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In this work, a comprehensive model is developed for the absorption of carbon dioxide into
aqueous mixtures of primary or secondary alkanolamines with tertiary alkanolamines. The
model, which is based on penetration theory, incorporates an extensive set of important reversible
reactions and takes into account the coupling between chemical equilibrium, mass transfer,
and chemical kinetics. The reaction between CO2 and the primary or secondary amine is modeled
according to the zwitterion mechanism. The key physicochemical properties that are needed for
the model are the CO2 physical solubility, the CO2 and amine diffusion coefficients, and the
reaction rate coefficients and equilibrium constants. Data for carbon dioxide absorption into
aqueous mixtures of diethanolamine and methyldiethanolamine are compared to model
predictions.
Introduction
Removal of acid gas impurities, such as CO2, is
important in natural gas processing. Natural gas,
depending on its source, can have varying concentrations of CO2. Some of the CO2 is often removed from
natural gas because, when present at high levels, it
reduces the heating value of the gas, and because it is
costly to pump this extra volume when it does not have
any heating value.
Aqueous solutions of alkanolamines are the most
widely used solvents for removing CO2. The most commonly used alkanolamines are the primary amine
monoethanolamine (MEA), the secondary amine diethanolamine (DEA), and the tertiary amine methyldiethanolamine (MDEA). Primary and secondary amines react
rapidly with CO2 to form carbamates. By the addition
of a primary or secondary amine to a purely physical
solvent such as water, the CO2 absorption capacity and
rate is enhanced manyfold. However, because there is
a relatively high heat of absorption associated with the
formation of carbamate ions, the cost of regenerating
primary and secondary amines is high. Primary and
secondary amines also have the disadvantage of requiring 2 mol of amine to react with 1 mol of CO2; thus,
their loadings are limited to 0.5 mol of CO2/mol of
amine. Tertiary amines lack the N-H bond required to
form the carbamate ion and therefore do not react
directly with CO2. However, in aqueous solutions,
tertiary amines promote the hydrolysis of CO2 to form
bicarbonate and the protonated amine. Amine-promoted
hydrolysis reactions are much slower than the direct
reactions of primary and secondary amines with CO2,
and therefore, the kinetic selectivity of tertiary amines
toward CO2 is poor. However, the heat of reaction
associated with the formation of bicarbonate ions is
much lower than that associated with carbamate formation, and thus, the regeneration costs are lower for
tertiary amines than for primary and secondary amines.
Another advantage with tertiary amines is that the
stoichiometry is 1:1, which allows for very high equilibrium CO2 loadings.
* Corresponding author: sandall@engineering.ucsb.edu.
Ind. Eng. Chem. Res., Vol. 39, No. 11, 2000 4347
Reaction Mechanism
When CO2 is absorbed into an aqueous solution of a
tertiary alkanolamine, R(1)R(2)R(3)N, and a primary or a
secondary alkanolamine, R(4)R(5)NH, the following reactions may occur:
K1,k1
(1)
K2,k2
(2)
K15
(15)
K16
(16)
K3,k3
K17
(5)
K4,k4,k-4
(4)
(5)
(4)
K5,k5,k-5
(14)
4348
u04
K4K5K13K16 )
K12 )
K13 )
K14 )
u07 u010
u02
u08
u06
u2 ) [R(1)R(2)R(3)N]
-
u4 ) [HCO3 ]
u3 ) [R R R NH ]
u5 ) [OH-]
u6 ) [CO32-]
u7 ) [H3O+]
u8 ) [R(4)R(5)NH]
u9 ) [R(4)R(5)NH2+]
u11 ) [H2CO3]
u10 ) [R(4)R(5)NCOO-]
u12 ) [H2O]
u011
u03
(1)
(2)
(3)
)[R R R N]initial
R1 ) -k1u1 +
(18)
(19)
R3 ) -k3u1u5 +
R4,...,10 )
[R R NH]initial} (20)
(5)
Electroneutrality balance
u03 + u07 + u09 - u04 - u05 - 2u06 - u010 ) 0
(21)
k1
u
K1 11
where
(29)
k2
u
K2 4
(30)
k3
uu
K3 3 4
(31)
R2 ) -k2u1u5 +
(28)
0
) and 11 nonlinear
We have 11 unknowns (u01, ... , u11
algebraic equations that we can solve for the liquid
bulk concentrations. We have found that Newtons
method did not converge unless the initial guesses
for the liquid bulk concentrations were very close to
the (unknown) solution. We, therefore, used the
Newton homotopy continuation method (Hanna and
Sandall19), which exhibited better convergence behavior.
The Partial Differential and Nonlinear Algebraic Equations That Describe the Diffusion/
Reaction Processes. Higbies penetration model (Higbie,20 Danckwerts21) was used to set up the diffusion/
reaction partial differential equations that describe the
absorption/desorption of CO2 into/from aqueous solutions of tertiary amines, R(1)R(2)R(3)N, and primary or
secondary amines, R(4)R(5)NH, in a laminar-liquid-jet
absorber or a stirred-cell absorber. All reactions were
treated as reversible reactions. The first 11 reactions
have finite reaction rates, which are given by the
following reaction rate expressions, where Ri is the
reaction rate expression for reaction i:
(27)
u04 u07
(26)
u04 u05
(3)
(25)
u09 u05
(2)
(24)
u03 u05
K15 )
(1)
(23)
u01 u08
Mathematical Model
u1 ) [CO2]
(22)
u01 u05
-k4 u1u8 1+
1
B
(BA)u ]
10
(32)
Ind. Eng. Chem. Res., Vol. 39, No. 11, 2000 4349
( )
A)
( ) ( )
( ) ( ) ( )
k5 u 9
+
k-4 K4K5
k8
k-4
k6 u3
+
k-4 K4K6
u12
k9
+
K4K8 k-4
k7 u7
+
k-4 K4K7
u11
k10 u4
+
(33)
K4K9 k-4 K4K10
and
B)
( ) ( ) ( ) ( )
( ) ( )
k5
k6
k7
k8
u +
u +
u +
u +
k-4 8
k-4 2
k-4 12
k-4 5
k9
k10
u +
u (34)
k-4 4
k-4 6
R11 ) -k11u10 +
k11
uu
K11 4 8
(35)
u10
2u10
) D10 2 + R11 - R4,...10
t
x
(41)
K12 )
u2
u3u5
(42)
K13 )
u8
u9u5
(43)
K14 )
u6
u4u5
(44)
K15 )
u11
u4u7
(45)
K16 ) u5u7
(46)
ui ) u0i , i ) 1, ... , 11
ui
) 0 at x ) 0, t > 0
x
2u1
2u4
u1u4 u6 u10 u11
+
+
+
) D1 2 + D4 2 +
t t
t
t
t
x
x
2u6
2u10
2u11
D6 2 + D10 2 + D11 2 (37)
x
x
x
Total tertiary amine, R(1)R(2)R(3)N, balance
(38)
(47)
(36)
u2 u3
2 u 2
2 u 3
+
) D2 2 + D 3 2
t
t
x
x
u3 u7 u9 u4 u5
u6 u10
+
+
-2
)
t
t
t
t
t
t
t
2u3
2u7
2 u 9
2 u 4
2u5
D3 2 + D7 2 + D9 2 - D4 2 - D5 2 x
x
x
x
x
2
2
u6
u10
2D6 2 - D10 2 (40)
x
x
CO2 balance
2u1
u1
) D1 2 + R1 + R2 + R3 + R4,...10
t
x
Electroneutrality balance
(39)
(48)
u1
) kg,1[P1 - H1u1(0,t)] at x ) 0, t > 0
-D1
x
(49)
4350
u1(0,t) ) u/1 )
P1
at x ) 0, t > 0
H1
d2l
4Q
D1
D1
u1
(0,t) dt
x
(52)
RA1
0
kl,1
(u/1- u01)
K15(T)
K15(298.15)
1
-H0 1
R T 298.15
(57)
(53)
E1 )
(56)
ln
The average rate of absorption of CO2 per unit interfacial area is then computed from the following equation:
RA1 ) -
2895
T
log10(k2) ) 13.635 -
(51)
17265.4
(55)
T
(50)
(54)
where u/1 and u01 are the interfacial and bulk concentrations of CO2 in the liquid, respectively.
Method of Solution for the Partial Differential/
Algebraic Equations. The method of lines was used
to transform each partial differential equation into a
system of ordinary differential equations in t (Hanna
and Sandall19). The systems of partial differential/
algebraic equations were transformed into larger systems of ordinary differential/algebraic equations, which
were then solved by using the code DDASSL (Petzold22)
in double-precision Fortran on an HP-735 computer.
Model Parameters
The nitrous oxide analogy method was used to estimate the CO2 solubility (Rinker and Sandall23) and the
CO2 diffusivity (Ashour et al.24) in the aqueous amine
solutions. The kinetics for CO2/MDEA were measured
by Rinker et al.,6 and the kinetics for the CO2/DEA
reaction were determined by Rinker et al.15 The diffusion coefficients of MDEA and DEA were estimated from
the diffusivity data of Hikita et al.25
We include here correlations that were used to
estimate various other reaction rate coefficients and
equilibrium constants that were obtained from the
literature. Values for the forward rate coefficient of
reactions 1 and 2, k1 and k2, respectively, were calculated from the following correlations, which were reported by Pinsent et al.26 for the temperature ranges of
273-311 K and 273-313 K, respectively:
Ind. Eng. Chem. Res., Vol. 39, No. 11, 2000 4351
temp range
(K)
equation
reference
293-573
Olofsson
and Hepler27
273-523
Read28
K14K16
273-323
K4K5K13K16
K13K16
K12K16
298-333
298-333
298-333
Danckwerts
and Sharma29
Barth et al.30
Barth et al.30
Barth et al.30
K16
K2K16
4352
[DEA]
(kmol/m3)
RCO2 105
measured
(kmol/m2s)
RCO2 105
predicted
(kmol/m2s)
0.844
0.808
0.692
0.586
0.532
0.232
0
0
0.040
0.173
0.293
0.355
0.696
0.959
1.22
1.29
1.45
1.65
1.71
2.40
3.28
1.22
1.35
1.44
1.65
1.76
2.69
3.32
Ind. Eng. Chem. Res., Vol. 39, No. 11, 2000 4353
Table 3. CO2 Absorption Data in 30 wt % Blends of DEA
and MDEA Obtained in the Laminar-Liquid-Jet Absorber
at 25 C
[MDEA]
(kmol/m3)
[DEA]
(kmol/m3)
RCO2 105
measured
(kmol/m2s)
RCO2 105
predicted
(kmol/m2s)
2.581
2.118
1.376
0.712
0
2.581
2.118
1.376
0.712
0
0
0.529
1.376
2.135
2.947
0
0.529
1.376
2.135
2.947
1.12
1.97
3.08
3.77
4.86
1.06
1.73
3.06
3.72
4.65
0.870
1.49
2.83
3.80
4.75
0.850
1.51
2.82
3.80
4.71
[DEA]
(kmol/m3)
RCO2 105
measured
(kmol/m2s)
RCO2 105
predicted
(kmol/m2s)
4.217
4.217
3.722
3.719
3.722
3.034
3.034
0.202
0.202
0.772
0.771
0.772
1.517
1.517
0.753
0.868
1.10
1.15
1.09
1.67
1.50
0.692
0.783
1.11
1.12
1.09
1.72
1.74
(58)
C0A L
As
(59)
Sh ) 0.0193Re0.845Sc0.5
(60)
where
Sh )
kl,1da
DA
Re )
FNLdi2
Sc )
FDA
(61)
4354
Ind. Eng. Chem. Res., Vol. 39, No. 11, 2000 4355
Notation
As ) gas-liquid interface area, m2
CA ) diameter of the laminar-liquid jet, m
Di ) coefficient of species i in the aqueous alkanolamine
solution, m2/s
DEA ) diethanolamine
DIPA ) diisopropanolamine
E1 ) factor of CO2, defined by eq 54
h0 ) spacing next to the gas-liquid interface for the
discretized spatial variable x, m
H1 ) physical equilibrium constant (Henrys law constant)
for CO2, H1 ) P/1/u/1, (kPa m3)/kmol
kapp ) rate coefficient for the reaction between CO2 and a
secondary or a primary alkanolamine, defined by eq 70,
m3/(kmol s)
kg,1 ) gas-phase mass transfer coefficient for CO2, kmol/
(kPa m2 s)
k0l,1 ) mass transfer coefficient for CO2 in the liquid phase,
defined by equation (52), m/s
ki ) rate coefficient of reaction i, s-1 for first-order
reactions, m3/(kmol s) for second-order reactions
k-i ) rate coefficient of reaction i
Ki ) constant for reaction i
l ) length of the laminar-liquid jet, m
L1 ) CO2 loading of the aqueous amine solution, (kmol
CO2)/(kmol amine)
MDEA ) N-methyldiethanolamine
MEA ) monoethanolamine
NL ) impeller speed, rev/s
P1 ) pressure of CO2 in the gas phase, kPa
P/1) partial pressure of CO2 in the gas phase, kPa
Q ) volumetric flow rate of the liquid, m3/s
Ri ) reaction rate of reaction i, kmol/(m3 s)
RA1 ) rate of absorption of CO2 per unit interfacial area,
defined by equation (53), kmol/(m2 s)
Re ) Reynolds number defined by eq 80
Sc ) Schmidt number defined by eq 80
Sh ) Sherwood number defined by eq 80
t ) independent time variable, s
T ) absolute temperature, K
ui ) concentration of species i in the liquid phase (which
is a function of x and t), kmol/m3
0
ui ) liquid bulk concentration of s pecies i (which is a
constant), kmol/m3
u/1 ) interfacial concentration of CO2 in the liquid, kmol/
m3
x ) independent spatial variable, m
Greek letters
) viscosity of the aqueous alkanolamine solution, kg/(m
s)
F ) density of the aqueous alkanolamine solution, kg/m3
) gas-liquid contact time, defined by eq 51 for a laminarliquid-jet absorber, s
Literature Cited
(1) Chakravarty, T.; Phukan, U. K.; Weiland, R. H. Reaction
of acid gases with mixtures of amines. Chem. Eng. Prog. 1985, 81
(4), 32-36.
(2) Donaldson, T. L.; Nguyen, Y. N. Carbon dioxide reaction
kinetics and transport in aqueous amine membranes. Ind. Eng.
Chem. Fundam. 1980, 19, 260-266.
(3) Haimour, N.; Bidarian, A.; Sandall, O. C. Kinetics of the
reaction between carbon dioxide and methyldiethanolamine.
Chem. Eng. Sci. 1987, 42, 1393-1398.
(4) Versteeg, G. F.; van Swaaij, W. P. M. On the kinetics
between CO2 and alkanolamines both in aqueous and nonaqueous
solutions II. Tertiary amines. Chem. Eng. Sci. 1988, 43, 587-591.
4356
(30) Barth, D.; Tondre, C.; Lappai, G.; Delpuech, J.-J. Kinetic
study of carbon dioxide reaction with tertiary amines in aqueous
solutions. J. Phys. Chem. 1981, 85, 3660-3667.
(31) Cotton, F. A.; Wilkinson, G. Advanced Inorganic Chemistry;
Interscience Publishers: New York, 1966.
(32) Smith, J. M.; Van Ness, H. C. Introduction to Chemical
Engineering Thermodynamics, 4th ed.; McGraw-Hill: New York,
1987.