Ind. Eng. Chem. Process Des. Dev.

1980, 19, 371-377

Hence, the char-C02 reaction cannot be approximated as

first order as done for the graphite. This is especially true
when the pressure diffusion effects are included (Figure
6).
Summary

In this paper the char-COp-CO reaction has been examined and carbon monoxide inhibition was shown to be
greater a t lower temperatures for the char system. Presence of the calcium decreases the inhibiting effects of CO
by effecting the reaction mechanism. Differences in the
char reactivity due t,o the char preparation method has
been found, and can be explained on the basis of char
oxygen content and surface area differences due to the
different pyrolysis techniques. An increase in the char
reactivity based on remaining char was found during the
course of reaction for bituminous, lignite, and subbituminous chars. A one-constant empirical expression has
been developed to account for this reactivity change as a
surface area development. A generalized kinetic expression
has been suggested to take into account CO inhibition,
surface area development, and diffusion effects.
Acknowledgment

This work was sulpported by grants from the United

States Department of Energy. We appreciate the useful
suggestions provided by C. Y. Wen. The assistance of T.
G. Panson and G. Stewart, Morgantown Energy Technology Center, through the use of their facilities is appreciated.
Nomenclature

A = empirical constant for surface area development

a = constant for correlating reactivity with CaO content
b = constant for correlating reactivity with CaO and 0 content
d = particle diameter, cm
F = deviation factor of kinetic surface development due to
CO inhibition
f = fractional conversion
G = carbon monoxide adjustment factor, the ratio: (reactivity
with C02-CO)/(reactivity with COP)
I = constant, basic carbon reactivity, g/g-min
k l , k 2 , k 3 = rate constants
K1, K P ,KI1,Kzl = cornbined rate constants
M = constant for correlating surface area development

37 1

n = factor for change in reactivity as a function of conversion

pco = partial pressure of CO, atm
pco2 = partial pressure of COz, atm
r = coefficient of correlation
S, = surface area of char, m2/g
SR= surface area of reference char, m2/g
t = time, min
X1 = Ca as CaO %
X p = oxygen organic %
7 = effectiveness factor
v = constant for surface

area development
p = constant for surface area development
Literature Cited
Agarwal, A. K., Muralidhara, H. S., Sears, J. T., Institute of Scientific Problems
Relevant to Coal Utilization, Morgantown, WV, May 24, 1977.
Austin, L. G., Walker, P. L.. Jr., AIChE J., 9, 303 (1963).
Berger, J., Siemieniewska. J., Tornkow, Fuel. 55, 9 (1976).
Bhatia, S., Perlrnutter, D., private communication, University of Pennsylvania,
1979.
Blake, J. H., Bopp, G. R., Jones, J. F., Miller, M. G., Tambo, W., Fuel, 45, 115
(19661.
Chauhan: S. P., Feldman, H. F., Starnbaugh, Oxiey, J. H., Am. Chem. SOC.
Div. Fuel Chem. Prepr., 22(1), 35 (1977).
Dutta, S..Wen, C. Y., Bett, R. J., Ind. Eng. Chem. Process Des. Dev. 16, 20
119771.

Erg,;
S:, J . Phys. Chem., 60, 480 (1956).
Fass, S. M.. Desai, G. V., Brown, L. F., West, R . E., Carbon, 12, 619 (1974).
Fuchs. W. E., Yavorsky, P. M., Preprints, 170th National Meeting, of the Arnerican Chemical Society, Chicago, Iii., Voi. 203, p 115, 1975.
Goring, G. E., Curran, C. P., Turbox, R. P., Gorin, E., Ind. Eng. Chem., 44, 1051
(1952).
Grabke, H. J., Carbon, 10, 587 (1972).
Guitsze, A., Jarecka, B., Carbon, 5, 314 (1967).
Hedden, K., Kopper, H. H., Schulze, V., 2.Phys. Chem. (Frankfufi am Main),
22, 23 (1959).
Hippo, E.,Walker, P. L., Jr., Fuel, 54, 245 (1975).
Jenkins, R . G., Nandi, S. P., Walker, P. L., Jr., Fuel, 52, 288 (1973).
Kalback, W. M., Brown, L.F., West, R. E., Carbon, 8, 117 (1970).
Kawahata. M., Walker, P. L., Jr., "Proceedings of the Fifth Carbon Conference",
Vol. 2, p 251, Pergamon Press, London, 1962.
Krasuk, J. H., Smith, J. M., Ind. Eng. Chem. Fundam., 4, 102 (1965).
Marsh, H., Rand, B., Carbon, 9, 47, 79 (1971).
Marsh, H., Siemieniewska, J., Fuel, 44, 355 (1965).
Mentser, M., Ergun, S., Carbon5, 331 (1967).
Reif, A. E., J . Phys. Chem., 56, 778 (1952).
Sears, J. T., Muralidhara. H. S., Wen, C. Y., Ind. Eng. Chem. Process Des.
Dev., companion paper in this issue (1980).
Suubera. E. M.. Peters. W. A,. Howard. J. 6 . . Ind. no. Chem. Process Des.
Dev:, 17, 37 (1978).
Turkdogan, E. T., Olsson, R. G., Vinters, J. V., Carbon, 8, 545 (1970).
Walker, P. L., Jr., Foresti, F. J., Jr., Wright, C. C., Ind. Eng. Chern., 45, 1703
(1953).

Receiued for reuiew October 24, 1978

Accepted January 21, 1980

Gas Holdup and Pressure Drop in Bubble Column Reactors

Donald N. Miller
Engineering Department, E. I. du Pont de Nemours & Company, Wilmington, Delaware 19898

Gas h'oldup and pressure drop measurements were made in a 0.229 m diameter X 9.14 m high glass column with
air and four different liquids in cocurrent upflow. Perforated plates with 0.00635 m holes and 2.85% open area
were inserted at 1.524 m spacing for half of the experimental runs. Two-phase flow rates were adjusted to cover
ranges of interest in bubble column reactor design. Relationships are developed with and without plates for vessel
diameters larger than 0.15 m and two-phase Froude numbers under 0.05. Resutts are compared with other published
open ,pipe data.

Introduction

Reactions with interphase mass transfer are often carried

out in sparged bubble columns. Oxidation and hydrogenation reactions are examples where both phases are
moved through the :reaction zone in cocurrent upflow.
0196-4305/80/1119-0371$01.00/0

Reaction typically takes place in the liquid phase, but mass

transfer of a reactant such as oxygen or hydrogen from gas
to liquid can limit overall reaction rate.
Design of reactors with two phase contacting requires
knowledge of the physical properties of the dispersions.
0 1980 American

Chemical Society

372

Ind. Eng. Chem. Process Des. Dev., Vol. 19, No. 3, 1980
T\rPRESSURE

GAGE

HOLES

50 G P M
PUMP

Figure 1. Equipment schematic.

Typically, reaction equipment with two-phase gas-liquid

contacting is in the bubble, bordering on slug flow regimes.
Superficial gas velocities range up to 0.30 m/s and liquid
velocities up to 0.05 m/s. Corresponding Froude numbers
are in the range zero to 0.01. Earlier published correlations
of aeration and pressure drop apply in higher velocity and
Froude number ranges. Also, many of these correlations
are based on data obtained in small diameter pipes where
wall effects influence two-phase flow behavior.
The size requirement for bubble column reactors is
continually increasing, and greater accuracy in scale-up and
design is becoming increasingly important. This study was
undertaken to review data on aeration (or gas holdup) and
pressure drop available in the literature and to develop
more accurate information within the operating ranges of
interest for reactor design.

Experimental Section
Apparatus. A schematic of experimental equipment
is shown in Figure 1. Air and liquid feeds were passed
in cocurrent upflow through a 0.229 m diameter glass
column, the diameter being chosen large enough to preclude any influence of wall effects on performance. Air
was fed through a 0.1270 m diameter ring sparger, with
96 0.003175-m diameter holes on the underside of the ring,
located at the bottom. Liquid feeds were pumped in under
the sparger through a nozzle centered in the bottom head.

The gas-liquid effluent was directed back to a 5.6&m3hold

tank, where the gas disengaged and was vented. The liquid
was then recirculated to the column with a 0.00315-m3/s
Pump.
Both gas and liquid feed rates were measured with rotameters. Pressure was measured at top and bottom of
the column with Bourdon gauges, and temperature was
measured with in-line thermometers.
The column fully assembled was 9.14 m high, containing
six 1.524-m flanged sections. Nozzles at the top of each
section were used for sampling and for periodic checks of
pressure and temperature.
During the last half of the experimental program, perforated plates were installed between column sections.
Each plate had 37 0.00635-m holes on 0.0349 m triangular
spacing.
Procedure. Gas and liquid feeds were turned on, rates
were adjusted to the desired settings, and the system was
allowed to equilibrate for at least 1800 s. Temperature and
pressure readings were taken and the feed rates were cut
off. Aeration was determined by measuring the static
height of clear liquid after gas disengagement. These
measurements were made during assembly and disassembly of the column.
During assembly, the aeration measurements were made
on one, two, four, and six sections. During disassembly
with perforated plates installed, measurements were made

Ind. Eng. Chem. Process Des. Dev., Vol. 19, No. 3, 1980

I"

. Air -- Water
Water - 0.M5%Triton X-100

i 03

Air

+ Air

- Water

A i r - Water - 0 W570Triton X-100

- 60% Corn S y r u p
o A i r - 6 0 % C o r n S y r u p - 0.W % T r i t o n

Air

o Air

x Air

- 601 Corn Syrup

- 605Corn Syrup - 0 O@CTriton -X-1M
__

-1

X-100

Annular

10

--

$ I

373

lbl I

IO-^

I
IO+

10'~

10.l

IO

lo2

lo3

NF,MlF
Figure 3. Oshinowo and Charles (1971) two-phase vertical upflow
chart.

10

102

I 03

i 04

GLA*/G/Gg

Figure 2. Cichy e t al. (1969) two-phase vertical upflow chart.

with six, four, three, and finally two sections.

Air with four different liquid feeds was tested during
assembly with one and six sections installed. Air and the
same four liquids were again tested on disassembly with
six and two sections. All other testing was done with
air-water only.
The four liquids were water, water with 0.005% Triton
X-100,60% corn syrup in water, and 60% corn syrup with
0.005% Triton X-1010 in water. The Triton X-100 surfactant was used to simulate lower surface tension; corn
syrup, for higher density and viscosity. The ranges of these
variables covered in the study were 0.035 to 0.073 N/m,
1000 to 1280 kg/m3, and 0.0009 to 0.049 Pas.
Surface tension measurements were made by the
"method of maximurn bubble pressure" recommended by
Sugden (1924). It was recognized that, with the highly
turbulent nature of the two-phase flows used in the test
work, bubble breakup and coalescence would be a rapid,
continuing process. If there were any tendency for surfactant to accumulate at the liquid interface, bulk liquid
surface tension measurements would not be fully representative of performance. The Sugden surface tension
technique imposes the desired gas bubbling dynamics as
an integral part of the experimental measurement.
A hydrometer wa13 used for density determinations.
Viscosity was measured with a Brookfield viscometer
Model LVF.
With each liquid and each column section combination,
measurements were made of temperature, pressure drop,
and gas holdup a t folur gas rates at each of three liquid
rates. Superficial liquid velocities averaged 0.000508,
0.00508, and 0.0495 m/s; superficial gas velocities averaged
0.00711, 0.0371, 0.0767, and 0.234 m/s.
Analysis of Results
Flow Regime. The experimental points of this study
are shown plotted on vertical, two-phase flow pattern
charts in Figures 2 and 3. Figure 2 is a Govier chart
(Govier et al., 1957) as extended by Cichy et al. (1969) to
include variations in fluid properties. Figure 3 is the chart
developed by Oshinowo and Charles (1971).
Two-phase flows in this study were chosen to cover
conditions in deep seal reactors, where gas-liquid con-

tacting and mass transfer between phases can influence

the overall rate of reaction. By Govier's classification, these
flows are in the bubble, bordering on plug flow regimes.
By Oshinowo's nomenclature, the flows are in the quiet
and dispersed slug regions. Quiet slug flow is described
as gas movement in large, well-defined bullet shaped
bubbles. Dispersed slug flow is described as being similar,
but with froth formation at the trailing edges of the bubbles.
Both Govier and Oshinowo supporting data were obtained in 0.0254 m i.d. vertical pipes. Vertical two-phase
flow behavior is influenced by pipe size for diameters up
to 0.1524 m. There is no transition to plug flow, for example, in larger pipe and vessel diameters where backmixing can occur to an appreciable extent. As demonstrated in earlier published data (Fair et al., 1962; Akita
and Yoshida, 19731, gas holdup is not significantly affected
as diameter is further increased above 0.1524 m.
Inspection of these two charts will also show that the
experimental points fall outside the range of flows covered
in earlier studies. Gas-liquid ratios (GLX+/GG, the modified Govier abscissa; and Rv112,the Oshinowo ordinate)
are within range, but the individual gas and liquid flow
rates are substantially lower (GG/X, the modified Govier
ordinate; and NFr/All2, the Oshinowo abscissa).
Aeration. As a%rst step in correlating results, aeration
measurements were compared with corresponding values
calculated using predictive procedures recommended in
the literature. There are a number of these, all differing
substantially.
Air-Water Correlations. A procedure described by
Hershey (1935) for air-water lifts utilizes the following
equations

4/(1 - 4) = 2.4 ( d ~ ~ l / 2 ] 0 ' 9 3h

< 4.57 m

(2)

where

Q' = QG - QL @/(I

4)

(3)
A linear fit of points calculated from these equations to
the corresponding experimental points gives an adjusted
multiple correlation coefficient of 0.932. This number
represents the fraction improvement afforded by the
correlation over the use of a mean value for all the points.
Perfect correlation would yield R A 2 equal to 1.0; no improvement over the mean would give RA2equal to zero.
A correlation reported by Gomezplata and Nichols
(1967) for air-water is based on the relationship
4 QG/(ZGA+ QC + QL)
(4)
-

374

Ind. Eng. Chern. Process Des. Dev., Vol. 19, No. 3, 1980

where ZG= 0.610 m/s for upflow. The linear fit of cab
culated to experimental points for these data has an RA2
of 0.961.
A correlation developed by Hills (1976) utilizes a slip
velocity
v
8

vG/@ -

vL/(1 - 4)

(5)
K

and is limited to V, I0.240 m/s.

4 = ((V, - 0.0732)/0.372)0.581

(6)

The RA2 for a linear fit of calculated to experimental points

for these data is 0.966.
Botton et al. (1978) report that the simple relationship

4 = VG0,75

4 = o.o0319VG/zk

(g(PL -

- 0.933

(8)

PG)g/PL2)1/4

x 10-5(VG/Zk)2 + 0.822 x
lo-s(vG/zk)3

(9)

The linear fit of these data gives RA2 = 0.724.

Several correlations on aeration in two-phase upflow
have been published by Hughmark (Hughmark and
Pressburg, 1961; Hughmark, 1962,1967). The earliest is
based on data obtained with air and six different liquids
(water, saturated sodium carbonate solution, kerosene,
trichloroethylene, and two oil blends) in 0.0254 m i.d. pipe.
These data were combined with the data of other investigators obtained in pipe sizes up to 0.1016 m i.d. in his
later correlations. The fit to his correlating parameter ZH
for d = 0.1016 m is
ZH = exp(-1.098

+ 0.316 In X

- 0.0293(1n X))

(10)

$ = VG/(VG/ZH- VL/(1- ZH))

(11)

The linear fit of calculated to experimental points yields

RA2 = 0.748.
A correlation developed by Akita and Yoshida (1973)
is based on air with 13 different liquids (water, two aqueous
glycol solutions, two aqueous methanol solutions, carbon
tetrachloride, and five aqueous NaCl solutions) and water
with three gases other than air (helium, oxygen, C02) in
a 0.1524 m i.d. pipe. Results were correlated as
= 0.2N&,1/8NGa1/12NFro

(12)

The RA2 = 0.838 for this linear fit to experimental data.

Mersmann (1977) makes use of the Akita and Yoshida
(1973) data along with his own experimental results to
obtain the following correlation

$/(I

(13)
- 4)4 = O . ~ ~ ~ V G ( P L ~-/ (PG)g))1/4(CDr)1/2
~(PL

CD, is the drag coefficient for bubble swarms, for which

Mersmanns data indicate 0.09 to be the minimum value.
Above this limit
CDr = 0.0483 ~ F 1 2 4 ( P L / P C ) 3 s ( P L / ( ~ ~- PG))13

0.01

0. 1

(14)

RA2 = 0.776 for the linear fit of data calculated with

1W

10

!
Z = N 1 6
1/8-14
Reh, +rh, t

Figure 4. K vs. 2, open column.

Mersmanns correlation to corresponding experimental

data.
Aeration and Pressure Drop Correlation. As a final
refinement, the experimental data were checked against
a correlation procedure recommended by Anderson and
Russell (1965). This procedure combines the correlation
of aeration with pressure drop, including generalized
physical properties for vertical two-phase flow. The aeration data are based on work by Hughmark (1962), using
his data along with air-water and steam-water flows in
pipes up to 0.0508 m i.d. The pressure drop also follows
a Hughmark (1963) development using data for air with
various liquids (surface tensions in the range 0.035 to 0.073
N/m, densities up to 1200 kg/m3, and viscosities up to
0.030 Pa.s), along with data for steam-water flows. Pipe
sizes up to 0.0635 m i.d. were used in obtaining the supporting pressure drop information.
The Anderson-Russell procedure utilizes the following
two-phase mean parameters for determining aeration
NReM

and

4/(1 - $)4

0. 1

(7)

is applicable for air-water where VG < 0.2 m/s and VL <

0.05 m/s. RA2 for a linear fit of calculated to experimental
points for this equation is 0.961.
Generalized Correlations. A recent correlation was
developed by Kumar et al. (1976) for air in fluids with
surface tensions ranging from 0.031 to 0.074 N/m, densities
from 800 to 1110 kg/m3, and viscosities of 0.0009 to 0.012
Pass. The liquid phases in this study were static.
Zk =

= 4(wG + w ~ ) / ( a d ( $ c l ~
(1 - $)FL)) (15)
VM

= 4(wG/PG
NFrM

YL =

+ wL/PL)
vM2/kd)

(ad)

( ~ L / P L ) / ( ~ G / P G+ ~ L / P L )

(16)
(17)
(18)

These parameters are combined in the following terms to

characterize a correlating factor K (Figures 4-8)

z = NReM1/6NFrM1/8YL-1/4

(19)

Hughmarks plot of K vs. Z is shown as the dashed curve

in Figure 8. Aeration is obtained from

4 = (1 -

YL)

(20)

Equations 15 through 20 are solved by an iterative procedure starting with an initial guess for $. As indicated
in Figure 4, the experimental K s fall considerably below
Hughmarks curve.
The pressure drop determination involves the summation of the two-phase friction drop of lost work AppTp
and static head Apg. Hughmarks plots for two-phase
friction drop referred to a fictitious liquid friction drop APL
vs. YL with N F , as
~ parameter are shown in the dashed
curves of Figure 6. As indicated in the low Froude number
range, two-phase friction drop decreases with decreasing

Ind. Eng. Chem. Process Des. Dev., Vol. 19, No. 3, 1980 375
31

JP

- 0.0058Triton

- 1

X-1W

, . .

,
. .

. ._ _

~~.

0 1
IKurnar et al

--

I---.

0.01

3. :

/,#I

-- ~i

0. 1

100

''

'
'

-Akita

et a l

-----

Anderson and Russell

This Study

103

10
116
Iray -114
Rei,, NFrh,
t

Figure 8. K vs. 2, comparison of generalized correlations.

Figure 5. K vs. 2, column with perforated plates.

approaches an assymptotic upper limit represented by the

solid curve of Figure 6, for which the following expression
applies
APTP/AL

APL/U

PM

PL

- 0.835 - 0.734Y~+ 0.1730YL2

(21)

+ Air

- Water. 0 W % T r l t o n

The adjusted R A 2 for the fit of this equation to the experimental data is 0.785.
The fictitious liquid friction drop ApL used as a reference
in eq 21 is obtained from a Reynolds number based on
inside vessel diameter and Fanning friction factor f

X-I00

N R =~~ W
~ L/(T~WL)
= 32fWL2/(7r2p~d5)

ApL/U
0 01

a 01

0.001

0.1

-7
.

.
.

= g/gc[(wG + WL)/(WG/PG +

..,.
~.
, , . ~..

AI',

0.01

1
0.1

-.
I

10
NRe 116

1:8

M NFrhl

103

-114

yL

Figure 7. K vs. 2, comparison of air-water correlations.

to a minimum a t N F = ~1 and
~ then increases with
furthher decrease in hrFrM.
Hughmark's data are limited to a minimum Nb of 0.05.
In this study, the experimental NFrM
range of interest is
0.00001 to 0.05. Below NFw = 0.05, two-phase friction drop

Npr

wL/PL)I

(25)

= (1

+2

. 3 d m

+ HG/HL)HL

(26)

where HG and HL are velocity heads through the holes

based on superficial gas and liquid velocities, respectively.
Aeration K s are plotted vs. the parameter Z for the open
column in Figure 4 and for the column with perforated
plates on Figure 5. The solid curves on the two figures
represent the best fits to the experimental points. The
aeration K equations follow

0.1

(24)

With perforated plates in the column, pressure drop

through the holes in the plates must be included in the
overall Ap. The correlation reported by Chisholm (1967)
has been used in this work

4PG + (1 - 4)PL

and the static head from

APS/U

(23)

The two-phase mixture density is calculated as

PM =

(22)

open column

K = exp(-3.13

+ 1.689 In Z

0.279(1n Z ) 2 ) (27)

for which R A 2 = 0.764

perforated plate column

K = exp(-3.06
for which

RA2

+ 1.624 In Z - 0.237(1n Z)2)

= 0.880.

(28)

376

Ind. Eng.

Chem. Process Des. Dev., Vol. 19, No. 3, 1980

Comparison of Correlations. Figure 7 shows the

aeration coefficient K vs. 2 back-calculated for the airwater correlations; Figure 8 is the corresponding plot for
the generalized correlations discussed earlier. The K values
calculated from the data of Hershey (1935), Gomezplata
and Nichols (1967), and Kumar et al. (1976) tend to be low
relative to those of this study and the aerations predicted
with these correlations will, therefore, be correspondingly
low. Pipe sizes used in the Hershey work are not available.
Gomezplata used 0.0508 m i.d. pipe and Kumar used
0.0508 to 0.1016 m i.d. pipe.
The Anderson-Russell (1965) correlation predicts much
higher K values than were obtained in this study. The pipe
diameters from which the supporting data were obtained
for this analysis were 0.0508 m and under. The aeration
data using the Anderson-Russell correlation will, therefore,
tend to be high for vessel sizes larger than 0.0508 m.
The K values obtained using the other correlations
bracket those obtained in this study reasonably closely,
although those from Akita (1973) tend to be somewhat
high in the lower gas velocity range. The Hughmark (1967)
correlation utilizes data from other literature sources for
pipe sizes larger than 0.1016 m. The Akita (1973), Hills
(1976), and Mersmann (1977) data were obtained in 0.1524
m i.d. pipe. Botton (1978) results are based on 0.250 and
0.480 m pipe diameters.
Conclusions a n d Recommendations
The Anderson-Russell aeration coefficient, K , shown
plotted vs. 2 as the dashed line in Figure 8, is recommended for two-phase upflow where the pipe diameters
are 0.0508 m and under.
The ICs obtained in the open pipe data of this study are
shown plotted vs. 2 as the solid curves in Figures 4,7, and
8. The corresponding K vs. 2 curve for the perforated
plate column is shown as the solid line in Figure 5. These
correlations are recommended for two-phase upflow where
the vessel diameters are 0.1524 m and larger.
The procedure for calculating aeration follows: (1)With
an initial guess for 4, calculate the liquid flow volume
fraction YL,the two-phase Reynolds number NhM,and the
two-phase Froude number NFw (2) With these numbers,
next calculate the parameter 2 using eq 19. (3) Select the
appropriate aeration coefficient K from Figure 4, 5, or 8.
For vessel diameters 0.1524 m and above, eq 27 gives K
as a function of 2 for an open column; eq 28 is the corresponding relationship for the perforated plate column.
(4) Calculate 4 using eq 20. (5) Check the calculated 4
against the original guess, choose a closer starting value,
and repeat the procedure until calculated and initial guess
$J'S are within the desired closure, say 5%.
Pressure drop is the summation of two-phase friction
drop APTP, static head Aps and, with perforated plate
inserts, the drop through the holes in the plates APp
utntal

ilPTP

+ Mp

(29)

Two-phase friction drop is a function of YL and NFrM.

Static head is obtained from eq 25; the drop through the
holes in the plates, from eq 26 multiplied by the number
of plates.
Below NFrY= 0.05, two-phase friction drop increases
with decreasing NFrM,approaching an asymptotic limit.
This limit has been determined to be
ApTP/hL

PM

- pL/hL

= 0.835 - 0.734Y~- 0 . 1 7 3 0 Y ~ ~

PL

(30)
The term

(APL/aL)/pL

is a fictitious friction drop which

is negligible and can be omitted for vessels larger than

0.229 m i.d.
Nomenclature
A = cross section, m2
CD,= drag coefficient for bubble swarms
d = inside diameter, m
f = Fanning friction factor
C G = gas mass flow, kg/m2 s
GL = liquid mass flow, kg/m2 s
g = acceleration of gravity, m/sz
g, = dimensional constant, 9.80 kg m/kg force s2
HG = gas velocity head, kg/m2
H L = liquid velocity head, kg/m2
h = height, m
K = aeration coefficient
U = len th increment, m
N B =~ gd fp L / u , Bond number
NF1 = u ~ P L ' / ( ~ L ~ -( PPG)g),
L
fluid number
N F =~ VG/(gd)'/',
~
gas Froude number
N F =~ V~ ' / g d , two-phase Froude number
',
number
NG, = gd 51p ~ ' / p ~ Galileo
N R =~4 ~W ~ / ( r d p L )liquid
,
Reynolds number
NRehl; 4(WG + W L ) / ( r d ( 4 & + (1- +)PL)), two-phase Reyno s number
Ap = pressure drop, kg/m2
A ~ =L liquid-phase friction drop, kg/m2
A p , = static pressure drop, kg/m2
Aptod = overall pressure drop, kg/m2
A p ~ p= two-phase friction drop, kg/m2
QG = gas flow rate, m3/s
QL2= liquid flow rate, m3/s
R A = adjusted multiple correlation coefficient
Rv = gas to liquid volumetric ratio
VG = superficial gas velocity, m/s
VL = superficial liquid velocity, m/s
VM = superficial two phase velocity, m/s
V, = slip velocity, m/s
WG = gas flow rate, kg/s
WL = liquid flow rate, kg/s
YL = liquid flow volume fraction
Z = aeration correlation parameter
ZG = Gomezplata correlation parameter
ZH = Hughmark correlation parameter
Greek Symbols
A = p ~ * (/ p ~ * d * ~ ) physical
l/~,
properties parameter ,
X = (pG*pL.*)'/', density parameter
MG = gas viscosity, Pa.s
pL = liquid viscosity, Pa-s
pw = water viscosity, Pa-s
pL* = p L / y w , viscosity arameter
P A = air density, kg/m B
pG = gas density, kg/m3
pL = liquid density, kg/m3
pM = two-phase density, k /m3
pw = water density, kg/m
p*G = pG/pA, gas density parameter
= pL/pw, liquid density parameter
u = surface tension, N/m
uw = air-water surface tension, N/m
u* = a/uw, surface tension parameter
6 = aeration, gas holdup volume fraction
x = vG/(pL*fJ*)1/3, Hughmark correlation parameter
IC/ = ( p ~ / p ~ * ~ ) ' / ~physical
/u*,
properties parameter
L i t e r a t u r e Cited

Akita, K., Yoshda, F., Ind. Eng. Chem. Process Des. D e v . , 12, 76 (1973).
Anderson, R. J., Russell, T. W. F., Chem. Eng., 72(26), 99 (1965).
Botton, R., Cosserat, D., Charpentier, J. C., Chem. Eng. J., 16(2), 107 (1978).
Chisholm, D., Brit. Chem. Eng., 12(9), 1368 (1967).
Cichy, P. T., Ultman, J. S., Russell, T. W. F.. I d . Eng. Chem., 61(6), 6 (1969).
Fair, J. R., Lambright, A. J., Andersen, J. W., I d . Eng. Chem. Process Des.
D e v . , 1, 33 (1962).
Gomezplata, A,, Nlchols, C. R., Chem. Eng., 74(4), 182 (1967).
58 (1957).
Govier, G. W., Radford, B.A., Dunn, J. S. C., Can. J . Chem. 5-19.,
Hershey. R. L.. D S c . Thesls, Massachusetts Institute of Technology, 1935.
Hills, J. H., Chem. Eng. J., 12, 89 (1976).
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Hughmark, G.A., Chem. Eng. Prog., 58(4), 62 (1962).
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Received for review May 4, 1979

Accepted March 6, 1980

Individual and Simultaneous Absorption of Dilute NO and SO2 in

Aqueous Slurries of MgS03 with Fe'I-EDTA
Eizo 'Sada' and Hidehiro Kumazawa
Department of Chemical Engineering, Kyoto University, Kyoto, 606, Japan

Ichibei Kudo and Takashi Kondo

Department of Industrial Engineering, Aichi Institute of Technology, Toyoda, 470-03, Japan

The absorption rates of (1) NO in aqueous solutions of Fe"-EDTA, (2) NO in aqueous solutions or slurries of MgS03
with added Fe"-EDTA, and (3) NO in the presence of SO2 in aqueous slurries of MgS0, with added Fe"-EDTA
were measured using a stirred vessel with a plane gas-liquid interface at 25 O C and 1 atm. The forward rate constant
of the complexing reaction, NO Fe"-EDTA e Fe"(EDTA)(NO),at various pH's was derived from the enhancement
factor for absorption of NO in aqueous solutions of Fe"-EDTA. The reduction of NO coordinated to Fe"-EDTA
with S
O
:
is found to be very slow as compared with the above compiexing reaction. Coexisting SO2 can promote
the absorption rate of NO by aqueous slurries of MgSO, with Fe"-EDTA. It is believed that coexisting SO2 plays
O
:
from the complex Fe"(EDTA)(SO:-)(NO) and that the presence of SO2 in the gas phase
a part of releasing S
effectively improves t h e pH of the solution at the interface toward favorable values for the reaction of NO with
Fe"-EDTA.

-+

Introduction
The removal of nit,rogen oxides (NO,) as well as sulfur
oxides (SO,) emitted from stationary combustion facilities
has recently been required to protect the atmospheric
environment. A number of wet and dry processes appropriate for the removal of NO, have been developed and
some wet scrubbing processes are capable of removing SO,
simultaneously. The wet scrubbing method, however, has
a significant disadvantage of inevitable waste-liquor
treatment. In considering such a drawback, it appears that
aqueous solutions of Fe(I1) chelate are promising liquid
absorbents of NO because of easy regeneration.
In our previous pa:per (Sada et al., 1978a), the kinetics
of absorption of NO in aqueous FeS04 solutions were
checked for wide operating conditions, i.e., for exposure
times of 0.2-5000 s and NO concentrations of 100 ppm99% by volume using a wetted wall column, a quiescent
liquid, and a stirred vessel with a plane gas-liquid interface. It was concluded that the chemical absorption process could be predicted satisfactorily by a theory of gas
absorption with reversible reaction of the form of A + B
~ r ?E. However, their absorption rates seem too low from
the standpoint of practical application. Recently, it was
shown that an aqueous solution of FeLEDTA (ferrous ion
coordinated to ethylenediaminetetraacetic acid) rapidly
reacts with dissolved NO and has a very large absorption
capacity for NO. Furthermore, it was reported that some
reducing agents such as Na2S03can reduce NO coordi0196-4305/80/1119-0377$01 .OO/O

nated to Fe"-EDTA and a high absorption rate can be

maintained.
It is one purpose of this paper to investigate the kinetics
of the complexing reaction between NO and Fe"-EDTA
as well as the reduction of NO coordinated to Fe'I-EDTA
with S032-by chemical absorption methods. To such an
end, the absorptions of dilute NO in aqueous solutions of
Fe"-EDTA and in aqueous slurries of MgSO, with added
Fe"-EDTA were performed using a stirred vessel with a
plane gas-liquid interface. From the experimental results
on the former absorption system, the forward rate constant
of the complexing reaction was determined, and it was
deduced from those of the latter absorption system that
the reduction of NO coordinated to Fe'I-EDTA by SO;is very slow and occurs only in the bulk of the slurry.
Therefore, conceivably sulfur dioxide coexisting with nitric
oxide cannot reduce the absorption rate of nitric oxide.
The merit of the usage of MgS03 slurry as a reducing agent
is high absorption capacity for SO2. Thus, it is considered
that an aqueous slurry of MgS0, with Fe"-EDTA is
suitable for simultaneous treatment of NO and SOz. Another purpose is to analyze the simultaneous absorption
mechanism.
Experimental Section
Experiments were carried out on the following absorption s stems: (1)absorption of NO in aqueous solutions
of FeIZEDTA, (2) absorption of NO, (3) absorption of SO2,
and (4) simultaneous absorption of NO and SO2in aqueous
0 1980 American Chemical Society