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# 2005 Institution of Chemical Engineers
www.icheme.org/journals Trans IChemE, Part A, February 2005
doi: 10.1205/cherd.03289 Chemical Engineering Research and Design, 83(A2): 196204

STRIPPING OF AMMONIA FROM AQUEOUS SOLUTIONS

IN THE PRESENCE OF CARBON DIOXIDE
Effect of Negative Enhancement of Mass Transfer
W. BUDZIANOWSKI
and A. KOZIOL
Institute of Chemical Engineering and Heating Equipment, Wroclaw University of Technology, Wroclaw, Poland

T
he stripping of ammonia from aqueous solutions in the presence of carbon dioxide in
the low concentration region is studied experimentally and theoretically. The phase
equilibria method of Edwards et al. (1978) is selected by comparison of different
methods with newer experimental data. The differential two adjacent films model enabling
component fluxes calculations is used in a stripper model. In the experimental part the sys-
tems NH3 water air and CO2 water air are used in order to select the best physical
mass transfer coefficients correlations. The system NH3 CO2 water-air modified with
strong acids or bases is used for experimental verification of the process model in a wide
range of process variables. Model predictions in conditions of negative enhancement of
mass transfer are presented. The influence of this effect on ammonia stripping efficiency in
the presence of carbon dioxide is analysed.

Keywords: stripping; negative enhancement of mass transfer; modelling; ammonia.

INTRODUCTION must be always taken into account. The equations of the

In this paper, the problem of stripping of ammonia from
aqueous solutions in the presence of carbon dioxide in
the low concentration region is approached. Ammonia
removal from aqueous solutions is an important industrial
problem. There are not many low cost and effective
methods of ammonia removal. One of them is stripping
with air/waste gases. This process allows to reduce even
low concentrations of ammonia, which is further absorbed
by concentrated acid and crystallized. The carbon dioxide
content in gas and/or liquid phase often becomes
an important parameter if deep ammonia removal is
required.
The system NH3 CO2 water is industrially important
and have been studied in the literature. Phase equilibria
were investigated theoretically (Edwards et al., 1975,
1978; Wilson, 1980; Kurz et al., 1995; Maurer, 1986;
Beutier et al., 1978; Bieling et al., 1989; Kawazuishi and
Prausnitz, 1987; Pawlikowski et al., 1982) and experimen-
tally (Goppert et al., 1988). Absorption accompanied by
chemical reaction has been studied extensively, but the
major part of the studies has dealt with absorption followed
by irreversible reactions. In desorption with chemical reac-
tions the liquid is always loaded with volatile chemicals.
Reactions often run very close to the equilibrium and
may change their direction since for desorption reversibility


Correspondence to: Dr W. Budzianowski, Institute of Chemical Engi-
neering and Heating Equipment, Wroclaw University of Technology,
Norwida 4/6, 50-373 Wroclaw, Poland.
E-mail: wojciech.budzianowski@pwr.wroc.pl
mass transfer model (e.g., film or penetration) cannot be
solved analytically for complex reversible reactions
(Versteeg et al., 1990). The numerical absorption model
for complex reversible chemical reactions was presented
by Versteeg et al. (1989). Simultaneous absorption and
reaction of two gases accompanied by irreversible reaction
was studied by Roper et al. (1962). This analysis is how-
ever, based on a restrictive boundary condition that bulk
liquid concentration of both gases is zero, which is only
possible in absorption when the fluxes are in stoichiometric
proportion. An approximate solution for irreversible reac-
tions was presented by Hikita et al. (1977). The occurrence
of a volatile liquid phase reactant still for irreversible reac-
tion was studied by Pangarkar (1974), Shaikh and Varma
(1984) and Ozturk and Shah (1986). Reversible reactions
have not been studied for the last two cases (van Swaaij
and Versteeg, 1992). Cornelisse et al. (1980) presented a
numerically solved absorption model for simultaneous
absorption of two acids (CO2 and H2S) into an aqueous
diisopropanolamine solvent. They observed the phenom-
enon called there forced desorption as a result of numerical
process simulations. Forced desorption occurs due to the
simultaneous absorption of another reactive species and
the reversible interactions that occur between the various
reactants and products near the gas liquid interface.
Blauwhoff et al. (1985) verified experimentally the
phenomenon forced desorption. Those authors received
better results for fluxes calculated with the film theory.
Yu and Astarita (1987a, b) investigated selective absorption
of hydrogen sulphide from natural gas enhanced by the film
effect i.e., pH shifts at the gas liquid interface resulted

196
 STRIPPING OF AMMONIA FROM AQUEOUS SOLUTIONS 197

from instantaneous H2S reactions as compared to slower

CO2 reactions. Recently two-step reversible reactions
have been analysed by Vas Bhat et al. (1999a, b, 2000).
In the present paper, simultaneous mass transfer of two
gases (base and acid) accompanied by parallel and conse-
cutive reversible chemical reactions is studied. The two
reactants are volatile and may be absorbed or desorbed.
Resistance against mass transfer is usually for carbon di-
oxide condensed in the liquid phase. In our experimental
conditions 15 35% of resistance against mass transfer for
ammonia was in the liquid phase. Complex reaction
phenomena in the film coupled to the mass transfer are ana-
lysed. An effect of negative enhancement of mass transfer
(both for absorption and desorption) is predicted for
which numerical results are presented. This effect for that
kind of reactive system has not been reported in the litera-
ture so far. Its influence on mass transfer is emphasized. Figure 1. An example of comparison of the phase equilibria methods.
T-360.2 K, CNH3 2 506 mol m23.
Very little attention in the literature has been paid to
desorption (Astarita and Savage, 1980). In industrial gas
treating plants absorption is often coupled with desorption
units where the solution is regenerated. Rajniak et al. The expression of Edwards et al. (1978) is used for
(1992) developed for the system NH3 CO2 a distillation ions gi:
column model using a theoretical stage concept. They  p 
used extended Uniquac Debye Huckel equation to pre- I 1 p
lngi Af z2i p ln (1 1:2 I ) (7)
dict activity coefficients. Bunert et al. (1995) dealt with 1 1:2 I 0:6
ammonia stripping with steam and air from technical
juices applied in the sugar industry. They developed a Binary interactions parameters terms exhibited very small
HTU/NTU process model. Since those models do not con- influence on results in the concentration region investigated
sider reaction kinetics their use is very limited for design and all were set to zero. The temperature dependence of the
purposes. chemical equilibrium constants and Henrys constants are
The experiments were carried out for the system NH3 reported by Kawazuishi and Prausnitz (1987) and Edwards
CO2 water air in a stripper unit. The experimental results et al. (1978).
are evaluated by means of a numerical solution of the strip-
per model.
TWO ADJACENT FILMS MODEL
Air stripping of ammonia in that system is accompanied
PHASE EQUILIBRIA by chemical reactions (1) (6). In desorption all reactions
The following liquid phase reactions are taken into must be treated as reversible. (1), (3) and (5) are instan-
account in the system NH3 CO2 water air: taneous. (2) and (4) are fast and their kinetics are reason-
ably well established by Pinsent et al. (1956 a, b).
NH3 H2 O ! NH  Reaction (6) is slow.
4 OH (1)
 The two adjacent films model is composed of the system
CO2 OH ! HCO 3 (2) of differential equations and the electroneutrality condition.
HCO3 ! CO 
3 H
(3) For this kind of reactions usually the power law kinetics is
NH3 CO2 ! NH2 COO H (4) assumed:
H2 O ! H OH (5) X
NR Y
NC
d2 Ci
CO2 H2 O ! HCO
3 H

(6) DLi  li,r k r (gj Cj )aj,r (8)
dx2 r1 j

We compared different phase equilibria methods. An

example of comparison of the methods of Edwards et al. Boundary conditions
(1978) and Wilson (1980) with newer experimental data Volatile components
of Goppert and Maurer (1988) is presented in Figure 1. 
The Edwards method provides better results compared dCi  kiGP  b 
 L pi  Hi Ci jx0 (9)
with the Wilson method. Moreover it is less empirical dx x0 Di
and may be extended to new components. Prediction
errors strongly depends on concentration and temperature Non-volatile components
but are usually in the range of 5 15%. Phase equilibrium 
may be calculated by a simultaneous solution of equations dCi 
0 (10a)
for chemical equilibria, components mass balance, electro- dx x0
neutrality and activity coefficients. Composition of a gas
phase is calculated from Henrys law. Ci jxd Cib (10b)

Trans IChemE, Part A, Chemical Engineering Research and Design, 2005, 83(A2): 196204
198 BUDZIANOWSKI and KOZIOL

Electroneutrality:

X
NC
zi Ci (x) 0 (11)
i1

Fluxes:

dCNH3
NNH3 DLNH3 j (12a)
dx x0
dCCO2
NCO2 DLCO2 j (12b)
dx x0

Concentration distribution in the gasliquid boundary

layers, fluxes of volatile components, enhancement factors,
production terms of species and so on are obtained as a Figure 4. CNH3 distribution in the gas liquid boundary layers (case 2: CO2
numerical solution of that two adjacent films model. Ammo- in excess). CiNH3 9.68  1025 mol m23, CbNH3 1024 mol m23,
23
nia desorption from a solution containing NH3 in excess and Cb,Tot
NH3 0.062 mol m , pbNH3 6  1025 Pa, NNH3 21.51  1029
CO2 absorption from air are shown in Figures 2 and 3 mol m22 s21, ENH3 6.24.
whereas desorption of both NH3 and CO2 from a solution
containing CO2 in excess in Figures 4 and 5. Gas phase

Figure 5. CCO2 distribution in the gasliquid boundary layers (case 2: CO2

Figure 2. CNH3 distribution in the gasliquid boundary layers (case 1: NH3
in excess).
CiNH3 0.732 mol m23, CbNH3 100 mol m23, Cb,Tot
b 23 22 21
pNH3 0 Pa, NNH3 22.05  10 mol m s , ENH3 1.02.
in excess). CiCO3 0.0346 mol m23, CbCO2 0.0376 mol m23, Cb,Tot CO2
0.10 mol m23, pbCO2 90 Pa, NCO2 22.25  1027 mol m22 s21,
ECO2 1.00.
NH3 115 mol m ,
23
partial pressure is recalculated into corresponding molar
concentration using Henrys law. Positive values of dimen-
sionless film thickness refer to liquid, negative values refer
to gas.
Ammonia takes part in reaction (1) which is instan-
taneous reversible (Eigen and Schoen, 1955) and (4)
which is second order fast reversible (Pinsent et al.,
1956b). In desorption depending on pH ammonia is trans-
ported from the bulk to the interface in unionized or ionized
form, then instantaneously transferred by reaction (1) and
fastly by reaction (4) into the volatile form. Carbon dioxide
is produced/consumed by reaction (2), (4) and (6). Pro-
duction/consumption of carbon dioxide by second order
reactions (2) and (4) depends on concentration of free
NH3 and OH2 in the liquid film.

Figure 3. CCO2 distribution in the gasliquid boundary layers (case 1: NH3 STRIPPER MODEL
in excess). CiCO2 0.0119 mol m23, CbCO2 6.80  1024 mol m23,
Cb,Tot 23 b
CO2 10 mol m , p CO2 31 Pa, NCO2 2.12  10
26
mol m22 s21, A stripper model developed here is based on flux calcu-
ECO2 2.53. lation. The parameters required were carefully collected

Trans IChemE, Part A, Chemical Engineering Research and Design, 2005, 83(A2): 196204
 STRIPPING OF AMMONIA FROM AQUEOUS SOLUTIONS 199

from literature data and if necessary verified with own or

literature independent experiments.
The differential element mass balance (Figure 6) gives the
following equations:

dpi Ni aAk P
(13a)
dz G
dCi Ni aAk
(13b)
dz VL

Figure 6. The differential element mass balance of counter-current

The boundary conditions for counter-current stripper: stripper.

z 0, Ci CiFeed (14a) Onda et al. (Dankwerts, 1970):

z Z Col , pi pFeed
i (14b)  G  G 0:7  G 0:33
Di a W h
kiGP 2 103  G G (ad)2
RT hG a r Di
NH3 and CO2 molar fluxes may be calculated in the strip- (16a)
per model directly from the two adjacent films model. For
some asymptotic situations approximate solutions may be and Puranik and Vogelpohl (1974):
used but their predictions should be verified with the full
model. 
0:041
wL
In this work literature correlations for mass transfer co- ae ad 1:045 a
efficients were compared with our experimental results. ah L
 L 0:133

The best results are acquired with the correlation of w s 0:182

Mohunta et al. (1969):  L
(16b)
ar s sc

 L 2=3  2 L 1=9
gz r gz r
kiL ae 2:5 103
EXPERIMENTAL PART
ah L hL
 L3 L 3 1=4  L 1=2 The experiments were carried out in a steel column with
W h a h
 (15) an internal diameter of 0.1 m and a height of 1 m filled with
2
gz r L4 r DLi
L
15 mm ceramic Rashig rings (Figure 7). Ammonia and

Figure 7. Experimental set-up. 1, stripper; 2, fan; 3, pump; 4, tanks; 5, heater; 6, humidifier; T, thermocouple.

Trans IChemE, Part A, Chemical Engineering Research and Design, 2005, 83(A2): 196204
200 BUDZIANOWSKI and KOZIOL

carbon dioxide solutions are fed in the top whereas humi-

dified air in the bottom of the column. Liquid composition
is analysed by combined pH and conductometry titration,
gas composition by analyser of Sensorex with cells
for NH3 SX-480, CEX-820 and for CO2 SX-303BP.
Several experiments were carried out with the system CO2
water air to obtain kLi ae and with the system NH3 water
air to obtain kGP e
i a for components in a stripper. Influence
of liquid phase resistance for calculation of kGP e
i a was
taken into account by the Mohunta correlation. Measured
coefficients are used for a verification of existing corre-
lations. It is found that the correlation of Mohunta and
Onda Puranik are in good agreement with the experimen-
tal results. The correlations of Norman and Taecker
(Danckwerts, 1970) predicts higher values of physical
mass transfer coefficients. Figure 9. Influence of pH on ammonia desorption.
VG 2 6.8  1023 m3 s21, VL 2 1.4  1025 m3 s21, T 2 294.7 K,
CNH3 2 99.3 mol m23, CCO2 2 9.3 mol m23, pH of experimental point 2
10.3 (modified with sodium hydroxide).
MODEL VERIFICATION
The process model described above, used as a computer
program was experimentally verified. Degree of desorption
is chosen as a test quantity defined as follows:
Out,Mod
RIn
i  Ri
D desMod
i In  100% (17a)
Ri
Out,Exp
RIn
i  Ri
D desExp
i  100% (17b)
RIn
i

The experiments were carried out in the system CO2

NH3 water air modified with sulphuric acid or sodium
hydroxide. The following parameters were varied
VG 2 3.0 4 9.5  1023 m3 s21, VL 2 0.69 4 5.6  1025
m3 s21, T 2 292 4 298 K, CNH3 2 40 4 140 mol m23,
CCO2 2 7 4 28 mol m23, pH 5.9 4 10.3. Experimental
and calculated results are found to be in good agreement.
The influence of air load on ammonia desorption
(Figure 8), the influence of pH on ammonia desorption
(Figure 9), the influence of temperature on ammonia deso-
rption (Figure 10) are in accordance with qualitative engin-
eering predictions.
Figure 10. Influence of temperature on ammonia desorption.
VG 2 6.7  1023 m3 s21, VL 2 1.4  1025 m3 s21, T of experimental
point 2 296.2 K, CNH3 2 93.4 mol m23, CCO2 2 19.6 mol m23.
Stripping of NH3 is usually less effective than stripping
of CO2. If deep ammonia stripping is required usually
high air load is used (Figure 8). Higher temperature
decreases the solubilities of both gases increasing ammonia
stripping (Figure 10). Maximum ammonia stripping is
achieved in the region of 10 11 pH (Figure 9). The deep
stripping of ammonia requires equipment of high efficiency
and careful process design. This is mainly due to low
Henrys constant, high dissociation constant, better dis-
sociation in a diluted solution, decreasing of pH with
ammonia desorption from a solution, interactions with
CO2 present in a solution or absorbed from air.

EFFECT OF NEGATIVE ENHANCEMENT OF

Figure 8. Influence of air load on ammonia desorption.
VG 2 3.3 4 9.2  1023 m3 s21, VL 2 0.69 4 1.4  1025 m3 s21, T 2 295 K,
CNH3 2 93.4 mol m23, CCO2 2 19.6 mol m23.
MASS TRANSFER
The considered system have an interesting feature. Mass
transfer of weak base ammonia is in certain regions influ-
enced by mass transfer of weak acid carbon dioxide and
mass transfer of CO2 may be influenced by mass transfer
of NH3. This feature may lead to an effect which is called

Trans IChemE, Part A, Chemical Engineering Research and Design, 2005, 83(A2): 196204
 STRIPPING OF AMMONIA FROM AQUEOUS SOLUTIONS
Figure 11. CNH3 and CCO2 profiles, ENH3 24.1.
here the negative enhancement of mass transfer. Ammonia
and carbon dioxide may directly react in the liquid phase
to form ammonium carbamate. Reactions (2) and (6)
in absorption/desorption of CO2 result in consumption/
production of OH2 in the liquid film. Carbamate ion
transports both compounds in the film since its depletion
results in larger driving force. The decrease/increase of
hydroxyl ion concentration in the liquid film shifts the
instantaneous reaction (1) into the direction of free
ammonia consumption/production. All those effects accom-
panying carbon dioxide mass transfer influence an ammo-
nia flux. As a result an ammonia flux is dependent on a
carbon dioxide flux which may result in the effect of
negative enhancement of mass transfer. In the case
when ammonia driving force (calculated here as the differ-
ence between the interface and bulk concentrations)
is positive whereas the flux is negative, the ammonia
enhancement factor is negative. The profiles in the gas
and liquid films are shown in Figures 11 14, data used
are in Table 1.
Desorption of carbon dioxide results in an increase of
hydroxyl ions and free ammonia concentration in the
liquid film. An ammonia flux changes its direction in the
liquid film. The ammonia interfacial flux is increased,
ENH3 24.1.
Figure 12. CNH3 and CCO2 profiles, ENH3 22.4.
Trans IChemE, Part A, Chemical Engineering Research and Design, 2005, 83(A2): 196204
201
Figure 13. CNH3 and CCO2 profiles, ENH3 1.06, ECO2 22.2.
Absorption of carbon dioxide results in an decrease of
hydroxyl ions and free ammonia concentration in the
liquid film. Ammonia is absorbed although its total driving
force is negative indicating desorption in a physical pro-
cess, ENH3 22.4. Ammonia is produced/consumed in
the region of large CO2 driving force mainly by reaction
(1) i.e., r(1) (4)
NH3  r NH3. The mechanism of depletion of NH3
in the liquid film is connected with reactions of absorbed
CO2 which results in depletion of hydroxyl ions which in
turn shifts reaction (1) into hydrolysis of free NH3 in the
film.
Desorption of ammonia results in a decrease of hydroxyl
ions and an increase of carbon dioxide concentration in the
liquid film. A carbon dioxide flux changes its direction in
the liquid film. CO2 is desorbed although its total driving
force is positive indicating absorption in a physical process,
ECO2 22.2.
Absorption of ammonia results in an increase of hydroxyl
ions and a decrease of carbon dioxide concentration in the
liquid film. Carbon dioxide is absorbed although its total
driving force is negative indicating desorption in a physical
process, ECO2 224.7. Carbon dioxide is produced/con-
sumed in the region of large ammonia driving force
mainly by reaction (4) i.e., r(4) (2) (6)
CO2  rCO2 rCO2. The
mechanism of depletion of CO2 in the liquid film is
Figure 14. CNH3 and CCO2 profiles, ECO2 224.7.
202 BUDZIANOWSKI and KOZIOL

Table 1. The parameters used in calculation of the data in Figures 11 18.

kGP 2  1025, kL 7.5  1025, m s21

mol m22 s21 Pa21
k 1, k 3, k 5 1 kH2O 0.02, s21
21 21
3
kNH3 0.313, m mol s kOH2 5.68, m3 mol21s21
D 1.5  1029, m2 s21 K, H calculated from
Kawazuishi and Prausnitz (1987)
and Edwards et al. (1978)
liquid composition
(Figures 1112)
23 23
Cb,Tot
NH3 0.624, mol m Cb,Tot
CO2 1, mol m
23
b
CNH3 0.001, mol m CCO2 0.377, mol m23
b

CbOH2 2.66  1025, mol m23 CbNH2COO2 1.49  1026, mol m23
gas comp. (Figure 11) pbCO2 31, Pa
pbNH3 0, Pa
gas comp. (Figure 12) pbCO2 10 000, Pa
pbNH3 0.0003, Pa Figure 16. Dependence of CO2 flux on NH3 driving force.
23 23
Cb,Tot
NH3 200 mol m , Cb,Tot
CO2 67 mol m , pbNH3 04000 Pa,
liquid composition b
pCO2 60 Pa.
(Figures 13 and 14)
23 23
Cb,Tot
NH3 200, mol m Cb,Tot
CO2 67, mol m
CbNH3 100, mol m23 CbCO2 0.001, mol m23
CbOH2 0.025, mol m23 CbNH2COO2 12.7, mol m23 bulk contains no ammonia in the example. This is not the
gas comp. (Figure 13) pbCO2 100, Pa case in Figure 18 and ECO2 becomes negative for large
pbNH3 0, Pa positive ammonia driving force.
gas comp. (Figure 14) pbCO2 60, Pa If wastewater already contain large amount of CO2 it
pbNH3 4000, Pa
should be considered that ammonia flux is a function of
CO2 driving force (Figure 15). Desorption of CO2 (negative
driving force) increases an ammonia flux in stripping. So
interfacial concentration of CO2 should be kept as low as
connected with direct reaction of absorbed ammonia with possible. Such conditions are enhanced by low gas phase
free CO2. CO2 content and low CO2 mass transfer resistance in the
Driving force is used here as CiCO2 2 CbCO2 or CiNH3 2 gas phase. Carbon dioxide is then firstly responsible for
b
CNH3. Absorption of CO2 (positive driving force) decreases higher pH value at the interphase than in the bulk, then sec-
an ammonia flux while desorption of CO2 (negative driving ondly acts as a transporting compound which transports
force) increases an ammonia flux in stripping (Figure 15). ammonia bounded as carbamate from the bulk to the inter-
The effect of negative enhancement of mass transfer phase. On the other hand if waste gas containing large
increases with absolute value of CO2 driving force. The amount of CO2 is used for stripping purposes the two
same may be concluded for CO2 (Figure 16). mechanisms indicated are responsible for low pH at the
It is shown in Figure 17 that the enhancement factor of interphase and the transport of ammonia from the
ammonia tends to +infinity when the physical ammonia interphase into the bulk in the form of carbamate.
flux tends to zero. For large positive driving force of
carbon dioxide only ENH3 0 is possible since the gas

Figure 15. Dependence of NH3 flux on CO2 driving force. Figure 17. Dependence of ENH3 on CO2 driving force.
23 23 23 23
Cb,Tot
NH3 0.624 mol m , Cb,Tot
CO2 1 mol m , pbNH3 0 Pa, pbCO2 Cb,Tot
NH3 0.624 mol m , CO2 1 mol m ,
Cb,Tot pbNH3 0 Pa, pbCO2
313000 Pa. 31 3000 Pa.

Trans IChemE, Part A, Chemical Engineering Research and Design, 2005, 83(A2): 196204
 STRIPPING OF AMMONIA FROM AQUEOUS SOLUTIONS 203

C molar concentration, mol m23

d nominal packing diameter, m
D diffusion coefficient, m2s21
D_des degree of desorption, %
E enhancement factor, ( )
G gas flow rate, kmol s21
gz gravitational acceleration, m2s21
H Henrys constant, Pa m3 mol21
I ionic strength, mol m23
K chemical equilibrium constant, r.(1.3,6) mol m23; (2,4)
m3 mol21;(5) mol2 m26 activity of water is expressed by
mole fraction
kH2O reaction (6) rate-constant, s21
kNH3 reaction (4) rate-constant, m3 mol21 s21
kOH2 reaction (2) rate-constant, m3 mol21 s21
kGP physical gas phase mass transfer coefficient,
mol m22 s21 pa21
kL physical liquid phase mass transfer coefficient, m s21
N molar flux, mol m22 s21
Figure 18. Dependence of ECO2 on NH3 driving force. p partial vapour pressure, Pa
23 23
Cb,Tot
NH3 200 mol m , Cb,Tot
CO2 67 mol m , pbNH3 04000 Pa, P total pressure, Pa
pbCO2 60 Pa. R gas constant, J mol21 K21
r chemical reaction rate, mol m2 3 s21
T temperature, K
V flow rate, m23 s21
CONCLUSIONS w superficial mass velocity, kg m22 s21
x co-ordinate perpendicular to interface, m
The stripper for ammonia removal from aqueous solu- ZCol, z column height, m
tions containing CO2 by air or waste gases can be designed zi ionic charges on species i
over a wide range of process parameters with the model
presented in this study. Phase equilibria in that system Greek symbols
a order of reaction
may be described by the Edwards method, physical mass d liquid film thickness
transfer coefficient may be calculated with the Mohunta g activity coefficient
and Onda Puranik correlations. In the experimental sec- l stochiometric coefficient
tion the process model was verified with the system h liquid viscosity, kg m21 s21
r density, kg m23
NH3 CO2 water air modified with strong acid or base. s surface tension, N m21
In comparison with experiments the presented model was
able to calculate absorption/desorption fluxes with reason- Superscripts
able accuracy and was able to predict the influence of b bulk
important process parameters (pH, temperature, air load) c critical
Feed feed
on the stripping efficiency. G gas
The effect of negative enhancement of mass transfer for i interface
simultaneous absorption/desorption and reaction of two L liquid
gases accompanied by complex reversible chemical reac- Tot total
tions with two volatile liquid phase reactants was predicted. Subscripts
In the negative enhancement of mass transfer conditions i,j component i,j
mass transfer of one component may be forced by the r reaction r
other to be absorbed/desorbed with higher rate or may be
forced to be absorbed/desorbed in spite of the fact that
its driving force is negative/positive. REFERENCES
Enhancement factors may be calculated with the two Astarita, G. and Savage, D.W., 1980, Theory of chemical desorption.
adjacent films model. This effect may strongly change con- Chem Eng Sci, 35: 649656.
ditions near the gas-liquid interface remaining conditions in Bieling, V., Rumpf, B., Strepp, F. and Maurer, G., 1989, An evolutionary
optimisation method for modeling the solubility of ammonia and carbon
the fluid bulk almost the same. The effect negative dioxide in aqueous solutions. Fluid Phase Equil, 53: 251 259.
enhancement of mass transfer increases with absolute Beutier, D. and Renon, H., 1978, Representation of NH3 H2S H2O,
value of the other component driving force. Absorption NH3 CO2 H2O, and NH3 SO2 H2O vaporliquid equilibria. Ind &
of carbon dioxide decreases while desorption increases an Eng Chem Proc Des Dev, 17: 220 230.
ammonia flux in stripping. The developments presented Blauwhoff, P.M.M. and van Swaaij, W.P.M., 1985, Simultaneous mass
transfer of H2S and CO2 with complex reversible reactions in an aqu-
in the paper enable more efficient stripping of ammonia eous diisopropanolamine solution. Chem Eng Proc, 19: 6783.
in the presence of carbon dioxide even in the opposite Bunert, U., Buczys, R., Bruhns, M. and Buchholz K., 1995, Strippen von
direction to the liquid concentration difference. Ammoniak. Zuckerind, 11: 960969.
Cornelisse, R., Beenackers, A.A.C.M., van Beckum, F.P.H. and van
Swaaij, W.P.M., 1980, Numerical calculation of simultaneous mass
NOMENCLATURE transfer of two gases accompanied by complex reversible reactions.
Chem Eng Sci, 35: 12451260.
Af DebyeHuckels parameter Danckwerts, P.V., 1970, Gas-Liquid Reactions. (McGraw-Hill, New York,
Ak cross-sectional area of a column, m2 USA).
a interfacial area per unit packed volume, m2 m23 Edwards, T.J., Maurer, G., Newman, J. and Prausnitz, J.M., 1978, Vapor-
ae effective interfacial area per unit packed volume, m2 m23 liquid equilibria in multicomponent aqueous solutions of volatile weak
ad dynamic interfacial area per unit packed volume, m2 m23 electrolytes. AIChE J, 24: 966976.

Trans IChemE, Part A, Chemical Engineering Research and Design, 2005, 83(A2): 196204
204 BUDZIANOWSKI and KOZIOL
Edwards, T.J., Newman, J. and Prausnitz, J.M., 1975, Thermodynamics of
aqueous solutions containing volatile weak electrolytes. AIChE J, 21:
248 259.
Eigen, M. and Schoen, J., 1955, Stobspannungsverfahren zur Untersu-
chung sehr schnell verlaufender Ionenreaktion in wasseriger Losung.
Zeitschrift fur Elektrochemie, 59: 483 494.
Goppert, U. and Maurer G., 1988, Vapor-liquid equilibria in aqueous
solutions of ammonia and carbon dioxide at temperatures between
333 and 393 K and pressures up to 7 MPa. Fluid Phase Equi, 41:
153 185.
Hikita, H., Asai, S. and Ishikawa, H., 1977, Simultaneous absorption of
two gases which react between themselves in a liquid. Ind Chem Eng
Fund, 16: 215219.
Kawazuishi, K. and Prausnitz, J.M., 1987, Correlation of vapor-liquid
equilibria for the system ammonia-carbon-dioxide-water. Ind & Eng
Chem Res, 26: 14821485.
Kurz, F., Rumpf, B. and Maurer, G., 1995, Vaporliquidsolid equilibria
in the system NH3 CO2 H2O from around 310 to 470 K: New experi-
mental data and modeling. Fluid Phase Equil, 104: 261275.
Maurer, G., 1986, Phase equilibria in chemically reactive systems. Fluid
Phase Equil, 30: 337352.
Mohunta, D.M., Vaidyanathan, G.S. and Laddha, G.S., 1969, Effective
interfacial areas in packed columns. Ind Chem Eng, 11: 3942.
Ozturk, S.S. and Shah, Y.T., 1986, Gas absorption with chemical reaction
involving a liquid reactant: penetration theory solution. Chem Eng Sci,
46: 6571.
Pangarkar, V.G., 1974, Gas absorption with reaction in a solution contain-
ing a volatile reactant. Chem Eng Sci, 29: 877 882.
Pawlikowski, E.M., Newman, J. and Prausnitz, J.M., 1982, Phase equili-
bria for aqueous solutions of ammonia and carbon dioxide. Ind Eng
Chem Proc Des Dev, 21: 764 770.
Pinsent, B.R.W., Pearson, L. and Roughton F.J.W., 1956a, The kinetics of
combination of carbon dioxide with hydroxide ions. Trans of the Fara-
day Soc, 52: 15121520.
Pinsent, B.R.W., Pearson, L. and Roughton F.J.W., 1956b, The kinetics of
combination of carbon dioxide with ammonia. Trans of the Faraday
Soc, 52: 15951598.
Puranik, S.S. and Vogelpohl A., 1974, Effective interfacial area in irrigated
packed columns. Chem Eng Sci, 29: 501 507.
Rajniak, P., Kralik, M. and Ilavsky J., 1992, A steady state equation-
oriented simulator for separation processes of solutions with weak elec-
trolytes. Comp Chem Eng, 16: S457S464.
Roper, G.H., Hatch, T.F. and Pigford, R.L., 1962, Theory of absorption
and reaction of two gases in a liquid. Ind Eng Chem Fundamentals, 1:
144 152.
Trans IChemE, Part A, Chemical Engineering Research and Design, 2005, 83(A2): 196204
Shaikh, A.A. and Varma, A., 1984, Gas absorption chemical reactions. The
case involving a volatile liquid component. Chem Eng Sci, 39:
16391641.
van Swaaij, W.P.M. and Versteeg, G.F., 1992, Mass transfer accompanied
with complex reversible chemical reactions in gas liquid systems: an
overview. Chem Eng Sci, 47: 31813195.
Vas Bhat, R.D., van Swaaij, W.P.M., Kuipers, J.A.M. and Versteeg, G.F.,
1999a, Mass transfer with complex chemical reactions in gas liquid
systemsI. Consecutive reversible chemical reactions with equal diffu-
sivities. Chem Eng Sci, 54: 121 136.
Vas Bhat, R.D., van Swaaij, W.P.M., Kuipers, J.A.M. and Versteeg, G.F.,
1999b, Mass transfer with complex chemical reactions in gas liquid sys-
temsII. Effect of unequal diffusivities on consecutive reactions. Chem
Eng Sci, 54: 137147.
Vas Bhat, R.D., Kuipers, J.A.M. and Versteeg, G.F., 2000, Mass transfer
with complex chemical reactions in gas liquid systems: two step revers-
ible reactions with unit stoichiometric and kinetic orders. Chem Eng J,
76: 127 152.
Versteeg, G.F., Kuipers, J.A.M., van Beckum, F.P.H. and van Swaaij,
W.P.M., 1989, Mass transfer with complex reversible chemical reac-
tionsI. Single reversible chemical reaction. Chem Eng Sci, 44:
22952310.
Versteeg, G.F., Kuipers, J.A.M., van Beckum, F.P.H. and van Swaaij,
W.P.M., 1990, Mass transfer with complex reversible chemical reac-
tionsII. Parallel reversible chemical reactions. Chem Eng Sci, 45:
183197.
Wilson, G.M., 1980, A new correlation of NH3, CO2, and H2S volatility
data from aqueous sour water systems. U.S. Environmental Protection
Agency, EPA-600/2-80-067.
Yu, W.C. and Astarita, G., 1987a, Selective absorption of hydrogen sul-
phide in tertiary amine solutions. Chem Eng Sci, 42: 419424.
Yu, W.C. and Astarita, G., 1987b, Design of packed towers for selective
chemical absorption. Chem Eng Sci, 42: 425433.
ACKNOWLEDGEMENT
The authors wish to thank State Committee for Scientific Research
(Poland) for their financial support to this investigation.
The manuscript was received 21 July 2003 and accepted for publication
after revision 7 December 2004.