect of alkali concentration on Kaa


in the literature1>17).
As shown in Fig. 6, the data
Tepe-Dodge17)
are in the range of high concentration

of
of

NaOHand shows the maximumpoint of Kgci at about

Fig. 5 Inter facial areas for gas absorption with pseudo


first-order

reaction

and wetted surface

areas for spheres

on

65

Assuming the reaction

to be a pseudo first-order,

for alkali solution can be calculated

kr

= reaction rate constant for second-order reaction


[mVkg-mole - hr]
= superficial
mass velocity of liquid
[kg/m2 -hr]
= rate of absorption
[kg-mole/m2 -hr]

1.8AT. The relation is seemed to be originated in the


changes of the diffusivity
and solubility
of solute gas in
electrolyte solution. The higher Cb is, the more viscous
the solution is and hence Dl, becomes smaller.

NA
P

= total pressure
= partial pressure

Kaa

== parameter
defined by {Cbq/vCai)
[-]
gas constant
[m3-atm/kg-mole- K]

by Eq. (ll) and (12).

As shown in Fig. 6, KGa calculated


for CO2-absorption
into NaOH solution agrees so well with the observed
value of Tepe-Dodge, and shows the maximum point at
1.75AT.
Eqs. (ll)

For KOH solutions,


Kgcl values calculated
by
and (12) is shown by a curve 5 in Fig. 6 and

the maximumpoint is found at about 4.5AT. This difference of Cb between NaOHand KOHsolution comes
from the fact that the variation of the viscosity of KOH
solution with Cb is smaller than that of the viscosity of

[atm]
[atm]
[-]

ratio of liquid diffusivities,


Don'/Deo.,
absolute temperature
mole ratio of solute in gas phase
mole fraction of solute in gas phase
height of packings

[K]

[-1
[-]
[ml

Greek letters
[-1
[-1
[kg/m-hr]
[kg/m3]

P = reaction coefficient defined by kiP/kz


7 = parameter defined by {\lkrCsDL /kz)

- viscosity

NaOHsolutions.

P = density
a = surface tension
[dynes/cm] or [kg/hr2]
Oc = critical surface tension of packing material

Conclusion

v
= stoichiometric
Subscripts

[ dynes/cm]

factor

[-]

The experiments of the absorption of carbon dioxide


into aqueous sodium hydroxide solutions were carried out
in the column packed with 15mm Raschig rings and 1/2in and 1-in Spheres.
Kaa for the chemical absorption is proportional
to the
1/3~1/2
power of the liquid rate in the range of 1.0~
0.05iV-NaOH. These values of Kgcl can be evaluated by
using the reaction factor of the film theory for gas ab-

2)
3)

sorption with second-order reaction derived by Krevelen,


with Eq. (1) for aw, Eq. (2) for kG and Eq. (3) for kL.
By means of the gas absorption with pseudo first-order

4) Danckwerts, P.V.: Trans. Faraday Soc, 46, 300 (1950)


5) Eng.
Danckwerts,
P. V., A. M. Kennedy and D. Roberts: Chem.
Sci., 18, 63 (1963)

reactions, it has been substantiated


that the wetted surface area of Eq. (l) may be approximately
equal to the

6)

inter facial area.

7)
Hikita,
8)
Leva,

The dependencies of Kaa on NaOHconcentration was

clarified and this tendency


experimental
data.

coincided

quite

well with

the

1, 2 = bottom and top of column, respectively


G, L = gas and liquid phase, respectively
Literature

cited

1) Blum, H.A., L.F. Stutzman


Chem.,

44,

Brian,
Brian,

P.L.T.:
P.L.T.,

E. Journal,
Hatta,
(1928)

and W.S. Dodds.:

2969 (1952)

Sc.
J.F.

D. thesis,
M.I.T.,
Hurley
and E.H.

Cambridge
Hasseltine:

Ind. Eng.
(1956)
A. I. Ch.

7, 226 (1961)

S.:

J. Soc. Chem. Ind.(Japan),

35,

1389(1932),

31,

869

H. and
T. Kataoka: Kagaku1, Kogaku,
20, 528(1956)
A. I. Ch. E.Journal,
224(1955)

M.:

9) Miwa, Y.: Sc. M. thesis, Nagoya University,


Nagoya (1964)
10)Eng.Nijsing,
andH.Kramer: Chem.
Set., 10, R.A.T.
88 (1959)O., R.H. Hendriksz

ll) 31, Onda,


K., H.Takeuchi and Y.Koyama: Kagaku Kogaku,
126 (1967)

Nomenclature

12)

a = inter facial area in packing


[m2/m3]
at
= total surface area of packing
[m2/m3]
<Xw . = wetted surface area of packing
[m2/m3]
Cai, C^io - inconcentration
of
component
absorbed
at
interface
and
the bulk of liquid,
respectively
[kg-moles/m3]

13) Pinsent, B.R.W., L. Person and F.J.W. Roughton: Trans.


Faraday Soc.y 52, 1954 (1956)
14)Eng.
Richards,
G. 325M., (1964)
G. A. Ratcliff and P.V. Danckwerts: Chem.
Sci., 19,

concentration

cB
D
G

GMi
g
H
KG
kG

66

of the reactant

average concentration

of liquid

[kg-moles/m3
]
[kg-moles/m3]

of the reactant

diffusivitymass velocity

superficial
superficial

in the bulk

of gas
molar velocity of inert gas
[kg-moles/m2

gravitational
constant
Henry's law constant

[ [kg/m2-hr]
m2/hr]
- hr]

[m/hr2 ]

[kg-moles/m3 - atm]
overall coefficient
[kg-moles/m2 - hr - atm]
gas-phase mass transfer coefficient
[kg-moles/m2 "hr "atm]
liquid-phase
mass transfer coefficient
[m/hr]
liquid-phase
coefficient for chemical absorption
[m/hr]

Onda, K., H. Takeuchi


Japan, 1, 6 (1968)

and

Y. Okumoto:

J.

Chem.

Eng.

15) Sherwood, T.K. and R. L. Pig ford: "Absorption and Extraction" 2 nd. p. 336, McGraw-Hill, New York (1952)
16)man:
Shulman,
H. L., C.F. Ullrich,1, 253A.Z. (1955)
Proulx and J. O. ZimmerA. I. Ch. E. Journal,

17)39, Tepe,
J. B. and B.F. Dodge: Trans. Am. Inst.
255 (1943)

18)67, Van563, Krevelen,


D.W. and P.J. Hoftijzer:
587 (1948)
19)XXIeme
Van Krevelen,
Congr.
20)

21) Yoshida,F.
22)

Weisman,
(1950)

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