I

ORNL/MIT-300

WSSR

Analysis of Barium Hydroxide and

Calcium Hydroxide Slurry
Carbonation Reactors
K. D. Patch
R. P. Hart
W. A. Schumacher

:r,;r ;o uriimirta
 ORNL/MIT-300

Contract No. W-7405-eng-26

EMPLOYEE RELATIONS DIVISION

ANALYSIS OF BARIUM HYDROXIDE AND CALCIUM

HYDROXIDE SLURRY CARBONATION REACTORS
K.D. Patch
R.P. Hart
H.A. Schumacher

Consultants
G.L. Haag, D.W. Holladay, and D.F. Green

Date Published - May 1980

Oak Ridge Station

School of Chemical Engineering Practice
Massachusetts Institute of Technology
K.J. Fallon, Director

Oak Ridge National Laboratory

Oak Ridge, Tennessee 37830
Operated by
Union Carbide Corporation
for the
Department of Energy
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 ABSTRACT
The removal of CO2 from air was Investigated by using a continuous-
agitated-slurry carbonatlon reactor containing either barium hydroxide
[Ba(0Ky or calcium hydroxide [Ca(0H) ]. Such a process would be applied
l4
2

to scrub C02 from stack gases at nuclear-fuel reprocessing plants. De­

contamination factors were characterized for reactor conditions which
could alter hydrodynamlc behavior. An attempt was made to characterize
reactor performance with models assuming both plug flow and various
degrees of backmlxlng In the gas phase. The Ba(0H) slurry
2

enabled Increased conversion, but apparently the process was controlled

under some conditions by phenomena differing from those observed for car­
bonatlon by Ca(0H)2. Overall reaction mechanisms are postulated.
 V

Contents

Page
1. Summary 1
2. Introduction i
2.1 Background 1
2.2 Theoretical Considerations 2
2.2.1 Overview 2
2.2.2 Integration of the Carbonatlon Rate Expression 5
3. Apparatus and Procedure 6
3.1 Apparatus 6
3.2 Procedure 8
4. Results and Discussion 8
4.1 Ca(0H) Reactor
2 8
4.2 Ba(0H) Reactor
2 13
5. Conclusions 17
6. Recommendations , 17
7. Acknowledgment 17
8. Appendix 18
8.1 Carbonatlon Rate and Interfaclal Area Expressions 18
8.2 Physical and Chemical Properties 19
8.3 D>ta and Computer Ana lysis 22
8.4 Location of Original Data 32
8.5 Nomenclature 32
8.6 Literature Referenced 33
8.7 Literature Surveyed 35
 1

1. SlfKARY

Removal of CO? (330 ppm) from an air stream was studltd 1n a contin­
uously sparged, agitated-slurry carbonatlon reactor. The C02 content of
the outlet gas was measured for barium hydroxide [Ba(0H)2] and calciua
hydroxide [Ca(0H)z] slurries at various operating conditions, and results
were compared with those of Sheppard et al. Qj>), who investigated ta(0H)9
slurries. Decontamination factors (DFsTrahged from 3 to 1200 for Ca(0Hj2
and from 60 to 2100 for Ba(0H)2. For both slurries, lower values of OF
were observed at higher gas flow rates and lower impeller speeds. On the
other hand, the importance of backmixing for the high-conversion Ba(0H)2
system apparently caused the DF's to pass through an optimum at conditions
toward the opposite extreme, whereas bactaixing had a smaller effect on
conversion by Ca(0H)2, which was primarily controlled by the available gas-
liquid interfacial area. Increased slurry loadings enhanced conversion
for Ba(0H)2 slurries, In contrast to the opposite effect noted foi Ca(0H)2
slurries. A gas-solid reaction which competes with reactions in the
liquid phase Is postulated for the Ba(0H)2 case.
An empirical relationship was developed for the Ca(0H)2 system, which
accounts for a degree of backmixing of the gas phase intermediate to that
inherent in the plug-flow and perfectly backmixed models. A nonlinear
regression yielded the optimal correlations:

0 9 7 1 0 1 1 2 3
a = (/.SxlO^N - ^ ^- ' ^}- cm /cm

4 0 54 0 34 43 3 0
n = (1.4 x 10 ) I f - U' S-°' df -

where a Is the gas-liquid interfacial area (cm^/cm^), n is the number of

equal CSTR's (constant stirred tank reactors) in series, N is the Impeller
speed (rps), U is the superficial gas velocity (cm/s), S is the weight
fraction of solids, and dj Is the impeller diameter (cm). Predicted values
for Interfacial area varied from 0.8 to 2.3 cm2/cm3, and values for the
number of equal-volume CSTR's were between 3 and 15. No correlation was
recommended for the Ba(OH)? system due to the lack of data obtained, the
unrealistic values achieved for a and n, and the differing hydrodynamlc
and chemical phenomena postulated.

2. INTRODUCTION

2.1 Background

Nuclear-fuel reprocessing plants emit stack gases that contain signifi­

14
cant amounts of carbon-14 In the form of C02. which should be removed to
prevent possible health hazards (5, 8 ) . Carbon-14 has a 5730-yr half-Ufa,
 2

and there Is some concern that It may be Incorporated into the food chain,
possibly leading to mutagenesis. Essentially complete removal of CO2 from
the gas stream can be accomplished by reaction with agitated alkaline slur­
ries. The carbonate product is very stable and satisfies many long-term
disposal requirements.
Agitation increases gas-liquid phase subdivision, as well as the degree
of liquid-phase mixing. Phase subdivision produces relative motion between
the phases and increases the gas-liquid interfacial area (2., 2 , 16, U . ) ;
both effects contribute to a higher reaction rate by increasing the overall
mass transfer. The interfacial area is the principle variable determining
the capacity of an agitated gas-liquid reactor (2_lJ.
Previous workers (3, 4, 5_, 6, 8, 12, 15) have investigated calcium
hydroxide [Ca(OH)?] slurries for removal of CO2. The carbonation reaction
for barium hydroxide [Ba(0H)2], however, has not been investigated. Study­
ing the significantly higher rate of reaction of Ba(0H)2, due to the much
greater solubility of the hydroxide (5.6 g/100 g H2O vs 0.2 g/100 g H2O),
should yield a better understanding of the overall carbonation process under
slurry conditions.
The objective of this study was to develop a model for the performance
of Ca(0H)2 and Ba(0K)2 slurry reactors by: (1) developing empirical rela­
tionships for interfacial area and degree of mixing as a function of the
hydrodynamic parameters of the reactor and (2) summarizing the results from
both alkaline slurries to develop a model that can be extended to other
systems.

2.2 Theoretical Considerations

2.2.1 Overview

Juvekar and Sharma (8) discuss the overall process for the absorption
of CO2 Into an alkaline slurry as outlined below:

2+
X(0H") (s) ^
2 X ( a q ) + 20H"(aq) (1)

C0 (g) ^
2 C0 (aq)
2 (2)

C0 (aq) • 0H"(aq) - • HCO3 * )

2
a q
(3)

HCO^aq) + 0H"(aq) - * H 0 + C0£"(aq)

2 <*>

2+
X ( a q ) * CO^'(aq) - %COJs) • (5)
 3

where X = Ba, Ca
Sections (4) and (5) are instantaneous, and thus the rate-controlling
step is either the dissolution of the hydroxide or the absorption and subse­
quent reaction of C0>. Reaction (1) is essentially at equilibrium due to
the excess of X(0H)2(s) present and the relatively small amount of CO2 ab­
sorbed from the gas. Combining the individual rate expressions for the
transport o f CO? through the gas film, transport o f CO2 into the liquid,
and reaction of CO2 with the hydroxy! ions yields the following rate ex­
pression (see Appendix 8 . 1 ) :

Ra = V W (6)
where
2
R = specific rate of CO2 absorption (gmol/s-cm )
a = gas-liquid interfacial area (cm2/cm3)
K, = psueo first-order rate constant (gmol/cn^-s-kPa)
P fl = average pressure of the gas in the contactor (kPa)
x = mole fraction of COg in the gas

The pseudo first-order rate constant in Eq. (6) is actually a function 1

of several parameters, as given by Danckwerts surface renewal theory (3):

H [ O H ] + K
^COK2 ~ L
K a
l . _~ (7)
H

1*
VW2^*T
2
h
where
B
DC0 2 diffusivity of C 0 in aqueous solution (cnrVs)
2

H » Henry's coefficient of solubility (gmol/cnP-kPa)

Kg * second-order rate constant (cmfygmol-s)
Kg • gas-s1de mass transfer coefficient (gmol/cm2-s-kPa)
K, • I1qu1d-s1de mass transfer coefficient In the absence of
chemical reaction (cm/s)
 4

Several authors (2, 8, jS) consider the liquid-phase mass transfer

coefficient to be essentially independent of the operating conditions such
as gas flow rate, bubble diameter, and mixing intensity; however, there
are conflicting opinions concerning this parameter. Danckwerts (3) reports
that %i is constant at relatively low speeds of agitation for which the mean
bubble diameter is greater than 2.5 mm. His values for K|_ then drop sharply as
the speed of agitation is Increased and thereafter remain constant. He
contends that K|_ decreases because bubbles behave hydrodynamlcally as rigid
spheres, with a relatively low KL» when they are reduced to diameters less
than 2.5 an. Miller Q l ) also reports that liquid-film-controlled mass
transfer is dependent on mean bubble size. Bubble shape, motion, and any
tendency for the interface to ripple, fluctuate, o- otherwise deform, might
also influence mass transfer, yery little information is available in the
literature on the gas-side mass transfer coefficient, K G , in mechanically
agitated V2ssels (JO).

Many conflicting investigations of interfacial area have been published

in the literature (Z\). Reith (_H) notes that experiments performed in
vessels with the same dimensions, filled with the same liquid, and operated
under Identical conditions, may lead to completely different interfacial
areas when different measuring methods (such as light scattering, light
reflection, and photography) are used. Calderbank (2)> by utilizing a
light-scattering technique, showed that the interfaci&l area across a par­
2 3
ticular radius of a 100-liter tank can vary from 0.7 to 1.08 cr. /cm . In
3
addition, extreme variations with reactor depth (0 to 1.2 cm2/cm ) are pos­
sible.

The expression most commonly cited for Interfacial areas is that de­
rived by Calderbank (2), who correlates interfacial area with the power
dissipated by the agitator:

0 , 4 2
aa s ! 44 P P°' #JL)l/2
}
1 4
'* a0.6 \t

0,7 0/3
[(djNp/ji) (Ndj/U) < 20,000]

where
3
P » power dissipated per unit volume of liquid (hp/ft )

P * density of the liquid (g/cm ) 3

5 1
a •
surface tension of the liquid (10 J/cm )
U «
superficial gas velocity (cm/s)
U
t *
upward velocity of bubbles (typically 26.5 cm/s)
 5

dj = impeller diameter (cm)

N = frequency of impeller rotation (s" )
u = liquid viscosity (g/cm-s)

Because Eq. (8) refers to pure liquids rather than to a mixed phase, its
usefulness in predicting interfacial areas in slurries is questionable. In
addition, the Calderbank correlation relies on an accurate estimate of the
power consumption which, for bubbling reactors, requires much empiricism.
The complexity of factors influencing power consumption in this case have
led some researchers to doubt the practicality of achieving universal rela­
tionships to predict power consumption accurately, except for the cases of
limited ranges of the relevant variables (18).

2.2.2 Integration of the Carbonation Rate Expression

Equation (6) can be integrated assuming: (1) K|_a is constant throughout
the vessel, (2) the liquid is mixed well, and (3) the gas phase is in plug
flow. It can then be shown that (see Appendix 8.1):

*n(DF) = a a (9)
where
OF = decontamination factor - inlet C 0 mole fraction/outlet CO? 2

mole fraction

3
V.a * aerated liquid volume (cm )

= m e c u a r
^air °l ^ weight of air (g/gmol)

Q » air flow rate at 21 °C and 101 kPa U/min)

P a 1 r * density of air at 2«°C and 101 kPa (g/cm ) 3

Equation (6) can also be Integrated after assuming that the gas phase can
be modeled as n equal-volume CSTR's in series, which accounts for varying
degrees of backmlxing In the gas phase (see Appendix 8.1);
 6

OF (1 + M n
} (10)

If n is unity, Eq. (10) models the behavior of the gas phase as being per­
fectly backmixed. The limiting behavior as n approaches infinity is that
of plug flow, as given by Eq. (9).

3. APPARATUS AND PROCEDURE

3.1 Apparatus

The experimental apparatus is shown in Fig. 1, and vessel specifica­

tions are listed in Table 1. The impeller, a 6-bladed Rushton turbine,
was driven through a 2:1 reduction gearbox by a compressed-air motor,
while the speed was monitored with a stroboscope. Water flowing through
cooling coils kept the temperature of the slurry at 292 K.

Table 1. Vessel Specifications

Tank diameter 27.3 cm

height 35.0 cm
Baffles number 4
width 2.7 on (1/10 tank diameter)
Impeller type 6-blade Rushton turbine
diameter 13.7 cm
position (above tank bottom) 11 cm (4/10 tank diameter)
Sparger type 0.95 cm open pipe
extension above tank bottom 5.5 cm

The reactor was operated 1n semi-batch mode by continuously passing

gas through a slurry. The air flow was measured by a calibrated rotameter
and entered the reactor through and open-pipe sparger located directly
under the Impeller. In all experiments the pressure above the slurry was
held at 112 kPa.
 BELLOWS
PUMP
EXIT GAS
STROBOSCOPE INFRARED A

DETECTOR

' i\ C )
KNOCKOUT BOTTLE? ^ I1 1 0 O

<©«K) —. 0 ( J ,
TO VENT
1— °'VOLTMETER1 I
PRESSURE GAUGE
THERMOMETE! CHART RECORDER

REACTOR

MASSACHUSETTS INSTITUTE OP T I C H N 0 L 0 6 Y
SCHOOL OP CHEMICAL ENOINEERINO PRACTICE
AT
OAK RIDGE NATIONAL LABORATORY

EXPERIMENTAL APPARATUS

INLET GAS DATE DRAWN BY PILE NO. PIO.

10-11-79 RPH CEPS-X-3001
 8

The sample stream of effluent gas passed through a series of three

knockout bottles to remove any entrained slurry or condensed water vapor.
A bellows punp maintained a constant flow to a Wilkes-Foxboro Model 1-A
Infrared Spectrometer set at a wavelength of 4260 ran. Exit CO, concen­
trations were measured at a path length of 20.75 m, with the temperature
and pressure kept at 320 K and 136 kPa respectively. The output was dis­
played on both a digital voltmeter and a strip-chart recorder. A calibra­
tion curve allowed conversion of measured voltages to CO2 concentrations.

3.2 Procedure

The reactor was charged with about 16 liters of slurry containing the
desired Ba(0H) solids concentration. The desired air (330 ppm CO2) flow
2

rate was set, followed by the adjustment of the Impeller speed. The exit
CO? concentration was continuously monitored on the strip-chart recorder, •
and on reaching steady-state conditions, the agitated slurry height and
exit CO2 concentration <*ere recorded. Care was taken to avoid any entrain-
ment of slurry from the reactor; thus upper limits on the flow rate and
impeller speed were established. The values of operating conditions are
presented in Table 2. •

Table 2. Experimental Variables

Variable Values

Impeller speed (rpm) 350, 450, 550, 650

Flow rate U/min) 10, C , 44

Weight % solids 12, 21
Slurry Ba(0H) • 8H 0
2 2

4. RESULTS AND DISCUSSION

4.1 Ca(0H) Reactor

2

Preliminary experiments conducted with BafOH)? slurries indicated

severe blockage of the T-sparger located beneath trie impeller. It was
postulated that the Increased rate of reaction, as compared with the '
Ca(0H)2 system, resulted In deposition of the carbonate onto the sparger.
To circumvent this problem, the T-sparger was removed, leaving an open-
pipe sparger. Experiments with Ca(0H)2 slurries were repeated and com­
pared with results obtained previously Q 5 ) (F1g. 2 ) .
 A OPEN PIPE SPARGER
100
O T-SPARGER

50 GAS FLOW RATE

(Jt/min)

£
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250 350 450 550
650
Impeller Speed (rpm)

Temperature * 292 K MASSACHUSETTS I N S T I T U T I Of TECHNOLOGY

SCHOOL Of CHEMICAL ENGINEERING PRACTICE
AT
C0„ Inlet Concentration * 330 ppm OAK RIDGE NATIONAL LABORATORY

EXIT C 0 CONCENTRATION VS IMPELLER SPEED

2

WT % C A ( 0 H ) SLURRY
2

DATE OUAWK «Y
IflLE NO.
IEPS-X-300
no.
 10

Mesterterp (20) also round that the method of gas injection made
little difference if gas were fed to the eye of the impeller. The results
shown in Fig. 2 corroborate his observation, with the exception of the
open-sparger run at a gas flow rate of 44 t/min. The inconsistently high
exit CO2 concentration at this higher flow rate could be due to some by­
passing of large gas bubbles around the impeller. The T-sparger previously
used was placed 7.6 cm from the bottom of the tank, whereas the current
opeh-pipe arrangement released the air 5.5 cm from the tank bottom. This
effect should be investigated further if more tests are to be run at high
gas flow rates with the current sparger arrangement.

The decontamination factors calculated from Fig. 2 range from about

3 to 1200. For both modes of gas introduction, the same qualitative be­
havior is observed. Extent of reactor conversion increases with increasing
impeller speed, but decreases with increasing gas flow rates. Increased
agitation is expected to increase the gas-liquid interfacial area because
bubbles will rupture and form ones of smaller diameter. This will enhance
the extent of conversion if the overall reaction is controlled by mass trans­
fer at the interface and If the increased backmixing associated with greater
agitation produces a less significant effect.
Increasing gas flow rate will Increase both the mean bubble diameter
and the gas holdup (11). The former effect will decrease the specific
interfacial area whereas the latter will increase it, so that the overall
reactor conversion is not obvious. In addition, greater gas flow rates
also lead to shorter residence times and consequently to lower degrees of
backmixing, which would tend to enhance reactor conversion. The results
in Fig. 2 indicate that the change in mean bubble diameter is the dominating
phenomenon under the conditions examined. For the purposes of hydrodynamic
modeling, it generally appears that backmixing of the gas phase can be
neglected as a first approximation.

By assuming the gas phase to be in plug flow, multiple linear regres­

sion techniques were used to obtain the following correlation for inter-
facial area from the data in Fig. 2 and the additional data of Sheppard
et aj.. (lj>) for Ca(0H) slurries (see Appendix 8.3):
2

0 6 3 0 4 2 0 1 1 6 0 4 4 2 3
a = 0.059 N ' U ' S" - dj ' cm /cm (11)

where N Is the impeller speed (rps), U Is the superficial gas velocity

(cm/s), S is the weight fraction of solids, and dj 1s the impeller diameter
(cm). The correlation predicts the Interfacial area will Increase with in­
creasing Impeller speed and gas flow rate, as was postulated above. Calcu­
3
lated Interfacial areas ranged from 0.5 to 2.0 cm^/cm , results which are
within the range of reasonable values (8, W, 21). Interfacial areas were
also calculated when assuming a backmlxed gas pfiase but those values, ranging
3
from 1.5 to 150 cm^/cm , seemed to be excessively large (see Appendix 8.3).

Many authors feel that the gas phase 1s best described by plug flow
(7, 11, 12) especially at low speeds of agitation; however, there are
 11 #

conflicting opinions as to whether a plug flow or backmixed model Is appro­

priate. Calderbank (2) finds that his results correlate best when complete
backmixing is assumed. Several authors Q i , 18, Jl) find that impeller-
induced coalescence of recirculating bubbles is significant and, under many
conditions, the gas bubbles leaving the impeller zone are composed mainly
of recirculating gas. In addition, it has been demonstrated that gas bub­
bles passing through the impeller region are much more likely to be coalesced
in pockets above the impeller blades than to undergo simple rupturing that
has been previously envisaged Q 9 ) . Thus, neither a simple plug-flow nor a
perfectly backmixed model for the gas phase can be considered adequate.

The experimental data also exhibit the inadequacy of a plug-flow model.

A comparison of measured decontamination factors with those predicted by the
plug-flew irodel is presented in Fig. 3. Although the correlation seems to be
acceptable a*, lower decontamination factors, reactor efficiency is overestimated
at conditions procicing higher decontamination factors. Backmixing appears
to significantly reduce the conversion efficiency if the reactor is operated
at low flow rates and high impeller speeds.

In an attempt to account for different degrees of backmixin<j in the gas

phase, the system was modeled as CSTR's in series. Simultaneous empirical
relationships were obtained for the number of equal-volume CSTR's n and the
interfacial areas a as functions of the measured hydrodynamic parameters
of the reactor. Using nonlinear regression (see Appendix 3.1), power-law
correlations of the following form result

4
n = (1.4 x 10 ) -0.54 yO.34 -0.43 ^ - 3 . 0
N s ( 1 2 )

3 0 9 7 0 1 3 - 0 1 1 1 1
a = (7.8 x N T ) N ' U * S ' dj ' (13)

The ir-odel predicts an increase In interfacial area with increases in

impeller speed, gas flow rate, and impeller diameter, as expected. A de­
crease in interfacial area is indicated for an increase in solids content,
possibly due to bubble coalescence at the solid particles. A trend toward
greater backmixing decreasing n) occurs with increasing impeller speed,
impeller diameter, and solids content, whereas an increase in gas flow
rate suggests an approach to plug-flow conditions. Values of Interfacial
area generated from this model range from 0.8 to 2.3 cm2/cmJ, and the num­
ber of equal-volume CSTR's varies between 3 and 15. ^lues of n greater
than 10 can be shown to indicate essentially plug-flow behavior (9).

A measure of the applicability of this model is shown in Fig. 4, where

measured and predicted decontamination factors are compared. In contrast
to Fig. 3, the correlation appears to be an improved representation of the
experimental data throughout the range studied.
 12

8-

6 -

!
*- 4 -

2-

tn x /Xr (experimental)
0

Temperature - 292 K MASSACHUSETTS INSTfTUTK O f TKCHN0LO6Y

SCHOOL OP CHEMICAL ENGINEERINC PRACTICE
x * mole fraction CO- AT
OAK RIDGE NATIONAL LABORATORY

PREOICTEO VS EXPERIMENTAL
DECONTAMINATION FACTORS
FOR PLUG-FLOW MODEL
|OATI DRAWN BY PILE NO. PIC.
10-14-79 RPH CEPS-X-300
 13

4.2 Ba(OH) Reactor

9

Initial studies involving Ba(0H) indicated that foaming of the slurry

2

was a significant problem which led to the entrainment and deposition of

slurry in the sample line and the first knockout pot. The gas flow rates
examined were consequently restricted to valuer less than 50 t/min.

The Ba(0H)2 slurries yielded substantially higher conversions than did

the Ca(CH)2 cases investigated. From Figs. 5 and 6, decontamination factors
for the former can be calculated as ranging from 60 to 2100. The different
qualitative behavior of thase curves also suggests the possibility of other
overall reaction mechanisms under these conditions.

Figure 5 illustrates the effect of flow rate on exit CO2 concentration

as a function of impeller speed. Note that exit CO2 concentrations are an
order of magnitude less than those obtained for Ca(0H)2 (Fig. 2 ) . The
Ba(0H)2 curves reach a CO2 concentration minimum at approximately 550 rpm,
in contrast to the Ca(0H)2 slurries, for which the CO2 concentration steadily
decreases with increasing impeller speed (Fig. 2 ) . Apparently the increased
backmixing at higher agitation speeds and lower gas flow rates is not bal­
anced by a corresponding increase in interfacial area. Slight changes in
the residence-time distribution at the high conversions of the Ba(0H)2 sys­
tem (^99.9%) could significantly alter the extent of reactor conversion
and lead to the effects observed.

The effect of solids content on CO2 conversion is shown in Fig. 6. The

apparent trend indicates that CO2 removal efficiency improves with increasing
solids content. The CafOH)? system manifests the opposite effect. The ex­
planation may lie in competing effects between bubble coalescence and gas-
solid reaction. As mentioned above (Sect. 4.1), increased solids concentra­
tion may increase bubble coalescence and thus decrease interfacial area and
conversion; however, it is also possible that a significant gas-solid reaction
exists. If the gas-solid reaction effect were more pronounced than the coales­
cence effect, one would expect the trend observed in Fig. 6. The literature
does not elucidate this problem but only states that conversion is highly
dependent on the system in question.

From the above discussion and attempted correlations using the experi­
mental data, It is obvious that the simple plug-flow model above could not
explain the observed behavior of the Ba(OH)? system. In addition, modeling
the system as a series of stirred tanks yields results that
are physically intractable. Since the optimal correlation predicts 0.1
CSTR In series and Interfacial areas on the order of I P cn?/ca&
5 0
f the re­
sults are clearly unrealistic. Undoubtedly the poor correlation is also
attributable to the lack of data; only 27 data points are available for the
nonlinear-regression correlation of eight paraiwters (96 data points are
used for the Ca(0H)2 correlation). Evidently a better knowledge of the
residence-time distribution of the gas and the variation of mass transfer
coefficients, as functions of the various hydrodynamic parameters, Is re­
quired to predict the behavior of hydroxide slurry carbonation reactors
operating at conversions exceeding 99%.
 14

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Temperature « 292 K
MASSACHUSf TTS INSTITUTf O f T f CNNOLOCT
x * mole fraction C0» SCHOOL OF CHEMICAL EWONEEItlNO PRACTICE
AT
OAK RIDGE NATIONAL LABORATORY

PREDICTED VS EXPERIMENTAL
DECONTAMINATION FACTORS
FOR n CSTR'S IN SERIES MODEL
DATE lORADN I V FILE NO. no.
10-22-79 I RPH CEPS-X-300
4 1
 1
15

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10.0-

5.0

a. 2.0
44 t/mln
CM
/
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c
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0.2

0.1 X X
150 250 350 450 550 550
Impeller Speed (rpm)

MASSACHUSf TTS INSTITUTE Of TCCNN0LO6T

SCHOOL 0^ CHEMICAL OfOMECUfNO MACTICI
AT
OAK RIDGC MATIO-AL LASORATOftT

Temperature - 292 K
EXIT C 0 CONCENTRATION VS IMPELLER SPEED
2

Inlet concentration of CO, 330 ppm FOR 21 WT X B a ( 0 H ) SLURRY

2

DATE MAIN tY Hit NO,

(-3Qol
ML- i.
 16

24 t/nin gas flow rate

5.0
Ba(0H)_ slurries

2.0
CM
o

c
1.0
o 12 wt X

0.5 wt X
01
o
c
oo

0.2

0.1 J. _L -L 1
150 250 350 450 550 650
Impeller Speed (rpm)

MASSACNUSf TTS INSTITUTE 0 * TECHNOLOGY

Temperature * 292 K SCHOOL OF CHEMICAL ENGINEERING PRACTICE
AT
OAK RIDGE NATIONAL LABORATORY
Inlet concentration of C 0 * 330 ppm
2

EXIT C 0 CONCENTRATION VS TMP&IER SPEED

2

FOR DIFFERENT SOLIDS LOADINGS

OATf DRAWN BY FILE NO. Fie.
10-22-79 RPH DEPS-X-300
 17

5. Conclusions

1. Ba(OH) has a much greater C 0 removal efficiency than Ca(CH) -

2 2 2

2. It Is possible to model Ca(0H) slurries by accounting for both

2

the Interfaclal area and degree of mixing as functions of the hydrodynamlc

parameters.
3. Ba(OH)? slurries cannot be characterized by using simple plug-flow
or backmixed models.
4. Ba(0H) slurries produce an Increase In COg removal efficiency
2

with Increasing solids concentration, wherecs the opposite behavior Is

noted for Ca(0H) slurries.
2

6. Recomnendatlons

1. A better knowledge of residence-time distributions of the gas

phase in the agitated contactor is necessary when attempting to correlate
interfacial areas in slurry reactors.
2. Additional Ba(0H) data are needed to better characterize system
2

behavior.
3. Relationships for mass transfer coefficients as functions of hydro-
dynamic parameters of the reactor are needed to improve modeling of slurry
systems.
4. Improvements in the reactor design could be made by placing the
sparger closer to the impeller to avoid gas bypassing and Increasing dead
height above the slurry surface to reduce entrainment of Ba(OH). foam.

7. Acknowledgment

The authors thank their consultants, 6.L. Haag, D.U. Holladay, and
O.F. Green, for their guidance and Inspiration, who always gave generously
of their time, assistance, and moral support.
 18

8. APPENDIX

8.1 Carbonation Rate and Interfacial Area Expressions

1
The rate of reaction of C0 in the liquid film is given by Dankwerts
2
surface renewal theory (3):

Ra = Kp a Pj (14)
where
KR = H ^Dco ^[OHM+K*

R - specific rate of absorption of CO2, gmol/cnP-s

a = interfacial area, cm^/cm*
H - Henry's coefficient of solubility, gmol/cm^-kPa
Dco 2 = diffusivity of CO2 in aqueous solution, cm2/s
K2 = second order rate constant, cmtygmol-s
3
[0H~] = hydroxide concentration, gmol/cm
s
Kf_ liquid side mass transfer coefficient, cm/s
Pj * partial pressure of C0 at the gas/liquid interface, kPa
2

The rate of reaction In the liquid must be balanced by the rate of trans­
port of CO2 through the gas film at steady state (8):

Ra - Kga (P - P,) 6 (15)

where Kg Is the gas side mass transfer coefficient (gmol/cnl-kPa) and Pg

1s the partial pressure of CO2 in the gas stream (kPa). Eliminating Pi
from Eqs. (14) and (15) gives:

to
* 1 • (VK )
[
6
3 8 P
G "" l K 3 P
6 (16)
 19

where Kj is a pseudo first-order rate constant, gmol/c«2-kPa-s. The par­

tial pressure of CO2 can be related to the total pressure by

PG - *P a v g 07)

where x is the mole fraction of CO2 in the air stream and P is the
average pressure in the contactor, kPa. Combining Eqs. ( K T and (17) we
obtain:

R a = K a P x { 6 )
l avg

Under the assumptions that the liquid phase is well-mixed and that the
gas travels through the contactor in essentially plug flow, we can write
the following differential mass balance on CO2:

-6 dx = RaA dz (18)

where G is the molar gas flow rate (gmol/s), A is the contactor cross-
sectional area (cm2), and z is the vertical height in the reactor (cm).
Combining Eqs. (6) and (18) and integrating between initial and final
conditions yields the equation given previously:

1n(£) = aa (9)

Treating the gas phase as n equal-volume CSTR's in series [as opposed

to an infinite number which is implicit in the development of Eq. (9)],
one can easily obtain:

+
r • " ir>"
f <"»

8.2 Physical and Chemical Properties

8.2.1 Henry's Law Constant

At 20°C the solubility of Ba(OH) in water is 5.6 g/100 g water;

2

therefore, the concentration of the OH" ions is 0.355 M. The Henry's Law
solubility constant for CO2 in pure water (H ) at 20°C is 3.9 x 10-7
0
3
gmol/cm -kPa (3_). The correction for the effect of ionic strength or
Henry's constant is (3):
 20

log({{-) - -h I (19)

where h is the sun of contributions referring to the species of positive

and negative ions present, and I is the ionic strength of the solution
defined as:

I - \ I C Z* t (20)

where Cj is the concentration of ions of valence Zj. Using these values

for h from DanckMerts (4), h = 0.115 and I = 0.532, and substituting into
Eq. (19), H was found to equal 3.4 x 10-7 gmo1/cm3-kPa,

8.2.2 Rate Constant (IU)

The reaction between CO2 and OH" is

C 0 + OH" - ^ > HCOJ

2 (21)

and the rate expression is

R * K [C0 ]C0H"3
2 2 (22)

At infinite dilution the rate constant in pure water K2 is 5900 i/gmol-s

at 20°C (4). A correction must be made for the ionic strength of the solu­
tion, using Fig. 6 in Oanckwerts and Sharma (4):

Kg = KJ + 3200 I (23)

where I is the Ionic strength. Therefore, the corrected rate constants

are:

Ba(0H) :
2 K 2 * 7600 A/gnol

Ca(0H) :
2 K 2 * 6050 A/gmol
 21

8.2.3 Diffusivity

The diffusivity of C 0 in water at 20°C when the viscosity is 1.1

z
2

x 10~ g/cro-s was found to be (13):

5 2
Dco 2 = 1.4 x 10" cm /s

8.2.4 Mass Transfer Coefficients

The liquid-side mass transfer coefficient for CO2, K , was estimated L

byJuvekarand Sharma (.7) to be:

2
K L = 6.5 x 10" cm/s

This value was constant over the. range of experimental conditions

considered. The gas-side mass transfer coefficient for CO2, KQ, was
estimated from measured values of Kga, where a is the interfacial area.
6 3
Values of this product are approximately 10~ gmol/cm -s-kPa (_7). I f
the interfacial area is assumed to be 2 cmZ/cnr.the value of KQ is aboit
5 x 10-7 gmol/cmZ-kPa-s.

8.2.5 Viscosity and Density

The slurry densities were measured by making up the appropriate

solution vol unethically and weighing the solution. Viscosities at 20°C
were measured with a Brookfield viscometer fitted with an ultfa-viscosity
spindle Which rotated at 60 rpm. The results are shown in Table 3.

Table 3. Viscosities and Densities

Solution % Solids 3
Dens ity (g/cm ) Vi­scosity (10-2 g/cm-s)
0.5 M Ca(0H) 2 3.64 1.018 1.099
1.0 M Ca(0H) 2 7.14 1.038 1.210

1.5 M Ca(0H) 2
10.56 1.056 1.484

0.4 M Ba(0H) 2
11.86 1.064 1.150
0.75 M Ba(0H)o 21.11 1.121 1.200
 Tc

8.3 Data and Computer Analysis

Three computer programs were written to analyze the data. Two were
statistical analyses programs, while the third placed the data into a
form convenient for analysis. The first program listed was the program
used to calculate interfacial areas and decontamination factors (DF).
Data were read in free fonnat from a data file, in this case F0R21.DAT.
Calculations of interfacial area and DF were stored along with the initial
data in a new data file, F0R22 DAT, which was compatible with the statis­
tical programs. Separate versions of the program were made for the
barium hydroxide data, the 1979 calcium hydroxide data from this study,
and the calcium hydroxide study of Sheppard et al. (15), along with
separate sets of data files. The original data and the calculated inter­
facial areas obtained by using ideal reactor models are tabulated in Table 4.

The other programs were written to use the Statistical Analysis

System (1_) package available on the IBM 360 computer at ORNL. The second
program listed attempted to correlate interfacial area using a General
Linear Models Procedure (GLM). The GLM program used a multiple linear
regression to fit the data to the specified model. In addition, a step­
wise regression procedure was used to find the collection of independent
variables that best fit the data. The third program used a nonlinear
regression procedure to fit the data to a n-CSTR's-in-series model. The
program produces least-squares estimates of the parameters of the non­
linear model specified.
 23

1. Program 1

TYPE CALCBA.F0R
OOIOO C*** THIS PR0GRAM CALCllLATFS INTFRFACIAL ARFAS CI.A.'S)
OOPOO C*** F0R BA(0H)2 SLURRIES BASF!) UP0N TV0 M0DELSS
00300 c*** 1. PFRFFCT BACRMIXING ( 0NF CSTR)
J
00400 c*** P. PFRFFCT PLUG FL0<
00500 c*** THF THF0RETICAL DEVELOPMENT IS DFTAIl FD IN CFPS-X-^OO
00*00 c***
00700 c*** THF VARIABLES USFD ARF:
00800 c*** AIRDEN DFNSITY 0F AIR CG/CC)
00900 c*** AIRPT M0LECULAR VEIGHT 0F AIR CG/G-M0I.)
01000 c*** ALPHA A RATI0 0F RFACTI0N RATF T0 GAS
0 1 100 c*** FL0<-' RATF. (CM)
0 1 POO c*** AMIX = BACKMIXED IN1FRFACIAL AREA {CMP/CM3)
0 1300 c*** APLHG = PLUG FL0V 1NTERFACIAL ARFA (CMP/CM3)
01400 c*** C0PIN = INLET C0P C0NCENTRATT0N CPPR)
01500 c*** C0P0HT = 0IITLFT C0? C0NCFN1RATI0N (PPR)
01*00 c*** DC0? = DIEFUSIVITY 0F C0P IN AOUE0IIS
0 1 700 c*** S0LIITI0N (CMP/S)
01R00 c*** DIMP = IMPELLrR DIAMFRFR (CM)
0 1900 c*** FL0I-'
V0LUMETRIC FL0V RATF
c*** HEIT = AERATED HEIGHT IN C0NTACT0R Cl./MIN)
OPOOO
c*** HEITC = UNAGITATED SLURRY HFIGHT CC*»>
0P100
02200 c*** HENRYS = HFNRY'S C0EFFICIFNT 0F S0L1IBILITY (CM)
OP.100 c*** CG-M0! /CC-ATM)
0P350 r,*** IDF = DEC0NTAMINATI0N FACT0R
OP 400 c*** IRPM = RFV0LUTI0NS PFR MINUTF 0F THF
0P500 c*** AGITAT0R (/MIN)
02*00 C*** IRIIN = DATA P0INT NUMBER
0P700 c*** NPTS = NUMBFR 0F DATA P0INTS
OPROO c*** 0H = CONCENTRATION 0F HYDR0XIDF (G-M0I / C D
0PR50 c*** PERS0L = PERCENT S0LIDS IN SLURRY S0LHTI0N
02900 c*** PIN = INLFT CAS PRESSURE CPSIG)
0 3000 c*** PAV = AVERAGE GAS PRESSURF IN RFACT0R (ATM)
03100 c*** •S = CR0SS-SFC7I0NAL AREA 0F C0NTACT0RCCM?)
0 3P00 c*** SLUfcY = SLURY "PSFUD0 MOLARITY" (M0L/1 )
03300 c*** VA = AERATED V0LIIMF (CO
03350 c*** VISC = VISC0SITY 0F SLURRY S0LUTI0N (CP)
03400 c*** XKG s GAS SIDE MASS TRANSFER COEFFICIENT
0 3500 c*** 0F C0P (G-M0L/CMP-S-AT*)
0 3600
0 3700
c*** XKL = LI GUID SIDE MASS TRANSFFR
0 3R00
c*** C0EFFICIFN1 0F C0P (CM/^y
03900
c*** XKR S A LUMPED RFACTI0N C0NSTANT (G-W0L/CMP-S-ATW)
0 4000
c*** XK1 = P S F U D 0 F I R S T 0 R D F R KATE C 0 N S T A N T
c*** (G-M0LA:MP-R-ATM>
04100 c*** X X ? = S E C 0 N D 0 R D F R RATF C O N S T A N T (CC/G-M0L-S)
04P00 DATA ,
AIRrF.N/'.OOl?O5/#AIR1' T/?R.9*4/,C0PIN/3.3F5/#
0 4300 !DC0?/1.4E-5/,HFNRYS/3.4OF-S/,0W/3.55F-<4/',S/5RS./,
04400 ?XKr,/5.E-5/>XKL/*.5F-?/,XK?/7.*F*/
04500 XKR = HENRYS * SORT( DC0? * XKP * OH • X K L * * ? )
04*00 XKJ = XKR / ().") * XKR/XKG)
04f20 C*** N0TF» PRFSSURF AH0VE C0NTACT0R MAINTAINFP AT 1 . 5 PSIG
 24

0*640 C*** ME ASSUME PRESSURE T0 BF DUE T0 0NLY THF HYDR0STATIC

046*0 C*** HEAD 0F VATER IN THE C0NTACT0R.
0*680 PAV = N I 15
04700 READ ( P N 1 0 ) NPTS
04R00 10 FORMAT C I )
04900 D0 1 0 0 J a N N P T S
0500C READ < ? 1 , P 0 ) I R U N , DIWP, IRPM, SLURY. P I N . FL0V, H F I T ,
05100 1HE1TC, C0P0UT
05P00 ? 0 F0RMAT C I » E , I , 6 E )
0S400 VA = S * HFIT
05500 ALPHA = 0 . 0 6 * XKI • PAW * VA * AIR^T/CFI 0«-» * AIRPEN)
05600 C * * * CALCULATE INTFRFACIAL AREA F0R PLl'G FL0V M0PFL
05700 APLUG = AL0G(COPIN/C0P0I>T)/ALPHA
05B00 C # * * CALCULATE INTFRFACIAL ARFA FOR RACKMIXFD M0PFL
05900 AMIX = CC0PIN/COP0UT - N O ) / A L P H A
05930 I F (SLURY . E O . 0 . 7 5 > RH0 = N 1 P 1
05960 I F (SLURY . E O . 0 . 4 0 ) RHM = 1 . 0 6 4
06000 IF (SLURY . F O . 0 . 7 5 ) PERS0L = 0 . P 1 1 1
!
06100 I F (SLl RY . E O . 0 . 4 ) PFRS0L = 0 . 1 1 R 6
06P00 I F (• SLURY . E G . 0 . 7 5 ) V I S C = NPOO
06300 IF (SLURY . E G . 0 . 4 ) VISC = N150
06400 C * * * CALCULATE DECONTAMINATION FACTOR
06500 IDF = C0PIN/COP0UT • 0 . 5
06600 C * * * ST0RF DATA IN F0RPP.DAT FOR ANALYSIS BY SAS F-R0GRA*
06700 V'RITF(PP. 3 0 ) I R U N , IRPM, FLO'*, DIMP. RHO, P F R S 0 L . V I S C ,
06«*00 IHEITC. H F I T . I D E , ALPHA, API UG, AMIX
06900 30 F0RMAT(I3,I4,F5. N F S . | » F 6 . 3 , F 6 . 4 , F 6 . 3 . P F 5 . I . I 5 . F R . 4 .
06950 IF5.P.F7.P)
0 7000 100 CONTINUE
07100 ST0P
07P00 END

2. Program 2

f
4 1 7 ) , B I N P . K . P . PATCH*
/ / • C L A S S CPU9N40S,PRINT=*>0,CARPS=99, 10=3
/ • R 0 U 1 E PRINT LOCAL
/ / EXEC SAS76
/ / S T F P L I B DP D S N = A . F . I N 1 o 3 0 7 . S A S . L I B R A R Y . P I S P - S H R
/ / S A S . S Y S I N PD •
*•*
THIS PROGRAM CORRELATES HY0ROPYNAMIC PARAMFTFRS *'ITH
INTFRFACIAL ARFA AND PLOTS THF RFSULTS. IT ALSO
ATTEMPTS TO FIT THF PATA TO THF BFST EMPIRICAL MODEL.I
***
THE BULK 0F THF PROGRAM CONTAINS MISCFLLANF0US
CORRELATIONS FRO* CFPS-X-PR1 (197R)I
DATA IHTFPi
*••
 25

RFAD VARIABLFS FROM Di^TA F I l . F :

FXPFRIMFNTAL RUN. SPFFD CRPM>; GASFI.0W RATF C L / M I N ) ,
IMPFLLFR DIAMFTFR C O W RM0 <G/CC)» FRACTIONAL PFRCFNT
SOLIDS I N SLURRY* SLURRY VISCOSITY CCP>» 'UNAGITATFD
SLURRY HEIGHT CCM), AFRATFD SLURRY HFIGHT fCM>»
DECONTAMINATION FACTOR, ALPHA CC.M), PLUG FLO* INTFRFACIA1.
ARFA C C M P / C O * BACKMIX INTFRFACIAL ARFA ( W / C C ) t
INPUT RUN 1 - 3 RPM * - 7 GASFLOI-' R - I P I^PPIAM 1 3 - 1 7 RH0 1B-P3
PF.RS0L 9*-?9 V I S C 3 0 - 3 S 0FFMT 3 * - 4 0 AFRHT i » l - ^ S PF Af-SO
ALPHA 51-SB APLUG S 9 - * 3 AMIX * 4 - 7 0 t
AGF = l ;
I F -N«* > 9 * THFN AGF = 9\
***
t»F ARE GOING T0 F I T A LINFAR M0PFL T0 THF FXPFRIMFNTAL
DATA USING AN FOUATI0N 0F THF FORM:
LNCIARFA) = A LNtRPM) • B LNfGASFL0W) . . . ;
***
C0NVFRT GAS FL0*«' RATF T0 SUPFRFICIAL VELOCITY CCM/S>»
FL0K = GASFLO*'!
It = GASFLO* * . 0 ? R 4 9 !
***
CAl CULATF THF RFYN0LDR NUMBER!
RFYN=IMP3IAM*IMPPIAM*RPM*RH0/VISr/*O»
***
CALCULATF THF FR0UDF NUMBFRj
FR0UPF= IMPPIAM*RPM*RPM/3A00/9R0»
*#*
C0NVFRT RPM T0 REVOLUTIONS PFR SFC0NPJ
RPS=RPH/fiO*
***
CREATE A PIMENSI0NLFSS VARIARI.Ff
NPSV = I M P P I A M * R P S / U i
***
TAKF LOGARITHMS 0F THF V'ARIABI.FS T0 BF CORRFI ATFP»
***
IMPFLLFR SPFFDl
LNRPS=L0GCRPS)»
***
IMPELLFR DIAMFTFRl
LNDIAM=L0G<IMPDIAM) |
***
SUPFRFICIAL VELOCITY!
LNOG=L0G(U)I
***
INTFRFACIAL AREA F0R PLUG FL0V MODEL!
LNAPLHGsL0GCAPLUG)»
**#
INTFRFACIAL ARFA, RACKMIX ASSUMPTION!
LNAMIXeLOG(AMIX)!
***
REYNOLDS NUMBER!
LNRFYN=L0G<REYN>!
***
VISCOSITY!
LNVISC«LOGCVISC>!
*#*
 26

NF.P DIMENM0NLFSS VARIABl.Fl

LNNDSV=L0G(NDSV)I
***
FR0MPE NUMBERS
LNFRs L0G<ER0UDE)t
***
PFR CENT S 0 L I D 5 I
LNPFRS0L=L0G<PF.R50L> I
***
DFC0NTAMINATI0N FACTOR!
LNPF = L 0 G ( P E ) f
***
RFAP I N DATA I
CARDSl
=F0R1P.DAT*

• **
PFRF0RH THF LINFAR M0PELS PR0CEDUREI
FR0C GLW PATA= I H T F P l
H0DEL LNDF LNAPLUG LNA*IX=LNRPS LNOG LNDIAM LNPPRS0L t
eiiTPirr 0 U T = RESULTS PRFDICTFD= CDF CAPLUG CAHTX
RESIDUAL* RDF RPLUG RMIXl
T I T L E PL'SCELa" C0RRFLATI0NI
***
P R I N T THF RESULTS*
PR0C P R I N T ;
***
MAKE SUBSETS 0F THF RESULTS F0R PLOTTING*
***
KAKF PL0TS 0F RESULTS*
PR0C PL0T DATA = RFSIILTS I
PL0T LNAPLUC*CAPLIIG=RP* LNAPLUG*CAPLMGsFI 0M l.NAPLUG*CAPI UG=AGFt
T I T L f l PL0T 0F L0G INTFRFACIAL ARFA (PLUG GASFL0f) V S . C0RRFI A T I 0 N *
PR0C PL0T DATA = RESULTSI
PL0T LNDF*CDE=RPH LNDF*CDF=FL0<-' LNDF*CDF = AGFt
T I T L F l PL0T 0F L0G DFC0NTAMINATI0N FACT0R V S . C0RREI ATI0N»
PR0C PL0T DATA * RESULTS1
PL0T L N A f I X * C A H I X = R P * LNA*IX*CA*MX=FI.0V LNA»MX*CA»*IX = AGEl
T I T L F l PL0T 0F 1.0G INTFRFACIAL ARFA CBACKMIX) V S . C0RRELATI0N>
r
PL0T R P F * R P * = F L 0 ' ' RPLIJG*RPM=FL0w RWIX*RPf*=FL0' »
T I T L F l PL0T 0F RFSIDHAL V S . RPH BY FL0V RATFSl
***
I
FR0C GLW DATA* I H T F P l
H0DEL LNAPLUG* LNFR LNNPSV L N P F R S 0 L / P I
0IITPUT 0UT = INT PREDICTED* CAPLUG RESIDUAL-- R F S I D l
T I T L E PLUGEL0*-' C0RRFLATI0NI
PR0C PL0T DATA* I N T f
PL0T LNAPLUG*CAPLUG=RP*I
T I T L E I PL0T 0 F L0G INTERFACIAL AREA V S . C0RRFLATI0NI
T I T L E ? INTERCEPT INCLUDED I N C0RRELATI0NJ
***
I
PR0C GLf* DATA* I H T E P l
H0DEL LNAPLUG* l.NRPS LNOG LNPFRS0L L N P I A M / P i
0UTPIIT 0 U T * N01NT PREDICTED* CAPl.UG RESIDUAL* RFSTDl
T I T L E PLUGEL0'-' C0RRFLATI0NI
 27

PR0C PL0T DATA= N0INTI

PL0T LNAPLIIG*CAPLUG=RPMJ
TITLEl PL0T 0F L0G INTERFACIAL AREA VS. C0RREATI0NI
TITLE? INTERCEPT WAS N0T INCLUDED IN CORRELATION!
***
i
PR0C GLM DATA= IHTFP»
MODEL LNAPLUG= LNRPS LNOG LNPERS0L / N0INT Pl
TITLE PLMGFL0W C0RRELATI0N»
***
t
PR0C GLM DATA= IHTFP;
MODEL LNAPLUG= LNFR LNRFYN LNNDSV LNPERSOL/Pl
TITLF PLUGFL0H C0RRFLATI0N. DIMFNSI0NLFSS VARIABLES*
***
f
PR0C GLM DATA* IHTFPi
M0DEL LNAPL!I6= LNREYN LNNPSV LNPERSOL/Pl
TITLE PLUGFL0W CORRELATION. REYNOLDS N0.» SMPF' ICIAI
GAS VFL. . AND PERCFNT SOLIDS.*
***
USE THE STEPWISE PROCEDURE T0 FIND THE RES M
PR0C STEPWISE DATA= IHTFPI
M0DEL LNAPLUG= LNRPS LNGG LNDIAM LNPFRS0I. / MAXRi
M0DEL LNAPLUG= LNRFYN LNFR I.NOG / MAXRl
/*
//
F.NDINPUT

3. Program 3

TYPE NLBA../CL
/ / f A S 3 J0B d * 4 | 7 ) , ' R I N P» K . D . PATCH'
//•CLASS CPU9I=*M,I0=P
/•ROUTE PRINT L0CAL
/ / EXEC SAS7*
/ / S T F P L I B DD PSN=A.EjN10.107.SAS.LIBRARY>DISP=SHR
/ / S A S . S Y S I N DD *
***
PR0GRAM T0 CORRELATE INTERFACIAL AREAS AND
DEGREE 0F MIXEDNESS FOR 1979 RA(0H>2 DATA
• ••
VARIABLE DESCRIPTION UNITS

A INTERFACIAL AREA (CMP/CM.1)

AlftFLOf AIR FL0*'RATE AT STP (L/MIN>
ALPHA A RATIO OF REACTION RATE
T0 GAS FLOW RATE (CM)
OF DECONTAMINATION FACTOR
HEIT AGITATED SLURRY HFIGHT (CM)
IMPDIAM IMPELLER DIAMETER CCM)
N N0. 0F CSTR'S IN SFRIES
PERS0L PERCENT SOLIDS
RPM AGITATOR SPEED (RPM)
RUN RUN NO.
U SUPERFICIAL VELOCITY (CM/S)
 28

• *•
RFAD VARIARl.FS FROM PATA F1I.F«
OATAl
INPUT R«W l - . l RI'K * - 7 A I R F I . 0 ' ' R - l ^ I P P P I A H 1 3 - 1 7
PFPSBL J>*-?9 MFIT Jk\-A<\ PF a * - S O ALPHA S I - S R i
#**
IISF. I N BF DFC0NTAKINATI0N FACTOR FOR CORRFI.AT t O N l
LNDF = L8CCPF)«
*•*
CALCW.A1F SHPFRFICIAI V F L O C I T t F R 0 * AIRFLOW AND
CONTACTOR CR0SS-SFCTI0NAL ARFA CSFS C*P> »
H = AIkFL0y*O.O?R49l
• •*
CONVFRT RPM TO RFSl
RPS = RPM/*O.Ol
CARDS!
=FPR??.PAT»
t
***
TANKS IN SFRIFS K0DFI.:
P0ST»iLATF C0NTACT0R CAN RF M0PFI FO AS N - C S T R ' S
I N SFRIFS. CORRFLATF ' N * AND ' A * AS F A C T I O N S
0 F THF HYPR0PYNAKIC V A R I A P L F S . I
**•
N01F: THF IKPFLI.FR PIAMFTFR VAS NOT VARIFO AND
I S THFRFF0RF NOT INC1.HPFD I N THF M0PFI 1
I R 0 C N L I N ITFR=SPO fFTH0D=KARRHARPT1
PARA*F1FRS A 0 = I . B F 9
Al=*..1
A?=-?.0
A.1=0.9SP
NO=0..1??S
NI=-O.RS9
N?=-C?PS
NTr-p.|4t
R0IINDS AO>0 NP>Pl
*#*
P0S1MLA.1F EMPIRICAL R F L A T I 0 N S H I P S AS F0l.l.0>-'Sf
A = AP*CRfT.»*An*CH»*A5>>*(PFRS0J * * A 3 > I
N = N O * r N r S * * N I ) * < H # * N ? ) * f f'FRSOl • *N.1> »
GAMMA = ALPHA«A/NI
GAMMAPI = GAMMA • I.O»
DFRA = (ALPHA/GAMMAIM)*At
PERN = (LOGCGAMMAPI) - fAMMA/GAMMAP1>*Nl
M0PFI. LNPF = N»L0G<CAMMAPl>»
DFK.AP=OFRA/APl
PFR.AlxPFRA*L0GCRPS)(
D E R . A ? * D F R A * l . 0 f <ll> I
DFK.A:UDFRA«L0G< PERSBL)t
DER.NO=DEKN/N0»
nFR.NIxPFRN*L0C<RPS)l
DER.N? = DERN*I OGCH) »
DFR .N.1spERN«L0GC PERS0L ) I
e i l T M I T 0HT«CSTR PKEPICTEP=LNPFl KFSIP'IAI. = RFSI 0
PARMS*M-f'Hf
DATA RESULTS!
SET CSTRl
ARFA»»'l*CKPS**r'?)*<l'«*r.1>*CPFRS0L«*PA>l
NCSTR*rS*CM'S»*f'*>*Ol**p7>*<rFRf.0l.«*PR>l
PR0C PRINT DATA»RESMLTSi
I'ROC PLOT DATA«PFSHl.TS»
PI.0T L N n E * L N D E I » R P S l
I.Aflfl I.NPE»L0G DECONTAMINATION FACTOR
L N P E | » L 0 G DECONTAMINATION FACTOR ( P R E D I C T E D ) I
T I 1 L F I.OC DECONTAMINATION FACTOR ACTUAL U S . PREDICTED!
T I T L E ? N - C S T P " S I N S F R I F S MODEI 1979 PA(OH>f> DATA!
I ROC PLOT 0ATA«RFSIII.T5l
PLOT R E S I D * I NPFlsRPS RFSI D*LNDF l » A I R F I . 0 ' ' »
/*
//
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 32

8.4 Location of Original Data

The original data are found in ORNL Databook A-9177-G, pp. 1-31, on
file at the MIT School of Chemical Engineering Practice, Bldg. 1505, ORNL.

8.5 Nomenclature

3
a gas-liquid interfacial area, cm^/cm
2
A contactor cross-sectional area, cm
3
[C0 ] 2 concentration of C 0 in liquid, gmol/cm
2

Deo- diffusivity of COp in aqueous solution, cm2/s

DF decontamination factor [x /x )
f

dj impeller diameter, cm
G molar gas flow rate, gmol/s
h sum of contributions effecting ionic strength [Eq. (19)]
3
H Henry's coefficient of solubility, gmol/cm -kPa
H Henry's coefficient of solubility of C 0 in pure water, gmol/cn^-kPa
2

I ionic strength of the solution

K, pseudo-first-order rate constant, gmol/cm^-kPa-s
3
K 2 second-order rate constant, cm /gmol-s
Kg gas-side mass transfer coefficient, 9 --kPa
K, liquid-side mass transfer coefficient, cm/s
K- a 1< wiped reaction constant, gmol/cnr^-s-kPa
K° second-order rate constant in pure water
MW* molecular weight of air, g/gmol
n number of equal-volume CSTR's in series
N impeller speed, rps
[OH'l hydroxide concentration, gmol/cm
 33

3
P power dissipated per volume of liquid, hp/ft
P_avg average pressure in contactor, kPa
P- partial pressure of CO- in gas, kPa
P. partial pressure of CO- at gas/liquid interface, kPa
Q air flow rate at STP, i/min
3
R specific rate of absorption of CO-, gmol/cm -s
S weight fraction solids
U superficial gas velocity, cm/s
U. velocity rise of bubbles, cm/s
3
VQ a aerated volume in contactor, cm
x mole fraction COg in gas stream
x f mole fraction CO- at contactor outlet
xo A mole fraction CO-2 at contactor inlet
z height in contactor, cm
Z. valence
Greek Symbols
06 x K P V cm
°' l avg a " a l r ^ 'air'
v liquid viscosity, 10" g/cm-s 2

3
p liquid density, g/cm
3
p ftir air density, g/cm
S 2
a surface tension, 10 J/cm or g/s

8.6 l i t e r a t u r e Referenced

1. Barr, A.J., J.H. Goodnight, J.P. Sail, and J.T. Heiwig, "SAS Users
Guide," SAS Ir^Mtute, Raleigh, N.C. (1979).
2. Calderbank, P.H., "Physical Rate Processes in Industrial Fermenta­
tion, Part I: The Interfacial Area in Gas-Liquid Contacting with Mechanical
Agitation," Trans. Instn. Chem. Engrs.. 36, 443 (1958).
 34

3. Danckwerts, P.V., Gas-Liquid Reactions, McGraw-Hill, New York,

1970.
4. Oc»nckwerts, P.V., and M.M. Sharma, "The Absorption of Carbon
Dioxide into Solutions of Alkalis and Amines (With Some Notes on Hydrogen
Sulphide and Carbonyl Sulphides)," Chem. Engr. (London). October, 244 (1966).
5. Holladay, D.W., "Experiments with a Lime Slurry in a Stirred Tank
for the Fixation of Carbcn-14 Contaminated COo from Simulated HTGR Fuel
Reprocessing Off-Gas," 0RNL/TM-5757 (1978).

6. Holladay, D.W., and G.L. Haag, "Removal of ^-Contaminated CO?

from Simulated LWR Fuel Reprocessing O^f-Gas by Utilizing the Reaction
Between CO2 and Alkaline Hydroxides in Either Slurry or Solid Form," 15th
DOE Nuclear Air Cleaning Conference, p. 30 (1978).

7. Juvekar, V.A., and M.M. Sharma, "Some Aspects of Process Design

of Gas/Liquid Reactors," Trans. Instn. Chem. Engrs., j>5, 77 (1977).

3. Juvekar, V.A., and M.M. Sharma, "Absorption of COo in a Suspension

of Lime," Chem. Eng. Sci. 28, 825 (1973).
;

9. Levenspiel, 0., Chemical Reaction Engineering, 2nd ed., Wiley, New

York, 1972.
10. Mehta, V.D., and M.M. Sharma "Mass Transfer in Mechanically Agi­
tated Gas-Liquid Contactors," Chem. E.g. Sci., 26, 461 ',1971).

11. Miller, D.N., "Scale-up of Agitated Vessels Gas-Liquid Mass

Transfer," AIChE Journal, 20, 445 (1974).
12. Morris, R.M., and E.T. Woodburn, "Testing of Certain Design Equa-
tiors for Predicting the Performance of a Calcium Hydroxide Carbonation
Reactor, Part I: Gas Bubble Dynamics and Interfacial Areas in a Stirred
Reactor," S.A. Chemical Processing, June-July, 88 (1967).

13. Perry, R.H., and C.H. Chilton, Chemical Engineers' Handbook, 5th
ed., McGraw-Hill, New York, 1973.

14. Reith, T., "Interfacial Area and Scaling-Up of Gas-Liquid Contac­

tors," Brit. Chem. Eng.. 11(12), 1559 (1970).
15. Sheppard, N.F., R.C. Rizo-Patron, and W.H. Sun, "Analysis of
Stirred-Tank Carbonation Reactors," ORNL/MIT-281, 0RNL (1978).

16. Sidemon, S., 0. Hortacsu, and J.W. Fulton, "Mass Transfer in Gas-
Liquid Contacting Systems," Ind. Eng. Chem., 58, 32 (1966).
17. Valentin, F.H.H., Absorption in Gas-Liquid Dispersions: Some
Aspects of Bubble Technology, E. & F.N. Spon, London, 1967.
 35

18. Van't Riet, K., J.M. Boom, and J.M. Smith, "Power Consumption,
Impeller Coalescence and Recirculation in Aerated Vessels," Trans. Jnstn.
Chem. Engrs., 54, 124 (1976).

19. Van't Riet, K., and J.M. Smith, "The Behavior of Gas-Liquid Mix­
tures near Rushton Turbine Blades," Cherc. Eng. Sci., 28, 1031 (1973).

20. Westerterp, K.R., "Design of Agitators for Gas-Liquid Contacting,"

Chem. Eng. Sci., 18, 495 (1963).

21. Westerterp, K.R., L.L. van Dierendonck, and J.A. de Kraa, "Inter
facial Areas in Agitated Gas-Liquid Contactors," Chem. Eng. Sci., 18, 157
(1963).

8.7 Literature Surveyed

1. Bates, R.L., P.L. Fondy, and R.R. Corpstein, "An Examination of

Some Geometric Parameters of Impeller Power," I&EC Proc. Pes. Dev., 1(4),
310 (1963).

2. Froment, G.F., and K.B. Bischoff, Chemical Reactor Analysis and

Design, Wiley, New York, 1979.
3. Gambill, W.R., "How to Estimate Mixture Viscosities," Chem. Eng.,
March, 151 (1959).

4. Luong, H.T., and B. Valesky, "Mechanical Power Requirements of

Gas-Liquid Agitated Systems," AIChE. Journal, 25, 893 (1979).

5. Reid, R.C> J.M. Prausnitz, and T.K. Sherwood, The Properties

of Gases and Liquids, 3rd ed., McGraw-Hill, New York, 1977.

6. Rushton, J.H., E.W. Costich, and H.J. Everett, "Power Character­

istics of Mixing Impellers," Chem. Eng. Progr., 46_(8), Part I, p. 395, and
46(9), Part II, p. 4J7 (1950).

7. Weast, R.C., ed., Handbook of Chemistry and Physics, 56th ed.,

C.R.C. Press, Cleveland, 1976.