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Abstract-The kinetics of absorption of lean CO, in a suspension of lime was studied in 5 and 20
cm i.d. bubble columns and a 12.5 cm i.d. mechanically agitated contactor. The absorption of CO* is
accompanied by a fast pseudo first order reaction. The rate of absorption in a batch of a suspension of
lime remains essentially constant up to a level of carbonation of about 90 per cent and thereafter it
decreases, due to the resistance associated with the dissolution of solids. The published data in the
literature and the reported mechanism have been reanalyzed.
r
-
Bs z = 2 = stoichiometric coefficient for
the overall reaction:
Bo
where, H = Henry’s law solubility coefficient, Where 4 is the enhancement factor, that is,
g mole/cm3 atm. the ratio of the liquid-side mass transfer co-
Eliminating [A*] and pi from Eqs. (l), (3) and efficient with reaction to that in the absence of
(5) we get: chemical reaction.
The penetration theory does not give an
analytic expression for 4 under the conditions
of the depletion of B in the film. However, the
film theory, with the assumption made by van
Krevelen and Hoftizer[7], and Hikita and
Asai [8], gives the following analytic expression:
Under certain circumstances the condition
given by expression (4b) may be satisfied but
that given by expression (4a) may not be satisfied.
For instance the condition given by expression (11)
(4a) may not be satisfied for low values of [B,]
and relatively high values of k[,.
Here, For greater accuracy the term D /DA in
Eq. (11) was replaced by &. The
emJ_1 (7)
differences in the predictions based on the
kL - penetration and film theories under the above
conditions are for practical purposes insignificant.
When the condition given by expression (4a)
is not satisfied it implies that a part of the MATERIALS
reaction between COZ and OH- occurs in the Lime used in this work was obtained from
film and the rest in the bulk liquid. Sturdia Chemicals (Rishikesh, U.P., India)
Danckwert’s surface-renewal theory gives Sodium hydroxide, sodium carbonate and sodium
the following equation for Ra: bicarbonate used were of technical grade. All
827
V. A. JUVEKAR and M. M. SHARMA
aqueous solutions were prepared with tap water. contactor. (In the case of bubble columns
A small amount of tricresyl phosphate was used agitation was provided by sparging air through
as an antifoami~ agent. the slurry.) Then air-CO, mixture of the desired
composition was introduced through the slurry
ANALYSIS and at the same time the stop watch was started.
The extent of the car~nation of a lime sample During a run, the height of dispersion of the
was determined by the acidimetric titration of liquid and the pressure of the gas at the inlet
the sample with standard hydrochloric acid using were noted. After a known interval of time, the
phenolphthalein as an indicator. flow of COz through the contactor was stopped.
A sample of the slurry was withdrawn while
EXPERIMENTAL the slurry was kept agitated. The temperatures
(a) Bubble column: Perspex bubble columns at the beginning and the end of the run were
of 5 and 20 cm id. were used. The gas was also noted.
introduced at the bottom of the column through For the sake of comparison, some work was
tubes of 1 cm and 2.5 cm diameter, respectively. also carried out on the carbonation of sodium
The super&&l gas velocity, based on the column hydroxide and buffer solutions of sodium
cross-sectional area,, was varied from 10 to 70 carbonate and bicarbonate.
cm/set. In this range of superficial gas velocity
the mode of the introduction of the gas is RESULTS AND DISCUSSION
unimportant provided the height of dispersion is A typical plot of the rate of carbonation against
at least four times the column diameter 191.The time is shown in Fig. 2. It has two distinct
ratio of the height of dispersion to the column regions:
diameter was maintained between 7 and 8. The (i) A constant rate period during which the
partial pressure of COz in the gas stream was rate of absorption of CO, and the concentration
varied by mixing it with air. The flow rates of air of OH- ions in the solution remain essentially
and carbon dioxide were measured with cali- constant. In this period the aqueous phase is
brated rotameters. A suitable mixing length was always kept saturated with OH- ions (C&J -
provided to ensure a thorough mixing of COz E&3).
and air.
(b) Mechanically agitated contactor: A 12.5 14
cm i.d. and 30cm high glass vessel (Corning
resin kettle) was used. It was provided with 12
standard vertical bathes, each one tenth of the
diameter of the vessel. The impeller used was a IO
pulleys.
4
PROCEDURE
to the required height. The slurry was first Batch time, min
agitated and the initial sample was withdrawn Fig. 2. Carbonation of lime: constant rate and failing rate
through the sample outlet at the bottom of the periods.
828
Absorption of CO2 in a suspension of lime
The following condition is satisfied in this The condition under which the solid dissolu-
region: tion becomes important is given by expression
(14):
gas phase in agitated gas-liquid dispersions is = 2 g ion/l.) in which calcium carbonate particles
almost completely mixed, when the speed of were suspended. The ratio of C032- ions to
agitation exceeds a certain critical speed. How- HC032- ions was kept equal to about 1. Under
ever, in the presence of fine solid particles the these conditions the pseudo first order rate
coalescence in the gas bubbles may be sub- constant (k,) for the reaction between CO2
stantially different. This may change the back- and OH- ions is about O-6 set-‘[6]. Assuming
mixing characteristics in the gas phase. Morris kL = 3 X 10e2 cm/set and DA = 2 X 10m5cm2/sec,
and Woodbum[3] have shown that in the we have,
presence of solid particles the gas phase moves
essentially in the plug flow even under the
-- 0.12 G 1.
conditions of fairly intense agitation. It was also kL
found in the present investigation that the
results were more consistent when the plug The rate of absorption under these conditions
flow model for gas was assumed than when the is given by Eq. ( 17):
backmix model was assumed (see Table 1).
Ra = kLaHpE, (17)
Physical properties of systems
Various system properties such as the where, plm = log mean partial pressure of C02.
solubility of COz in aqueous solution of OH- A plot of kLa against the superficial gas
ions, the rate constant for the reaction between velocity, uG, based on the column cross-sectional
COz and OH- ions, diffisivity of CO, in aqueous area is shown in Fig. 3. Equation (18) correlates
solutions of OH- ions were estimated by the the above data:
procedures outlined by Danckwerts and
Sharma [6] k,a = 5.65 x 1O-3 vGo.5s. (18)
The solubility of lime in water at 30°C was
takenas2aOX 10-5gmo1e/cm3[13]. Sharma and Mashelkar[9] have shown that
for gas-liquid systems, k,a in bubble columns is
MASS TRANSFER COEFFICIENTS IN proportional to O-7 power of the superficial
GAS-LIQUID-SOLID SYSTEMS
gas velocity. The lower exponent of vG in the
Bubble column presence of solids is perhaps due to the fact that
(a) Determination of kLa. The values of kLa in the presence of solid particles there is a forma-
in bubble columns were obtained by carrying tion of slugs of gas at larger gas velocities.
out the absorption of CO, in an aqueous buffer (This matter is further discussed in the latter
solution of Na,C03-NaHCO,, (ionic strength part of this paper).
Rate of a
Partial Partial Log mean absorption (cmp/cm3
pressure of pressure of partial of co, x lo-’ slurry) a
Superficial CO2at the CO, at the pressure of (g mole based on based on
gas velocity inlet (atm outlet (atm CO* (atm set cm3 backmix plug flow
(cmlsec) x 102) x loz) x lop) slurry model model
Vessel dia. = 12.5 cm, impeller dia. = 7.5 cm, impeller speed = 1130 rev/min, temperature = 33°C.
830
Absorption of CO2 in a suspension of lime
Absorbent (4a) and (4b) are satisfied and therefore the rate
Column diameter
(cm) of absorption of CO, is given by Eq. (6). How-
A- Ca(OH), 5 ever, during the carbonation of NaOH, OH- ion
A-CalOHL+NaOH 5
l-tia<OHj; 20 concentration continuously decreases with time
0-C~OH)~+NaOH 20 and therefore the rate of absorption of COz also
decreases with time. Approximate values of
The above values of effective interfacial area interfacial area were obtained under the follow-
were checked by dete~ining interfacial area ing assumptions: (i) the time average rate of
in COrNaOH system in which Ca(OH)2 absorption was obtained from the change in the
particles were suspended. For this system we concentration of NaOH during the experiment.
have the following data: (ii) [B,] was taken as the arithmetic mean of the
For 1M NaOH carbonated in bubble column initial and final concentration of NaOH (iii)
with 10% COz in air, log mean partial pressure of COz was based on
the average rate of absorption of COz. In a typical
!l?d!pLlO,l case the change in the concent~tion of NaOH
L
mv
during a run was from 2.5 to 1*1M. The above
and assumptions are unlikely to result in an error
of more than 10 per cent in the calculation of
(21) the values of the interfacial area.
The interfacial area values thus obtained are
Thus the conditions given by expressions compared with those obtained from the carbona-
832
Absorption of CO, in a suspension of lime
tion of lime (see Figs. 3 and 5). The two sets of gas in excess of that required for the incipient
values are in fair agreement. fluidization of solid particles passes through the
suspension as large bubbles. Thus the gas velocity
Efect of CO2 partial pressure on the rate of which is above that required for the incipient
carbonation fluidization is expected to be less effective in
An increase in the partial pressure of COZ increasing the gas-liquid interfacial area as
beyond a certain value leads to the depletion of compared to a situation where solid particles
OH- ions at the gas-liquid interface. This leads are absent.
to a reduction in the rate of COZ absorption per In the mechanically agitated contactor it was
unit CO, partial pressure. The rate of absorption observed that the superficial gas velocity had a
under these conditions can be obtained from negligible effect on the interfacial area in the
Eq. (10). range of the impeller speeds considered (Fig. 6).
Table 2 shows the rate of absorption of COZ The critical impeller speed, beyond which the
as a function of COZ partial pressure. The values gas velocity has no effect on the interfacial area,
of interfacial area were obtained from the as obtained from the equation proposed by
observed rate using Eq. (10). It appears that these Westerterp et al. [l 11, was found to be about
data can be satisfactorily correlated. 600 revlmin. The speeds of stirring used in the
Table 2. Effect of CO* partial pressure on the rate of carbonation of lime suspension
EFFECT OF SUPERFICIAL GAS VELOCITY present work are lOOO-2000revlmin. and are
ON EFFECTIVE GAS-LIQUID INTERFACIAL much higher than the above value.
AREA
Figure 4 shows that the interfacial area in
bubble columns, in the presence of fine solid EFFECT OF THE IMPELLER SPEED ON THE
particles, is a weak function of superficial gas EFFECTIVE GAS-LIQUID INTERFACIAL
velocity (aaVG0”3). Sharma and Mashelkar [9] AREA
have shown that in absence of solid particles, A plot of the effective interfacial area against
the gas-liquid interfacial area in bubble columns, particle loading is shown in Fig. 7. It is seen from
varies as O-7 power of the superficial gas velocity the plot that upto 20 per cent particle loading
upto a value of V, equal to about 35 cm/set. A (w/v), the interfacial area is practically inde-
pronounced slugging of the gas was visually pendent of the particle loading. Even for higher
observed in the presence of solid particles. particle loadings the effect on the interfacial
Davidson et al. [15,16] have observed that the area is insignificant.
833
CES Vol. 2SNo. 3-K
V. A. JUVEKAR and M. M. SHARMA
I I I I I I I
0 10 20 30 40 50 60 70
Particle loading, g/l Fig. 8. Effect of superlicial gas velocity on the gas hold-up in
bubble columns.
Fig. 7. Effect of particle loading on gas-liquid interfacial area. Curve
Curve 0 - 5 cm id. bubble column.
0 - 5 cm i.d. bubble column, VG= 21 cmlsec. A- 20 cm i.d. bubble column.
A- 125cm i.d. mechanicahy agitated contactor speed of
agitation: 2050 revlmin.
ANALYSIS OF THE DATA OF MORRIS
AND WOODBURN
Gas hold-up in bubble column Morris and Woodbum have interpreted their
Hovmand and Davidson [ 151 have proposed data for the constant rate period on the assump-
a slug flow model to correlate the gas hold-up in tion that the gas-film resistance is the controlling
gas-liquid-solid fluidized beds at superficial factor. This assumption was made on the basis
Absorption of CO, in a suspension of lime
of the following points, which are most unlikely of the published work on carbon dioxide absorp-
to be correct: tion. Danckwerts and Sharma[61 have analysed
(i) The reaction CO,+ OH- + HCO,- is practically all the available information on the
very fast and hence these authors assumed that absorption of CO, in aqueous alkaline solutions.
this reaction is not the rate controlling step. It is clear from their work that the absorption of
The liquid-side mass transfer coefficient CO* in aqueous solutions containing hydroxyl
(k,), under the experimental conditions used by ions is essentially liquid film controlled.
these authors (vessel dia. 20 cm, impeller dia. For 2M caustic soda solution carbonated by
10 cm, impeller speed 2000 revlmin), can be 10% CO, in air, we have the following data:
estimated from the data of Mehta and Sharma
[ 121 to be about 6 X 10e2 cmlsec. y_,,
Consider a case when 10% COz in air is used L
@$@J_
L
1.7 -#
$+cMl.
A
and
Thus the conditions given by expressions (4a)
and (4b) are satisfied and the rate of absorption
fi
J-
4 -
A
10.
is given by Eq. (6).
Further we have:
Thus the conditions given by expressions (7)
and (4b) are satisfied which means that the rate HavD&[&l_ o.09
.
of overall process is controlled by both the ditTu- ka
sion of COz as well as the reaction between COz
and OH- in the liquid film. This shows that the contribution to the total
The condition for the gas-side resistance resistance by the gas film is only about 9 per cent
to be the controlling factor is given by and hence the process is essentially liquid
fipgd/(DAh (B,) + kLz)/kGa a 1. For the present film controlled.
caSe we have: kGa - 5 X low4g mole/cm3 set The experimental data of Morris and
atm[l4]. Woodbum can be reanalysed as follows:
Consider a run (Table 3, run 4 [4]) taken under
Here:
the following conditions:
a&‘t,‘&kdBs) + kLz_ o.oo3 e 1
Log mean COz partial pressure = 9.75 X IO-’ atm AcknowIedgeme&- We thank Dr. P. A. Ramachandran who
Henry’s law solubility constant (H) of COz in had initially carried out some experimental work on the
carbonation of lime.
water at 3O’C = 2.88 X 10e5 g mole/cm3 atm
DifTusivity of Cot in water at 30°C DA = 2-l x NOTATION
10e5 cm’/sec [A*1 solubility of carbon dioxide in an aqueous
Second order rate constant for the reaction solution, g mole/cm3
between COz and OH- ions, k2 = 1.24 X 104l/g a effective gas-liquid interfacial area,
mole set cm2/cm3 of dispersion (bubble column)
Saturation concentration of OH- ions, (I?,) = cm2/cm3 slurry, mechanically agitated
4 x 10V5g ion/cm3. kL is assumed to be about vessel
6 x lo+ cm/set on the basis of the data solid-liquid interfacial area, cm2/cm3
obtained in this work. LB; concentration of OH- ions at the gas-
Here, liquid interface, g ion/cm3
[&I concentration of OH- ions in the bulk
m = 0.102 cm/set liquid phase, g ion/cm3
and
[&I saturation concentration of OH- ions in
aqueous solution in equilibrium with
Ca(OH)2 (solid), g ion/cm3
internal diameter of bubble column, cm
diffisivity of CO, in aqueous solution,
Solubility of COz at log mean partial pressure, cm2/sec
diffisivity of OH- ions in aqueous
(A*) = H~lrn solution, cm2/sec
= 2.81 X 10e6 g mole/cm3 particle diameter, cm
(&) gravitational acceleration, cm/sec2
z. = 7.12.
Henry’s coefficient of solubility, g mole/
cm3 atm.
Thus the conditions given by the expressions fractional gas hold up
(7) and (4b) are satisfied and the rate of absorption fractional gas hold up at the incipient
of COz is given by Eq. (8). fluidization
kc is assumed to be about 1 X 10m4g mole/cm’ gas side mass transfer coefficient, g
sec. mole/cm2 set atm
Substituting all the values in Eq. (8) the inter- liquid side mass transfer coefficient,
facial area value is calculated to be 0.48cm2/cm3 cmlsec
of slurry. This value of a appears to be reason- solid-liquid mass transfer coefficient,
able in view of the fact that a low speed of cm/set
agitation was employed. pseudo first order rate constant, set-’
second order rate constant, cm3/g
mole set
CONCLUSION m particle loading, g/cm3 liquid
The absorption of COa in a suspension of lime PQ partial pressure of CO2 in gas stream, atm
is accompanied by fast reaction in the gas- Pi partial pressure of CO2 at the gas-liquid
liquid film. The gas side resistance for the interface, atm
transport of COz to the gas-liquid interface is Ph log mean partial pressure of C02, atm
negligible. The data obtained from bubble R specific rate of absorption of C02, g
columns and the mechanically agitated contactor mole/cm3 set
can be correlated on the basis of the above model. T absolute temperature, “K
836
Absorption of CO, in a suspension of lime
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PI MORRIS R. M. and WOODBURN E. T., S. A. Ckem. Proc. 1967 Cp. 158.
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[I41 MEHTA V. D., Ph.D. Thesis, University of Bombay, India 1970.
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837