Article

pubs.acs.org/IECR

Experimental Studies and Rate-Based Process Simulations of CO2

Absorption with Aqueous Ammonia Solutions
Zhenqi Niu, Yincheng Guo,* Qing Zeng, and Wenyi Lin
Department of Engineering Mechanics, Tsinghua University, Beijing 100084, China
*
S Supporting Information

ABSTRACT: A pilot plant at laboratory scale for absorption of CO2 has been constructed and operated to test the CO2 removal
by aqueous ammonia solutions. The design of the pilot plant is based on a standard absorption and desorption flow sheet and
partial or complete separation of gas mixtures. Pilot plant data for CO2 removal efficiencies, effects of CO2 loading, and
temperature profiles are obtained. A rate-based model, RateFrac in Aspen Plus simulator, is used to simulate the CO2 absorption
of the pilot plant. The simulation results of the CO2 capture predicted by the rate-based model are in good agreement with the
experimental data of the pilot plant. Further, the optimization covering operational parameters is carried out using the rate-based
model.

1. INTRODUCTION constructed and operated to test the technical and economic

Fossil fuels will play a major role in the world energy supply
and production for the next several decade years. About 75% of
the anthropogenic emission of CO2 to the atmosphere during
the past 20 years is due to fossil fuel burning.1 Fossil-fueled
power plants generate the largest amount of CO2 emission.
CO2 capture from power plant flue gas is a key measure to
reduce CO2 emission.
Four technical routes have been applied for the capture of
CO2: precombustion, postcombustion, oxy-combustion, and
chemical looping combustion.2,3 In recent years, there are
several carbon capture technologies to be developed, for
example, chemical absorption,4,5 membrane separation,6
adsorption methods,7 biological fixation,8 and hydrate-based
separations.9 For the existing and new power plant, chemical
absorption method is suitable, which is one of the most
common and cost-effective industrial technologies today.10,11
However, the cost to capture CO2 from flue gas using current
technologies is high (about 20% of reduction in the thermal
efficiency of power station).12
The monoethanolamine (MEA) scrubbing is widely used in
the gas purification and carbon capture processes. However, the
operating cost of the MEA process is high due to huge energy
consumption in regenerating and operation problems such as
corrosion and solvent degradation.13 Aqueous ammonia is
considered as the promising substituted solvent.14−19 The
advantages of aqueous ammonia are high CO2 loading capacity,
no absorbent degradation, potential of capturing multiple flue
gas components (SO2, NO2, CO2), low energy requirement,
and resistance to oxidation. Many researchers have studied the
CO2 capture using aqueous ammonia, including reaction
mechanism,20−22 kinetics,23 removal efficiency,17 and mass
transfer coefficient.24
As mentioned above, a body of laboratory work has
accumulated for the fundamental features of CO2 absorption.
However, industry-led research work on the aqueous ammonia
based capture process at both lab and pilot plant scale is at the
initial stage. Several pilot and demonstration plants have been
feasibility of ammonia based postcombustion capture pro-
cesses.25−28 Alstom Corp. is developing the chilled ammonia
process as described in the open literature.25,29,30 The chilled
ammonia process absorbs the CO2 at low temperature (2−10
°C), and the CO2-rich stream is desorbed at temperatures of
100−150 °C and pressures of 30−2000 psi, which is higher
than atmospheric pressure. Puxty et al.31 has found that the
overall mass transfer coefficient for aqueous ammonia was at
least 1.5−2 times smaller than MEA at the low temperature.
Therefore, it needs to improve the technique performance for
the chilled ammonia process. Yu et al.28 reports that CSIRO
and Delta Electricity have jointly constructed a research scale
pilot plant at Munmorah power station. The pressure of
stripper is 300−850 kPa, which is also higher than atmospheric
pressure. Although the high pressure of the product CO2
reduces the CO2 compressor power, the high pressure of the
stripper increases the temperature of reboiler, which results in
more steam consumption. Steam loss is the main energy
consumption of the CO2 capture process. Powerspan has
developed an aqueous NH3-based CO2 capture process, called
ECO2, in which the absorption takes place at temperatures
above 20 °C.26 Park et al.27 study the optimal conditions of the
absorbent concentration, rich CO2 loading, and regeneration
temperature in a continuous CO2-capture process. The
ammonia gases in flue gas from absorber and in desorbed gas
from stripper are all scrubbed by water. In their lab pilot plant,
the heat consumption includes not only NH3 abatement
regenerator heat duty and the reboiler heat duty of CO2-rich
solvent desorption but also the heat duty of washing water
desorption for scrubbing the desorbed gas from stripper.
Compared with the MEA process, industry-led research work,
study on, e.g., ammonia loss, process selection, energy
Received: December 27, 2011
Revised: February 27, 2012
Accepted: March 8, 2012
Published: March 8, 2012

© 2012 American Chemical Society 5309 dx.doi.org/10.1021/ie2030536 | Ind. Eng. Chem. Res. 2012, 51, 5309−5319
Industrial & Engineering Chemistry Research
Figure 1. Simplified flow sheet of the laboratory pilot plant.
Table 1. Correlation Parameters of Metal Wire Gauze Structured Packing
number of theoretical plates, 1/m specific surface area, m2/m3
10−12 750
consumption, and practical experience, is still scarce in the
public domain. Therefore, it is necessary to study intensively
the CO2 absorption and desorption processes.
Process simulation also provides the means to interpret
laboratory experiments and quantify the process performance
among various CO2-capture processes using aqueous ammonia.
Darde et al.29 have presented thermodynamic analysis of the
chilled-ammonia process. It calculates the activity coefficient for
the liquid phase using the extended UNIQUAC model and the
gas phase fugacity using the Soave−Redlich−Kwong (SRK)
equation for the volatile compounds. Mathias et al.30 have
quantitatively evaluated the chilled-ammonia process for CO2
capture using thermodynamic analysis and process simulation.
The Electrolyte-NRTL model for the NH3−CO2−H2O system
has been used in the Aspen Plus simulator. It should be noted
that the process simulation model used by Darde et al.29 and
Mathias et al.30 assumes physical and chemical equilibrium and
does not consider reaction kinetics and vapor-to-liquid mass
transfer rate in the absorber. It is known that the rate-based
modeling approach is rigorous and offers higher model fidelity
over the traditional equilibrium-stage modeling approach.32
Therefore, developing the rate-based process modeling of CO2
absorption with aqueous ammonia is necessary.
Industrial or pilot plant data available for aqueous ammonia
separation processes are still limited in the public literature.
Besides, the research of the rate-based model for CO2
absorption using aqueous ammonia solution is still at the
initial stage. The motivation of this paper is to investigate the
feasibility of CO2 removal by an ammonia process in a pilot
plant at laboratory scale. A rate-based absorption model,
RateFrac, based on Aspen Plus process simulator, is used to
simulate the pilot plant, and the experimental results will
provide the validity of rate-based modeling of the CO2 capture
process by ammonia.
2. EXPERIMENTAL INSTALLATION
2.1. Description of the Laboratory Pilot Plant. A
simplified flow sheet for the pilot rig is shown in Figure 1. The
design of the pilot plant is based on a standard absorption and
desorption flow sheet and partial or complete separation of gas
Article
void fraction, % pressure drop, MPa/m density, kg/m3 liquid loading, m3/m2·h
87 4.6−6.6 × 10−4 210 0.2−20
mixtures. This is an integrated pilot plant operating with
absorber, stripper, separation system, and connected unit
operations. All of columns and reactors are made of 304
stainless steel. The packing is metal wire gauze structured
packing (Tianjin Septech Co., Ltd. DZ-II-750Y). Its correlation
parameters are shown in Table 1. The internal diameters of
absorber 1 and absorber 2 are 0.15 and 0.16 m, respectively.
The packing height of the both absorbers is 1.47 m. The
packing height of absorber 2 can be varied within 1.47 m, which
allows investigation of the effect of packing height on CO2
removal. There are two methods to generate flue gas: one is by
methane combustion in a furnace, and the other is by mixture
of air and CO2. The flow rates of methane, air, and CO2 are
0.8−1.0, 10.0−16.0, and 0−2.0 m3/h, respectively. The flue gas
enters the lower part of absorber 1. The flow sheet incorporates
two absorbers, which can be run in series or in parallel. In the
case of series operation, the solvent enters absorber 2 first and
then absorber 1. In the absorbers, the aqueous ammonia and
flue gas stream were in a counter flow pattern.
In the ammonia pilot plant CSIRO and Delta Electricity
constructed,28 ammonia loss at the stripper gas outlet is
reduced due to high pressure of the stripper. The ammonia
concentration can be controlled at 200 ppm under a pressure of
850 kPa at temperatures of 20−25 °C. However, these pressure
and temperature conditions in the stripper condenser and
reflux lines lead to the precipitation of ammonium bicarbonate.
The buildup of solids can block the stripper condenser and
reflux pipes, leading to a shutdown of the pilot plant. Blockage
also occurs in instrument tubing, leading to false readings and
affecting the operation. In order to solve this problem, the
stripper and separation system of gas mixture, containing CO2
and ammonia, are adopted in this study. The pressure of
stripper and separation system is near the atmospheric pressure.
The lower pressure decreases the temperature of reboiler that is
about 85−95 °C. Low-grade thermal energy may be applied for
the heat of reboiler, which will be a substitute for the steam
from steam turbine. The temperature of stripper condenser and
separation system is about 50−70 °C. The precipitation of
ammonium bicarbonate or ammonium carbonate will decom-
pose in this temperature, so blockage of condenser and pipes
5310 dx.doi.org/10.1021/ie2030536 | Ind. Eng. Chem. Res. 2012, 51, 5309−5319
Industrial & Engineering Chemistry Research
will not be a problem. Ammonia loss at the stripper gas outlet is
obvious at this pressure and temperature condition. The
separation system is used to separate the CO2 and NH3 gas.
The system is based on the principle that NH3 is absorbed by
water easier than CO2. The ammonia gas is dissolved by CO2-
lean stream from reboiler at high gas velocity.33 After cooling
and ammonia makeup, the stream from separation system is
reused for absorption of CO2.
In order to simplify the operation, the absorption and
stripping experiments were conducted separately, and only the
absorber data are reported here. Data for the pilot absorber unit
and operating conditions are shown in Table 2. The pressure of
Table 2. Operation Conditions for the Absorber
parameter
liquid flow rate (L/h) 60−180
ammonia concentration (wt %) 7.6−8.5
rich solution loading (mol/mol) 0.084−0.482
lean solution loading (mol/mol) 0−0.397
temperature lean stream to absorber 2 (°C) 18.0−29.0
flue gas flow rate (m3/h) 9.0−16.0
CO2 concentration of flue gas (v/v, %) 6.9−15.7
temperature of flue gas to absorber 1 (°C) 17.7−138.0
absorber is atmospheric pressure. The packing height of
absorber 2 can be varied which allows investigation of the
effect of packing height on CO2 removal. The tests were
performed with 7.6−8.5 wt % ammonia solutions.
2.2. Measurements. The gas and liquid sampling points
were given in Figure 1. Five gas sampling points are arranged
along absorber 1 height. The concentration of CO2 is measured
by an infrared gas analyzer (Beijing Huyuan Analytical
Instrument Institute Ltd.). At first, the sampling gas is induced
into a small gas washing bottle loading sulfuric acid, where most
of NH3 is absorbed. Then, the sampling gas enters into the gas
dryer filled with desiccant CaCl2, where water vapor and the left
NH3 are absorbed. The concentration of NH3 is measured by a
laser analyzer (Beijing Define Technology Ltd.). Sampling pipe
and measuring cell in the analyzer are heated to the
temperature of 120−130 °C in order to minimize the reaction
between CO2 and NH3. The full scales of measurement ranges
of CO2 and NH3 analyzer are 20% (v/v) and 10% (v/v),
respectively. The CO2 and NH3 analyzers are calibrated to a
precision of about ±2% F.S. (full scale) after each run, with at
least 4−5 different concentrations covering the whole range of
interest. All temperature probes (PT-100 resistance temper-
ature sensors) were calibrated to a precision of about ±0.5 °C.
After a change in operational conditions, the plant is run for
at least 30 min to ensure steady state operation. Liquid samples
are withdrawn from the system for analysis, and operational
data are recorded at the same time. The liquid sampling points
are arranged at the absorber inlet and outlet. Each time, the
liquid sample titration analysis is conducted within 10 min.
Standard wet chemistry titration is performed with an
automatic titrator (Metrohm 877 Titrino plus) in the analytic
lab for the determination of CO2 and NH3 content in the liquid
samples. The titration method is summarized as follows:
Hydrochloric acid titrating solution (0.1 N HCl) is added to an
aliquot of a diluted sample with a dropwise add velocity. When
the first and second inflection points of titration curve are
attained, the usages of HCl are EP1 mL and EP2 mL,
respectively. EP2-EP1 and EP2 are used to calculate CO2 and
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NH3 concentration in the liquid samples (apparent composi-
tion). Supposing components in the solution are H2O, NH3,
CO2, H3O+, OH−, NH4+, NH2COO−, HCO3−, CO32−, N2,
NH4HCO3, and CO2, loading of solutions in this paper refers
to the molar ratio of CO2 to NH3 in the solvent as follows:
CO2 loading = [CO2 ]tot /[NH3]tot
{[CO2 ] + [NH2COO−] + [HCO3−] + [CO32 −]}
=
{[NH3] + [NH 4+] + [NH2COO−]}
(1)
where [ ] is the concentration of components, mol/L. The total
CO2 and NH3 concentrations are attained by titration analysis.
The ion and molecule concentrations are calculated by rate-
based modeling.
The CO2 removal efficiency in absorber refers to percentage
of the amount of CO2 absorbed in the absorber per unit time
(kg/h) with respect to the CO2 mass flow rate at the inlet of
absorber. The calculation method is given as follows:
y − y2
ε= 1 × 100%
y1(1 − y2 ) (2)
where ε is the CO2 removal efficiency; y1 is the CO2 mole
fraction at the inlet of absorber 1; y2 is the CO2 mole fraction at
the outlet or some position of absorber.
Individual liquid and gas phase mass balances for CO2 could
be obtained on the basis of the content of CO2 in both phases.
The accuracy of the balances is defined as percent deviation:
Liq CO − GasCO2
2
Devexp(moleflow) = × 100%
max(Liq CO , GasCO2)
2
(3)
where LiqCO2 is the increased amount of CO2 in absorber
liquid, mol/h; GasCO2 is the decreased amount of CO2 in
absorber gas, mol/h.
2.3. Evaluation of Experimental Data with CO 2
Absorption. The pilot plant experiments of absorption were
conducted for all 19 runs. Their operational parameters are
shown in Supporting Information, Table S1. The CO2 loading
of CO2-rich solutions at absorber outlet was measured only for
cases 11−19 (as shown in Supporting Information, Table S2).
Deviation can be calculated by eq 3. The highest absolute value
of deviation is 9.35%. This systematic deviation is so small that
it is acceptable and actually can be taken as a support for the
quality of the experimental data. This indicates that the liquid
and gas phase measurement methods are appropriate.
3. MODEL DEVELOPMENT
The absorber was modeled with RateFrac, the rate-based
distillation module of Aspen Plus. The details of RateFrac
model can be found in Aspen Plus Documentation.34 This
approach required that a rigorous thermodynamic model, a
rigorous rate model, and transport property models be
implemented in Aspen Plus.
3.1. Thermodynamic Model. The RateFrac model used
the rigorous Electrolyte-NRTL thermodynamics to predict
enthalpies, entropy, equilibrium vapor pressures of NH3, CO2,
and H2O, and solution speciation. Thermodynamic models for
electrolyte systems require a chemistry model. The chemistry
model of NH3−CO2−H2O system is presented in Table 3.
Chemical equilibrium is assumed in the chemistry model. CO2
dx.doi.org/10.1021/ie2030536 | Ind. Eng. Chem. Res. 2012, 51, 5309−5319
Industrial & Engineering Chemistry Research Article

Table 3. Chemistry Model for the NH3−CO2−H2O System

chemistry ID chemistry type
1 equilibrium
2 equilibrium
3 equilibrium
4 equilibrium
5 equilibrium
6 salt
chemical equation
2 H2O ↔ H3O+ + OH−
CO2 + 2 H2O ↔ HCO3− + H3O+
HCO3− + H2O ↔ CO32− + H3O+
NH3 + H2O ↔ NH4+ + OH−
NH3 + HCO3− ↔ NH2COO− + H2O
NH4HCO3(S) ↔ NH4+ + HCO3−

is absorbed by ammonia solution, and weak electrolytes of

NH3·H2O and H2CO3 are formed. Absorbed CO2 in solution
exists as molecular CO2, carbamate, bicarbonate, and carbonate Figure 2. Comparison between the model calculations and data39 for
anions, while NH3 in solution exists as molecular NH3, the partial pressure of CO2.
carbamate anion, and ammonium cation. The chemical
equilibrium expression shown in eq 4 is used for the chemical
equilibrium reactions. During the CO2 absorption with low
concentration aqueous ammonia at 25 °C, it is observed that
carbamate formation is dominating at the early stage of
absorption. Then, the bicarbonate formation took over the
domination at the later stage while the carbonate remained
unchanged. During the absorption of CO2, the NH4HCO3
precipitation may form, and its chemical expression is also
present as eq 4. The parameters A, B, C and D shown in Table
4 are regressed against equilibrium data from Miles and

Table 4. Parameters A, B, C, and D in Eq 4

chemistry Figure 3. Comparison between the model calculations and data39 for
ID A B C D the partial pressure of NH3.
1 132.899 −13445.9 −22.4773 0
2 231.465 −12092.1 −36.7816 0 3.2. Rate-Based Model. In RateFrac model, separate
3 216.049 −12431.7 −35.4819 0 balance equations are written for each distinct phase, and mass
4 −1.256563 −3335.7 1.4971 −0.0370566 and heat transfer resistances are considered according to the
5 −4.5834 2900 0 0 two-film theory40 with implicit calculation of interfacial fluxes
6 3.1644715 −3483.7909 0 0 and film discretization for the nonhomogeneous film layer. The
rate model used in the absorber was made consistent with the
Wilson35 and Trypuć and Kielkowska.36 The Redlich−Kwong Electrolyte-NRTL thermodynamic model. In the absorber, the
equation of state and electrolyte−NRTL method are used to reactions involving CO2 at each theoretical stage were
computer vapor properties and liquid properties, respectively. described with a kinetic model. The kinetic reaction model of
The electrolyte−NRTL model used here is the nonideality the NH3−CO2−H2O system is presented in Table 5. The
model that is available in Aspen Plus.37 The NRTL parameters
for electrolyte pairs were regressed against vapor−liquid Table 5. Kinetic Reaction Model for the NH3−CO2−H2O
equilibrium data from Göppert and Maurer38 and Kurz et al.39 System
reaction ID reaction type chemical equation
ln K eq = A + B /T + C ln(T ) + DT (4)
1 equilibrium NH3 + H2O ↔ NH4+ + OH−
2 equilibrium 2 H2O ↔ H3O+ + OH−
where Keq is the equilibrium constant for chemistry ID 1−6 and
3 equilibrium HCO3− + H2O ↔ CO32− + H3O+
A, B, C and D are adjustable parameters.
4 kinetic CO2 + OH− → HCO3−
CO2, NH3, and N2 are selected as Henry-components to
5 kinetic HCO3− → CO2 + OH−
which Henry’s law is applied and the Henry’s constants are
6 kinetic NH3 +CO2 + H2O → NH2COO− + H3O+
retrieved from Aspen Plus databanks for these components
7 kinetic NH2COO− + H3O+ → NH3 +CO2 + H2O
with water. In the reactions calculations, the activity coefficient
8 salt NH4HCO3(S) ↔ NH4+ + HCO3−
basis for the Henry’s components is chosen to be aqueous.
Therefore, in calculating the unsymmetric activity coefficients
equilibrium reactions 1−3 are the same as the chemistry model.
of the solutes, the infinite dilution activity coefficients will be
calculated on the basis of infinite-dilution condition in pure The reactions of CO2 with OH− and the reactions of CO2 with
water, instead of in mixed solvents. NH3 are rate-controlled reactions (reactions 4−7 in kinetic
The simulation results are obtained from flash calculations at
the temperature and the composition of experimental cases. reaction model), and the general power law expression is
Figures 2 and 3 show the simulation results together with
experimental data of Kurz et al.39 It can be seen that the model ⎛ T ⎞ n ⎡⎛ − E ⎞⎛ 1 1 ⎞⎤
predictions are in good agreement with the vapor−liquid r = k ⎜ ⎟ exp⎢⎜ ⎟⎜ − ⎟⎥
⎝ To ⎠ ⎢⎣⎝ R ⎠⎝ T To ⎠⎥⎦ (5)
equilibrium data.
5312 dx.doi.org/10.1021/ie2030536 | Ind. Eng. Chem. Res. 2012, 51, 5309−5319
Industrial & Engineering Chemistry Research Article

where r is the rate of reaction; k is the pre-exponential factor; n 4. COMPARISON BETWEEN EXPERIMENTS AND
is the temperature exponent; E is the activation energy. The RATE-BASED MODEL PREDICTIONS
factors k, n, and E are given in Table 6. The kinetic parameters As mentioned above, pilot plant at laboratory scale had been
for reactions 4−7 in Table 5 are derived from the work of constructed and operated to test the ammonia process. Rate-
Pinsent et al.41 based rigorous simulation of the process is beneficial to
comprehend and estimate the CO2 absorption processes with
Table 6. Parameters k, n, E in Eq 5 NH3. The experimental data provides the verification of rate-
reaction ID k n E, cal/mol
based NH3 model. The model is meant to be used as a guide
for modeling more sophisticated CO2 capture processes with
4 4.32 × 1013 0 13249
NH3 for process development, debottlenecking, and plant and
5 2.38 × 1017 0 29451
equipment design.
6 1.35 × 1011 0 11585
4.1. CO2 Removal Efficiency. The absorption experiments,
7 4.75 × 1020 0 16529
operational parameters, and the CO2 removal efficiency ε
simulation results for all 19 cases are shown in Supporting
RateFrac model in Aspen Plus provides four different flow Information, Table S1. The CO2 removal efficiencies of
models, which are Mixed, CouterCurrent, Vplug, and VPlug- experimental and simulated data of cases 1−16 are compared
Pavg. CounterCurrent flow model is chosen to determine the in Figure 4. It can be seen that the correspondence between
bulk properties required to evaluate the mass and energy fluxes
and reaction rates. The bulk properties for each phase are an
average of the inlet and outlet properties.
The RateFrac module of Aspen Plus is used to integrate the
heat transfer and multicomponent mass-transfer relationships
for a packed absorber. Mass transfer rate depends on the binary
mass transfer coefficients, the averaged mole fraction driving
force, and interfacial area. The flow model determines the
averaged mole fraction driving force. The mass transfer
coefficients and interfacial area are calculated by empirical
correlation formula.42 The packing is set as CY structured
packing. Its correlation parameters are shown in Table 1.
Interfacial area factor is used to match the experimental value.
Figure 4. Comparison of the experimental and the simulated CO2
Besides, liquid holdup is an important parameter. In the removal efficiency.
simulation model, gas phase reactions are ignored. Liquid
holdup is used to calculate the reactions of bulk liquid. Liquid experimental and simulated values is good at the different
holdup is suitable to be set as 3−5% of free volume,43 and 4% operational conditions of cases 1−16.
of free volume is chosen in this paper. The heat transfer The profile of the experimental and the simulated ε along
coefficient may be estimated by Chilton-Colburn method.44 packing height is shown in Figure 5. The packing height is
Heat transfer area is assumed as calculated interfacial area. Gas-
film and liquid-film mass- and heat-transfer coefficients were
obtained as a function of liquid and gas flow rates and
properties with the default correlations of RateFrac.
3.3. Transport Property Models. Rate-based process
models require transport property models applied for heat
transfer, mass transfer, interfacial area, liquid holdup, etc.
Transport property models include viscosity, thermal con-
ductivity, diffusion coefficient, and surface tension.
For the liquid viscosity, the Jones-Dole electrolyte correction
model is used to calculate the corrected value of viscosity of
liquid mixture. The interaction parameters between NH3 and
H2O are regressed against experimental NH3−H2O viscosity
data from Pleskov and Igamberdyev45 and Frank et al.46 The Figure 5. Comparison between the experimental and the simulated ε
Jones-Dole model parameters of CO32− and HCO3− are profile for case 11.
regressed against K2CO3−H2O viscosity data from Pac et al.47
counted from the bottom of packing in the absorber. In cases
and KHCO3−H2O viscosity data from Palaty,48 respectively.
For NH4+, Aspen Plus databank values are used. 1−11, only absorber 1 is used, the packing height is 1.47 m, and
For the liquid thermal conductivity, the Riedel electrolyte the ammonia concentration of inlet liquid is 4.677 mol/L. Five
correction model is used.49 Thermal conductivity of compo- gas sampling points were arranged along absorber 1 height. The
nent NH2COO− does not have the experimental data, and sampling gas may contain droplets, which would cause reaction
value of zero is used. Electrolyte solutions diffusion coefficient of CO2 and ammonia in sampling pipes. Therefore, in the
is calculated using the Nernst−Hartley model. Diffusion middle section of absorber 1, the measured ε is higher than the
coefficient of component NH2COO− does not have the simulated ε. At the outlet of absorber, droplets and reaction in
experimental data, and nominal value is used. Liquid surface sampling pipes may be ignored. In general, the tendency of the
tension is calculated by the Onsager−Samaras model. experimental and the simulated ε is in good agreement.
5313 dx.doi.org/10.1021/ie2030536 | Ind. Eng. Chem. Res. 2012, 51, 5309−5319
Industrial & Engineering Chemistry Research
4.2. The Effect of CO2 Loading. In the aqueous ammonia-
based CO2 capture processes, NH3 loss is an important issue.
Decrease of the NH3 mole fraction of outlet gas is beneficial for
meeting national emission standard of ammonia easily. Under
the required ε, improving the CO2 loading of CO2-lean
solutions is beneficial for decreasing the NH3 mole fraction of
outlet gas and increasing the CO2 loading of CO2-rich
solutions. Besides, with the CO2 loading of CO2-rich solutions
increasing, the heat duty of regenerator will decrease. Thus, it is
necessary to investigate the effect of the CO2 loading of CO2-
lean solutions on ε, NH3 concentration, and CO2 loading of
CO2-rich solutions.
The CO2 loading of CO2-lean solutions of cases 15−19
increases from zero to 0.397, and other operation parameters
are in accordance among 5 cases. The effects of the CO2
loading of CO2-lean solutions on ε, NH3 concentration, and
CO2 loading of CO2-rich solutions are shown in Figures 6, 7,
Figure 6. Comparison between the experimental and the simulated ε
with CO2 loading increasing.
Figure 7. Comparison between the experimental and the simulated
CO2 loading of rich solution with CO2 loading increasing.
and 8. It can be seen that the ε decreases quickly with the CO2
loading increasing. When the CO2 loading is higher than 0.22,
the ε drops to lower than 80%. The CO2 loading of CO2-rich
solutions increases with the CO2 loading increasing. Higher
CO2 loading of CO2-lean solutions is beneficial for decreasing
the NH3 mole fraction of outlet gas, which will reduce the NH3
abatement regenerator heat duty. In conclusion, at this
operation condition, the best CO2 loading of CO2-lean
solutions is 0.124−0.150 in order to achieve 90% of CO2
removal efficiency.
In Figures 6−8, simulation results show that the rate-based
model can predict the variation tendency of main optimization
parameters. At the lower CO2 loading of CO2-lean solutions,
the correspondence of experimental and simulated results is
good. However, at the larger CO2 loading, the discrepancy is
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Figure 8. Comparison between the experimental and the simulated
NH3 concentration with CO2 loading increasing.
large. The reaction mechanism is not in agreement with the
chemistry model and kinetic reaction model for the NH3−
CO2−H2O system (as shown in Tables 3 and 5), which leads to
large deviation between the experimental and the simulated
data.
4.3. Temperature Profiles. Figure 9 shows the predicted
temperature profile together with the experimental data for case
Figure 9. Comparison between the experimental and the simulated
temperature profile for case 14.
14. In Figure 9, the dashed line represents vapor temperature
and the solid line represents liquid temperature. In case 14, the
absorber incorporates absorber 1 and absorber 2, which run in
series. Five temperature measuring points are arranged along
absorber 1 height. It is not possible to determine whether the
temperature probes within the column measured liquid or gas
phase. The temperature plots for the two phases therefore use
the same internal temperatures, while the gas and liquid
temperatures at the ends are added to the set. At the position of
zero packing height, the temperatures of inlet gas and outlet
liquid are measured, respectively. At the inlet and outlet
position of absorber 2, only liquid temperature is measured.
Since the liquid out of absorber 2 is pumped into the top of
absorber 1, the temperature has a discontinuous section at the
connection of two absorbers. At the lower part of packing, the
vapor temperature is higher than liquid temperature, so the
measuring internal temperatures are close to the vapor
temperature; the temperature of lower part of packing is
changing rapidly.
The overall agreement between the experimental and the
simulated ε, the CO2 loading of CO2-rich solutions, NH3
concentration of outlet gas, and the temperature is good.
This indicates that the rate-based model for CO2 capture by
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Industrial & Engineering Chemistry Research
Figure 10. Effects of the packing height on ε, CO2 loading, NH3 concentration of outlet gas, and temperature.
Figure 11. Effects of the NH3 concentration of CO2-lean solutions on ε, CO2 loading, NH3 concentration of outlet gas, and temperature.
aqueous ammonia solution can be applied for process
simulation and optimization analysis.
5. PROCESS OPTIMIZATION WITH RATE-BASED
MODEL SIMULATIONS
Process optimization can be divided into two main procedures:
absorption and desorption. In this study, only the absorption
process optimization is investigated in order to attain the
control mechanism and optimization approach. Moreover,
process optimization with rate-based model simulations will
provide theoretical guidance for energy-saving technology. For
the CO2 absorption, main optimization target parameters are ε,
CO2 loading of CO2-rich solution, and NH3 concentration of
outlet gas. The optimization parameters and their setting
operational parameters for process optimization with the rate-
based model are shown in Supporting Information, Table S3.
5.1. Optimization of Packing Height. Packing height has
effects on construction cost, operation, and process conditions.
Figure 10 gives the effects of the packing height on ε, CO2
loading, NH3 concentration of outlet gas, and temperature of
rich solution. Figure 10a shows that the packing height has an
obvious effect on the ε. It can be seen that the ε and the CO2
loading of CO2-rich solutions increase to stable values with the
packing height increasing. Mass transfer rate is related to
interfacial area. Improving packing height leads to the
increment of interfacial area obviously, which enhances the
mass transfer. When the packing height is higher than 4.0 m,
the increased mass transfer area has a little effect on the CO2
absorption. Figure 10b shows that the NH3 concentration of
outlet gas has a little augment with the packing height
increasing, and the temperature of rich solution increases from
25 to 32.5 °C. With the packing height increasing, the amount
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of CO2 reacted with ammonia is increasing, and reaction heat
release is increasing. The release heat makes the temperature of
CO2-rich solutions increase. It is concluded that there is a best
packing height, which is 3−4 m in this operation condition.
5.2. Optimization of Concentration. Effects of the NH3
concentration of CO2-lean solution on ε, CO2 loading, NH3
concentration of outlet gas, and temperature of rich solution are
shown in Figure 11. It can be seen that the concentration of
aqueous ammonia solution plays an important role on the CO2
removal efficiency. With the NH3 concentration of CO2-lean
solution increasing, the ε increases to a high level and keeps a
stable value, the CO2 loading of rich solution decreases, the
NH3 concentration of outlet gas increases quickly, and the
temperature of rich solution reaches to a peak value. When the
NH3 concentration of CO2-lean solution is higher than 4 mol/
L, improving the concentration of aqueous ammonia has a little
effect on the CO2 removal efficiency under the condition of this
study, but the NH3 concentration of outlet gas increases
sharply. As mentioned above, on the basis of the premise that
the required ε could be realized, it is necessary to reduce the
NH3 concentration of outlet gas and improve the CO2 loading
of CO2-rich solution as much as possible. NH3 leakage will give
rise to NH3 loss and environmental pollution. When the NH3
concentration of CO2-lean solution is 3.5−4 mol/L, the
temperature of rich solution reaches to its highest value,
which is beneficial for the regeneration of CO2-rich solution.
Thus, the best NH3 concentration of CO2-lean solution is 3.5−
4 mol/L, which is the obvious difference comparing aqua
ammonia in the chilled ammonia process; its NH3 concen-
tration may reach up to 28%(w/w). When the ε increases to a
high level and keeps a stable value, reaction heat release also
keeps a constant value, but the heat consumption due to the
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Industrial & Engineering Chemistry Research Article

Figure 12. Effects of the CO2 concentration of flue gas on ε, CO2 loading, NH3 concentration of outlet gas, and temperature.

Figure 13. Effects of the temperature of liquid on ε, CO2 loading, NH3 concentration of outlet gas, and temperature.

Figure 14. Effects of the temperature of flue gas on ε, CO2 loading, NH3 concentration of outlet gas, and temperature.

evaporation of NH3 increases when the NH3 concentration of
CO 2 -lean solution increases. It is found that the NH3
concentration of flue gas is high at the high NH3 concentration
of CO2-lean solution. Besides, the specific heat of ammonia
solution also increases a little with the NH3 concentration of
CO2-lean solution increase. Therefore, the temperature of CO2-
rich solution decreases when the NH3 concentration of CO2-
lean solution is greater than 4 mol/L.
Figure 12 shows effects of the CO2 concentration of flue gas
on ε, CO2 loading, temperature of rich solution, and NH3
concentration of outlet gas. With the inlet concentration of
CO2 increasing, the CO2 removal efficiency decreased a little,
the CO2 loading of CO2-rich solutions increases, the temper-
ature of rich solution increases, and the NH3 concentration of
outlet gas keeps a nearly constant value. With the CO2
5316
concentration of flue gas increasing, the amount of CO2
reacted with ammonia is increasing, but the flow rate and the
concentration of aqua ammonia is not changed. Therefore, the
ε is declined, and reaction heat release is increasing. The release
heat makes the temperature of CO2-rich solutions increase. In
order to attain large CO2 loading of rich solution, on the basis
of the premise that the required ε is higher than 90%, the best
CO2 concentration of flue gas is chosen as 12−13%.
5.3. Optimization of Temperature. In the process of
CO2 absorption, temperature is an important parameter
influencing reaction kinetics, heat and mass transfer rate, and
diffusion rate. Effects of the temperature of liquid on ε, CO2
loading, NH3 concentration of outlet gas, and temperature of
rich solution are shown in Figure 13. It can be seen that the ε
reaches to the highest value at the temperature of 33 °C. In the
dx.doi.org/10.1021/ie2030536 | Ind. Eng. Chem. Res. 2012, 51, 5309−5319
Industrial & Engineering Chemistry Research
Figure 15. Effects of the flow rate of flue gas on ε, CO2 loading, NH3 concentration of outlet gas, and temperature.
literature of Diao et al.,17 their experimental results also show
that the CO2 removal efficiency reaches its highest value at 33
°C, which further validate the simulation results of rate-based
NH3 model. As shown in Figure 13a,b, when the temperature
of liquid increases from 13 to 56 °C, the CO2 loading of rich
solution and the NH3 concentration of outlet gas grow rapidly
in the same way, and the temperature of rich solution increases
to a high level and keeps a constant value. The growth of the
CO2 loading of rich solution arises from increment of the NH3
concentration of outlet gas. Considering the ε and the NH3
concentration at the outlet, the best temperature of liquid is
lower than 30 °C. When the temperature of CO2-lean solution
is 33 °C, the highest temperature in the packed tower is 47.1
°C.
In the packed absorber, the temperatures of gas and liquid
increase with the temperature of CO2-lean solution increasing.
The high temperature accelerates mass transfer rate, heat
transfer rate, diffusion rate, and reaction rate, which is beneficial
to increase the CO2 removal efficiency, while the backward
reaction rates speed up at the same time, which will lead to the
ε decreasing. These inverse mechanisms result in the peak value
of the CO2 removal efficiency.
Effects of the temperature of flue gas on ε, CO2 loading, and
NH3 concentration of outlet gas are shown in Figure 14. When
the temperature of flue gas increases from 25.5 to 150 °C, the ε,
the CO2 loading, and the NH3 concentration of outlet gas
remain almost unchanged. Whereas the temperature of rich
solution increases from about 31 to 37 °C, the increment of
liquid temperature is not obvious due to the small specific heat
ratio between flue gas and solution. Therefore, before flue gas
entering into absorber, it does not need a cooling operation,
and increasing the temperature of flue gas appropriately will be
beneficial to the removal of CO2.
5.4. Optimization of Gas Flow Rate. Figure 15 shows
effects of the flow rate of flue gas on ε, CO2 loading, and NH3
concentration of outlet gas. It is found that the CO2 removal
efficiency decreases from 100% to about 40% when the flow
rate of flue gas increases from 4 to 48 m3/h. The CO2 loading
of rich solution grows quickly at first and later increases to a
nearly stable value. The NH3 concentration of outlet gas
reaches to a peak value when the gas flow rate is about 30 m3/h
due to the high value of liquid temperature at the top of
absorber as shown in Figure 15b. At the top of absorber (the
first stage in rate-based model), absorbent contacts with flue gas
that will leave the absorber immediately. Liquid and vapor tend
to thermodynamic equilibrium. Temperature has a remarkable
effect on the vapor liquid equilibrium. A temperature increase is
5317
Article
beneficial for the ammonia evaporation. In this operation
condition, the best flow rate of flue gas is about 15−16 m3/h.
6. CONCLUSIONS
Experimental studies and rate-based process simulations of CO2
absorption with aqueous ammonia solutions have been carried
out. A pilot plant at laboratory scale for absorption of CO2 has
been constructed and operated to test the feasibility of CO2
removal by aqueous ammonia solutions. CO2 removal
efficiencies and temperature profiles along the packing height
are obtained. The effects of the CO2 loading of CO2-lean
solutions on CO2 removal efficiency, NH3 concentration of
outlet gas, and CO2 loading of CO2-rich solutions are
investigated. Experimental results show that the best CO2
loading of CO2-lean solutions is 0.124−0.150 in order to
achieve 90% of CO2 removal efficiency. In order to minimize
ammonia loss and reduce the heat duty of regenerator, it is
necessary to reduce the NH3 concentration of outlet gas and
improve the CO2 loading of CO2-rich solutions as much as
possible. Besides, a rate-based absorption model, RateFrac,
based on the Aspen Plus process simulator, is developed to
simulate the pilot plant. Simulation results of the rate-based
model are in good agreement with the experimental data.
Further, optimization analysis for operating parameters of the
pilot plant is carried out. The operation parameters include the
packing height of the absorber, the ammonia concentration of
lean solution, the CO2 loading of lean solution, the temperature
of liquid, and the flue gas flow rate. It is shown that process
optimization with the rate-based model can provide theoretical
guidance for energy-saving technology.
■
*
ASSOCIATED CONTENT
S Supporting Information
Details of operational parameters and results for the experi-
ments and simulations. This information is available free of
charge via the Internet at http://pubs.acs.org.
■ AUTHOR INFORMATION
Corresponding Author
*Telephone: (8610) 6277 2112. Fax: (8610) 6278 1824. E-
mail: guoyc@tsinghua.edu.cn.
Notes
The authors declare no competing financial interest.
dx.doi.org/10.1021/ie2030536 | Ind. Eng. Chem. Res. 2012, 51, 5309−5319
Industrial & Engineering Chemistry Research
■
ACKNOWLEDGMENTS
This research was supported by Beijing Municipal Commission
for Science & Technology under Grant No. Z08040902950803.
■
NOMENCLATURE
A, B, C, D = adjustable parameters
DevExp = deviation of individual liquid and gas phase mass
balances for CO2, %
E = activation energy
GasCO2 = decreased amount of CO2 in absorber gas, mol/h
k = pre-exponential factor
K = equilibrium constant
LiqCO2 = increased amount of CO2 in absorber liquid, mol/h
n = temperature exponent
r = rate of reaction
R = universal gas constant
T = absolute temperature
T0 = reference temperature
y1 = CO2 mole fraction at the inlet of absorber
y2 = CO2 mole fraction at the outlet or some position of
absorber
ε = CO2 removal efficiency, %
Subscripts
eq = at equilibrium
■
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