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Solubility and Diffusivity of N2O in Aqueous 4-(Diethylamino)2-butanol Solutions for Use in Postcombustion CO2 Capture
Teerawat Sema,*, Mohamed Edali, Abdulaziz Naami, Raphael Idem,*,, and
Paitoon Tontiwachwuthikul*,,
International Test Centre for CO2 Capture (ITC), Faculty of Engineering and Applied Science, University of Regina, Regina,
Saskatchewan, S4S 0A2, Canada
Joint International Center for CO2 Capture and Storage (iCCS), Department of Chemical Engineering, Hunan University,
Changsha, 410081, P. R. China
ABSTRACT: In this work, the solubility and diusivity of nitrous oxide (N2O) in aqueous 4-(diethylamino)-2-butanol (DEAB)
solutions were measured. Solubility was measured in a stirred cell reactor over the temperature range of 298343 K and
concentration range of 0.683.77 M. On the other hand, diusivity was measured in a laminar jet absorber over the temperature
range of 298318 K and concentration range of 1.02.5 M. An attempt was made to correlate the solubility data with well-known
models (semiempirical model, RedlichKister equation, and polynomial model). It was observed that only the polynomial model
correlated the solubility of N2O in aqueous DEAB solution satisfactorily with an AAD of 0.1%. Similarly, an attempt was made
to correlate the diusivity data with well-known models (semiempirical model and modied StokesEinstein model). The
semiempirical model provided better predicted N2O diusivity data compared with the experimental data with an AAD of 3.4%.
These data can then be used to determine the physical solubility and physical diusivity of carbon dioxide (CO2) in aqueous DEAB
solutions using the N2O analogy.
1. INTRODUCTION
Greenhouse gas emissions and their potential eects in terms
of global warming and climate change problems have become an
important issue in recent years.1 Among the greenhouse gases,
carbon dioxide (CO2) is considered to be the major target
because of its abundance. It is generally agreed that removal of
CO2 from large point exhaust gas streams of industrial processes
such as electric power plants, reneries, and natural gas processing plants becomes essential in order to make any impact in CO2
emissions mitigation. Several technologies have been used for
CO2 removal, such as absorption, adsorption, cryogenics methods, membranes systems, and microbial systems.2 Amine-based
CO2 capture technology has been widely used for postcombustion CO2 removal and to provide the most appropriate and costeective options compared with other technologies,3,4 especially
in coal-red power plants which usually have a low CO2 concentration
and a low pressure of the exhaust stream.
A newly developed amino alcohol solvent, 4-(diethylamino)2-butanol (DEAB), is considered as a promising solvent to
capture CO2 due to its energy eciency for regeneration, high
absorption capacity, and cyclic capacity for CO2 removal.5,6
However, a good solvent not only should provide energy
eciency, high absorption capacity, and cyclic capacity but also
should have a fast absorption rate, low degradation rate, and low
corrosion rate.
In order to develop the reaction kinetics model, several
physical, chemical, and thermodynamics properties of the amine
solution are required, such as physical solubility of CO2 or CO2
Henrys constant, physical diusivity of CO2, density, viscosity,
equilibrium constants for the CO2amine system, and CO2
absorption rate data.7 Even though physical solubility and
r 2011 American Chemical Society
physical diusivity of CO2 at various temperatures and concentrations are essential for developing the reaction kinetics model,
they cannot be measured directly because CO2 reacts chemically
with aqueous amine solutions. Thus, measurements of nitrous
oxide (N2O) solubility and diusivity through the N2O analogy
can be used to determine the solubility and diusivity of CO2 in
aqueous amine solutions.810 This is due to the similarity of the
molecular weight, chemical conguration, volume, and electronic
structure between CO2 and N2O.11 The N2O analogy for
determining solubility and diusivity are shown in the following
equations.
HeCO2 amine HeN2 O amine
DCO2 amine DN2 O amine
HeCO2 H2 O
HeN2 O H2 O
DCO2 H2 O
DN 2 O H 2 O
1
2
ARTICLE
(kPa m3/kmol)
298
3179
303
3553
313
4423
323
5484
333
7894
343
9043
2. EXPERIMENTAL SECTION
2.1. Chemicals. DEAB is a newly developed potential solvent
which was synthesized according to the procedure described by
Tontiwachwuthikul et al.6 in our solvent synthesis laboratory at
the International Test Centre for CO2 Capture (ITC), University of Regina. Aqueous solutions of DEAB of desired concentrations were prepared by adding a known amount of deionized
water to predetermined amounts of DEAB. N2O, CO2, and
nitrogen (N2) with a purity of 99.9% were supplied by Praxair
Inc., Canada.
2.2. N2O Solubility. The apparatus and experimental technique used for determining N2O solubility were modified from
the works of Munder et al.12 and Park et al.13 The solubility
experiment was performed in a rotary-type 600 mL stainless
steel autoclave reactor (model Parr 5500, Parr Instrument Co.,
Moline, IL) connected to a controller (model Parr 4843, Parr
Instrument Co., Moline, IL). The reactor consists of a variablespeed impeller, a heating mantle, cooling coils, a gas feed port, a
thermocouple, and a pressure transducer.
Initially, the amine solution was degassed using an ultrasonic
bath (VWR model 75D, VWR international, ON, Canada), and
then 300 mL of the degassed amine solution was loaded into the
reactor. The desired temperature and agitation speed were set
and controlled by the controller, and then the vacuum was turned
on. After shutting down the vacuum pump, the liquid was under a
certain pressure due to liquid vaporization. The pressure was
measured as equilibrium, PV. Then a certain amount of N2O
(nN2O) was fed to the reactor. The amount of nN2O can be
determined by measuring the pressure in the reactor before N2O
injection (P1) and after N2O injection (P2)
nN2 O P2 P1
Vg
ZN2 O RT
HeN2 O
RA 4Ce DLh1=2
Ce
P N2 O
HeN2 O
10
PN2 O Vg
ZN2 O RT
PN2 O
CN 2 O
nlN2 O
Vl
6
926
ARTICLE
temp. (K)
temp. (K)
0.68 M
1.34 M
1.97 M
3.19 M
3.77 M
298
6676
5285
3965
2699
2416
313
7103
5706
4228
2844
323
7600
5918
4457
333
8102
6354
4857
343
8623
6808
5274
A0
A1
A2
A3
A4
298
7192.7
587
2574.6
932.7
100.9
2665
313
323
7690.2
8767.6
475.1
768.6
2500
1869.2
877.3
741.3
90.5
80
3077
2868
333
9423.7
1099.5
1682
686.5
74.1
3410
3184
343
10063.3
1322.4
1598.5
667.8
71.8
3824
3640
To correlate the N2O solubility results at various concentrations and temperatures, there are several models which have been
applied in the literature such as the semiempirical model,17
RedlichKister equation,19 and polynomial model.18 In this
study, these three dierent models were used to develop the
predictive models for N2O solubility of aqueous DEAB solution.
3.2.1. Semiempirical Model. It was reported by Wang et al.17
that the semiempirical model gives a good estimation of N2O
solubility of various aqueous amine solutions of MEA, diethanolamine (DEA), MDEA, 2-amino-2-methyl-1-propanol (AMP),
and diisopropanolamine (DIPA). The model can be written as
ln HeN2 O Solution H2 O DEAB k1 k2 t k3 t 2 k4 H2 O
H2 O ln HeN2 O H2 O
14
12
The predicted values were found to t well with the experimental values with an absolute average deviation (AAD)
of 3.6%.
3.2. N2O Solubility in Aqueous DEAB Solutions. The
solubility measurements of aqueous DEAB solutions were done
over the temperature range of 298343 K and the concentration
range of 0.683.77 M. The results are shown in Table 2 and
plotted in Figure 2. It can be observed that HeN2O increases with
increasing temperature and decreases with increasing DEAB
concentration. Conversely, the N2O solubility into aqueous
DEAB solution is found to decrease with increasing temperature
and increases with increasing DEAB concentration.
A4 2xDEAB 14
16
ARTICLE
temp. (K)
1.0
298
1.89
1.0
1.0
308
318
2.16
2.49
298 K
308 K
318 K
1.0
2.39
1.68
1.20
2.0
298
1.04
2.0
4.53
3.05
2.06
2.0
308
1.31
2.5
5.99
3.98
2.64
2.0
318
1.59
2.5
298
0.68
2.5
308
0.91
2.5
318
1.22
viscosity (mPa s)
ARTICLE
4. CONCLUSIONS
1 The solubility of N2O in pure DEAB solvent decreases as
the temperature is increased. HeN2ODEAB can be calculated
using a predictive model (eq 13) with an AAD of 3.6%.
2 N2O solubility into aqueous DEAB solution decreases with
increasing temperature and increases with increasing DEAB
concentration. HeN2OSolution can be estimated using a
polynomial model (eq 17) with an AAD of 0.1%.
3 Diusivity into aqueous DEAB solution increases with
increasing temperature and decreases with increasing
DEAB concentration. Diusivity can be calculated using a
semiempirical model (eq 21) with an AAD of 3.4%.
18
19
AUTHOR INFORMATION
Corresponding Author
ACKNOWLEDGMENT
Financial support from the International Test Centre for CO2
Capture (ITC) at the University of Regina and the Natural Sciences
and Engineering Research Council of Canada (NSERC) is gratefully
acknowledged.
NOMENCLATURE
Ai = temperature-dependence coecient
AMP = 2-amino-2-methyl-1-propanol
C = concentration, mol/L
Ce* = equilibrium concentration of gas at interface, mol/L
CN2O = concentration of N2O at equilibrium, mol/cm3
D = diusivity of gas in liquid, cm2/s
DCO2amine = diusivity of CO2 in aqueous amine solution,
cm2/s
DN2Oamine = diusivity of N2O in aqueous amine solution,
cm2/s
DCO2H2O = diusivity of CO2 in water, cm2/s
DN2OH2O = diusivity of N2O in water, cm2/s
DEA = diethanolamine
DEAB = 4-(diethylamino)-2-butanol
DIPA = diisopropanolamine
DMMEA = dimethylmonoethanolamine
h = jet height, cm
HeN2O = solubility of N2O, kPa m3/kmol
HeCO2amine = solubility of CO2 in aqueous amine solution, kPa
m3/kmol
HeN2Oamine = solubility of N2O in aqueous amine solution, kPa
m3/kmol
HeN2ODEAB = solubility of N2O in pure DEAB, kPa m3/kmol
929
ARTICLE
Greek Letters
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