Energy

Procedia
Energy
Energy Procedia
Procedia 00 (2008)1171–1178
1 (2009) 000–000
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GHGT-9

Modeling CO2 Capture with Aqueous Monoethanolamine

Jorge M Plazaa, David Van Wagenera, Gary T. Rochellea,*1
a
Department of Chemical Engineering, The University of Texas at Austin, 1 University Station C0400, Austin, TX 78712, USA
Elsevier use only: Received date here; revised date here; accepted date here

Abstract

Hilliard [1] completed several thermodynamic models in Aspen Plus® for modeling CO2 removal with amine solvents, including
MEA-H2O-CO2. This solvent was selected to make a system model for CO2 removal by absorption/stripping. Both the absorber
and the stripper used RateSepTM to rigorously calculate mass transfer rates. The accuracy of the new model was assessed using a
recent pilot plant run with 35 wt % MEA. Absorber loadings and removal were matched and the temperature profile was
approached within 5oC. An average 3.8% difference between measured and calculated values was achieved in the stripper. A
three-stage flash configuration which efficiently utilizes solar energy was developed. It reduces energy use by 6% relative to a
simple stripper. Intercooling was used to reach 90% removal in the absorber at these optimized conditions.
©
2008Elsevier
c 2009 ElsevierLtd.
Ltd.
AllB. All rights
rights reserved
reserved.

Keywords: Kinetics; Absorption; Stripping; Carbon dioxide; MEA; modeling

1. Introduction

CO2 capture by amine absorption and stripping is currently considered the most feasible option for the removal of
carbon dioxide from coal- and natural gas- fired power plants. Monoethanolamine (MEA) is the proven solvent for
this application. Previous models have been developed for this system. Freguia [2] developed a model using
AspenPlus® RatefracTM that incorporated kinetic work by Dang [3] and modified VLE by Austgen [4] to include
work by Jou et al. [5]. Ziaii [6] used Aspen Plus® RateSepTM with the thermodynamic framework by Freguia and
approximated Aboudheir [7] kinetics. This paper presents results with a new MEA model that uses a rigorous
thermodynamic model developed by Hilliard [1] and kinetics extracted from values obtained by Aboudheir [7] with
a laminar jet. The model was developed with the Aspen Plus® RatesepTM framework and was validated with a pilot
plant run with 35 wt % MEA. Additionally, an innovative stripper configuration was optimized and its
corresponding absorber was specified.

2. Thermodynamic model

The absorber and stripper models use the thermodynamic representation by Hilliard [1]. Hilliard used the
electrolyte nonrandom two-liquid (e-NRTL) activity coefficient model in Aspen Plus® to develop a rigorous and

* Corresponding author. Tel.:1-512-471-7230; fax:1-512-471-7060.

E-mail address: [email protected]
doi:10.1016/j.egypro.2009.01.154
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consistent thermodynamic representation of mixtures of MEA – H2O – CO2. His model differs from previous
models in that it represents additional data on amine vapor pressure, enthalpies of absorption, heat capacity, and
NMR speciation. This framework uses Gibbs free energy and enthalpy values within Aspen Plus® to maintain
thermodynamic consistency.

3. Absorber MEA model and validation

Kinetics are based on selected measurements of CO2 absorption by Aboudheir [7] in a laminar jet. These data
were used to evaluate the forward rate constants for the formation of carbamate using Aspen Plus® RateSep™. An
absorber model was set up using the Hilliard thermodynamic model and kinetics were represented using two
reversible reactions:

2 MEA + CO2 ↔ MEAH+ + MEACOO- (1)

14610 1 1 2
3− = 5.31 9 − − 2
(1a)
8.314 298

102740 1 1
3− = 4.75 5 − − − + (1b)
8.314 298

MEA + CO2 + H2O↔ HCO3- + MEAH+ (2)

49000 1 1
3− = 9026 − − 2
(2a)
8.314 298

114250 1 1 − +
3
3− = 2917 − − (2b)
8.314 298 2

The bicarbonate reaction (2) rate constants were evaluated using data at 25oC for reaction of tertiary amines and
CO2. This data was correlated with the base dissociation constant (pKb) in Rochelle [8]. The values of the reaction
constant for tertiary amines were fit as a function of pKb.and the forward rate constant for MEA (pKb=4.45) was
extracted from this fit and converted to an activity/mole fraction basis with the activity coefficients from the Hilliard
model. The energy of activation was approximated using data for MDEA (49 kJ/gmol) [8]. The forward reaction
rate constant for the bicarbonate reaction was calculated with the conditions defined by the data set selected from
Aboudheir and then used along with the equilibrium constants to determine the reverse rates for the bicarbonate
reaction.

Nine points from Aboudheir [7] were used to determine the forward carbamate formation rate (1a). Three at 313
K (40oC), loading of 0.2767 and the rest at 333 K (60 oC), with loadings of 0.1104 and 0.2819. A laminar jet was
modeled in Aspen Plus® using the bicarbonate constants and thermodynamics from Hilliard [1]. Density, viscosity,
thermal conductivity, and surface tension of the MEA – H2O – CO2 system, along with carbon dioxide diffusivity in
water, were corrected based on work by Aspen Technology, Inc. [9]. Initially the energy of activation was set to
zero and the reported flux by Aboudheir was matched by changing the pre-exponential factor in the power law. The
resulting rate constants were averaged among the same temperature and loading conditions and then regressed to
obtain values for the pre-exponential factor and activation energy. The activity of MEA was squared to represent
apparent effects of changes in loading.

4. Pilot plant model validation

The proposed model was adjusted to match experimental data from a pilot plant run with 9 m MEA at the
University of Texas at Austin [10] using the parameter estimation tool in Aspen Plus® 2006.5.
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4.1 Absorber Model Validation

The operating mode was similar to that

reported by Chen [10], but the air was not
Table 1: Pilot Plant Reconciliation, 9 m MEA, 6.10 m absorber
recycled back to the absorber. The packing, 0.43 m Diameter
absorber packing (Flexipac AQ Style 20)
was modeled using Flexipac 1Y with 12
equal stages using the countercurrent flow Actual
model. The liquid mass transfer film was Pilot Plant Specified Reconciled Deviation
Variable Value deviation Value (%)
represented with 16 segments. The
interfacial area was calculated using a new Area Factor 1.0 ---- 0.816 ----
correlation developed by Tsai [11]. Heat Rich ldg (mol CO2/mol
loss was neglected. MEA) 0.48 1% 0.469 2.3
Inlet Gas (mol/hr) 34572 5% 33346 3.5
Variables and parameters used for the
YCO2 – In 0.119 5% 0.1192 0.0
reconciliation and their chosen standard
deviations along with the resulting model YCO2 – Out 0.047 5% 0.0501 5.7
predictions are presented in Table 1. The o
TG – In ( C) 25.1 1 25.1 0
only manipulated model parameter was the o
TG – Out ( C) 42.2 20 46.1 3.9
interfacial area factor which corrected the
calculated interfacial area. High standard TL – In (oC) 39.9 4 38.2 1.7
deviations (20oC) were specified for the o
TL – Out ( C) 44.9 4 46.7 1.8
outlet gas and the top column temperatures o
Column T ( C)
because they were considered less reliable.
The water (water – Lean) and CO2 content Top 39.2 20 34.8 4.4
(CO2 – Lean) of the lean feed were treated T1 53.7 2 53.8 0.1
as reconcilable experimental values. The
T2 67.8 2 70.8 3.0
resulting values give a lean loading of
0.365 which is 1% greater than the T3 67.1 2 69.4 2.3
measured value (0.36). Figure 1 compares T4 64.7 2 67.0 2.3
the resulting model temperature profiles Bottom 48.1 3 46.7 1.4
with the experimental results. The point at
a relative position of -0.1 represents a Water – Lean (mol/hr) 143600 0.5% 143700 0.1
measurement downstream of the column. CO2 – Lean (mol/hr) 8202 2% 8307 1.3
CO2 Removal (%) 60.0 1% 59.9 0.2
The reconciled flow rates,
compositions, and the CO2 removal are 75
within 1 to 6% reported values,
reflecting moderate adjustments to close 65
the mass balance. CO2 removal and
other pilot plant measurements were 55
matched by adjusting the wetted area
T (oC)

prediction of the Tsai model by a factor

45
of 0.82.
Liquid
35
4.2 Stripper Model
Vapor
25
This Aspen Plus® simulation work
assumes equilibrium reactions in the -0.1 0.1 0.3 0.5 0.7 0.9
TM Top Z/ZTotal Bottom
stripper. The RateSep tool rigorously
calculates the heat and mass transfer for Figure 1: Temperature profiles. 9 m MEA pilot plant run (▲)
each stage of the simple stripper. The measured (▬) reconciled
packing mass transfer and interfacial area model by Bravo et al. [12] was used to estimate liquid mass transfer
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coefficients and area of packing. The reboiler was modeled as equilibrium. The necessary pumps and intercooled
vapor compression were included, except for the pilot plant which did not require a compressor.

A nonconventional stripper section was used to simulate the reboiler configuration of the pilot plant. The reboiler
was configured to heat only a fraction of the sump drawoff (Figure 2). The column is identical to the absorber,
containing 6.1 m of packing (Mellapak 250Y) with a 0.43 m diameter. The pilot plant provided data for various
points in the process, but several crucial values were unknown. For example, the split ratio of lean amine flow was
not manipulated or measured, and it could not be calculated.

A three-stage flash configuration was developed for the

stripper (Figure 3). Unlike configurations with reboilers, a
countercurrent heat exchanger is used to preheat the rich stream
exiting the cross heat exchanger before the stripping equipment.
Preheating results in higher stripping temperatures, which yields
greater CO2 selectivity. High stripping temperatures were
previously avoided to reduce the risk of thermal degradation of
the solvent. However, if thermal degradation is not an issue for
new solvents, it would be preferable to use higher temperatures.
Additionally, by using a countercurrent exchanger to heat the
rich stream, a solar energy source with a variable heating
temperature is expected to operate more efficiently. The flash
assumes chemical and thermal equilibrium. The stripper was
sized to remove CO2 3000 tons/day of CO2 from a coal-fired
power plant. A 5° cold side approach was specified on the cross
heat exchanger, and a 10° LMTD driving force was specified
for all other heat exchangers.

ℎ −
= 0.75 ∗ ∗ +∑ / (3)
ℎ

− −
Figure 2: PFD of Pilot Plant Stripper = 0.75 ∗ ∗ +∑ (4)
−

The stripper performance of all

simulations was evaluated using equivalent
work, which calculates the total electrical
energy usage of a power plant. The standard
form is shown in equation 3, and this
equation was integrated when a variable
temperature energy source (solar heat) was
used in the three-stage flash configuration
(equation 4). This variable temperature
source had an inlet temperature of To and an
outlet temperature of Tf.

Figure 3: Three-stage flash for stripping; compressor intercooled at

each suction to 40°C
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98
Adjusted temperatures
Redistributor
(little insulation)
94 Plant data
Temperature (°C)

90
Aspen calculation

86
0 0.2 0.4 0.6 0.8 1
Z/Ztotal
Figure 4: Temperature Profiles in Pilot Plant and Aspen Simulation (Stripper).
Rich loading = 0.48, 63% removal. "Aspen calculation": no heat loss, 75% split to
reboiler, 20 ft CMR NO-2P packing. "Adjusted temperatures": 5 ft CMR NO-2P

4.3 Stripper Model Validation

The October, 2007 pilot plant run using 9 m MEA was also evaluated using the stripper model. Table 2
summarizes important data and calculations from the process. There were six thermocouples in the column at
various heights, each indicated by i in Table 2.

Data regressions were initially used in Aspen Plus® in an attempt to reconcile the results, but all regressions
failed to produce close agreement. The best solution was determined to be adjusting heat duties in selected stages
within the column to simulate heat loss. Pilot plant results did not include a profile of heat loss in the column, so it
was specified to match column temperatures. The split ratio in the reboiler and its duty were adjusted to match the
reboiler temperature and lean loading. Figure 4 displays the column profile as a function of stage for the plant data,
the initial Aspen calculation, and the final Aspen calculation with a matched temperature profile by adjusting to heat
loss. The agreement between
the values in Table 2 Table 2: Stripper Pilot Plant Results
demonstrates that the CO2
removal at the pilot plant was Pilot Aspen Pilot Aspen
verified with the model. The Variable Plant Plus® Variable Plant Plus®
simulation predicted a nearly Lean stream Column data
identical reboiler duty, and T (°C) 44.9 44.9 T 1 (°C) 87.6 86.7
the heat loss was only 12% Flow (kg/min) 73.3 70.9 T 2 (°C) 86.3 86.3
greater than the calculated Ldg (mol/mol) 0.36 0.36 T 3 (°C) 87.9 87.9
heat loss at the pilot plant. Rich stream T 4 (°C) 90.4 90.4
The average variation T (°C) 50.2 50.4 T 5 (°C) 91.0 91.0
between measured and Flow (kg/min) 70.6 69.0 T 6 (°C) 95.3 95.3
Ldg (mol/mol) 0.48 0.48 Reboiler T (°C) 102.7 102.7
calculated values was 3.8%.
Heat exchanger Ts Q (kW) 143.0 143.3
Lean in (°C) 44.9 44.9 Q loss (kW) 22.6 24.9
5 Optimization case Lean out (°C) 91.6 93.1 Sump T (°C) 98.2 97.8
study Rich in (°C) 98.6 99.7 Column P, bot (kPa) 105.0 105.0
Rich out (°C) 50.2 50.4 ΔP, top (kPa) 0.14 0.14
5.1 Improving Stripper Performance ΔP, bot (kPa) 0.15 0.15
Performance Eq Work - 41.2 Outlet vapor T (°C) 87.4 87.0
(kJ/mol CO2) Packing ht (m) 6.10 1.52
The three-stage flash configuration was run with 9 m MEA, and a constant rich loading of 0.495 was used
corresponding approximately to 5 kPa P*CO2 in the absorber. The lean loading was optimized to minimize the total
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equivalent work. The equivalent work for various conditions was compared against the equivalent work for a similar
system of conditions for a simple stripper, both atmospheric and 1.6 atm columns. The three-stage flash and simple
stripper configurations responded differently to changes in lean loading; however, both configurations yielded an
optimum lean loading of 0.40. Figure 5 displays the equivalent work response to lean loading for four scenarios:
solar-heated, three-stage flash with an exiting lean pressure of 110 kPa, steam-heated, three-stage with an exiting
lean pressure of 110 kPa, the baseline simple stripper configuration with steam heat operating at both 1 atm and 1.6
atm.

44 40
1 atm stripper

Eq W (kJ/mol CO2)
Eq W (kJ/mol CO2)

38
40
Simple Stripper
1 atm
36 1.6 atm stripper

1.6 atm 2.1 atm stripper

36
34
Steam Heating 3 Stage Flash
3 Stage Flash Solar Heating
32 32
0.31 0.36 0.41 0.46 0 10 20 30 40 50
To-Tf (°C)
Loading (mol CO2 / mol MEA)
Figure 5: Equivalent work response to lean loading. 9 m Figure 6: Equivalent work response to heating
MEA, 0.495 rich loading, 0.40 lean loading, 5°C cross fluid temperature difference. 9 m MEA, 0.495
exchange cold side temperature approach, 10°C driving rich loading, 0.40 lean loading, 5°C cross
force in reboiler/preheater, compression to 5MPa exchange cold side temperature approach, 10°C
driving force in reboiler/preheater, compression
to 5MPa.
The 1.6 atm simple stripper was considered to be the most appropriate comparison to the three-stage flash because
the maximum temperatures of these configurations were relatively equal: at the optimized lean loading the highest
temperature was 105°C. Whether using solar or steam heating, the three-stage flash required less energy than the
1.6 atm simple stripper. The three-stage flash with solar heating required 2.0 kJ/mol CO 2 less energy than the 1.6
atm stripper. The difference in performance using steam and solar heating for all simple strippers and the three-
stage flash was investigated (Figure 6). The y-intercepts represent steam heating with a constant heating
temperature, and the rest of the curves demonstrate the change in energy consumption when varying the ΔT with a
constant 10°C LMTD. The trends demonstrate that the three-stage flash is always an improvement over the simple
stripper, but it performs best with solar heating. A reboiled stripper would not benefit from solar heating.

Table 3: Defined specifications for absorber design

5.2 Absorber Design
Lean stream Gas inlet
T(°C) 40
An absorber was specified based on the
T (°C) 40
Pressure (kPa) 101.1
optimum flow and loading conditions defined
P (kPa) 101.1
by the stripper (Table 3). The absorber
Flow (kmol/s) 57.6 Flow (kmol/s) 6.1
requirements were to obtain the maximum
Ldg (mol CO2/mol MEA) 0.40 YCO2 0.133
Rich stream YH2O 0.066 removal matching the lean and rich loadings.
Ldg (mol CO2/mol MEA) 0.495 YN2/O2 0.81 Three absorber configurations were analyzed:
Column Specifications no intercooling, middle, and optimum
Dia. (m) 80% flooding 11.4 Packing Flexipac 1Y intercooling. Intercooling was evaluated in the
model by specifying a stage liquid temperature
to 40oC (using cooling water). Intercooling was set in the middle of the absorber and at an optimum defined by the
position of the intercooled stage that gave the minimum packing height. Initially 90% removal of CO 2 was
specified. However, the simple absorber presented a pinch at the bottom of the column that made it impossible to
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reach this value. The gas inlet flow was increased to 11 kmol/s in a
Table 4: Absorber results
second case reaching 50% removal to match the rich loading with the
simple absorber. Table 4 shows the results for each case. Temperature
and CO2 profiles for the simple absorber with 15m of packing and an Packing
Removal Intercooling Height (m)
optimized intercooling for 90% removal (Figures 7 & 8) are also included.
None Infeasible
The rich and lean loading from the stripper were matched using an 90% Mid column 6.07
intercooled absorber. The simple absorber is limited by a mid-column Optimized 5.16
absorption pinch that coincides with the temperature bulge. Intercooling None 18
breaks the pinch and reduces the temperature bulge, increasing the 50% Mid column 2.62
performance of the absorber. Results show that optimum placing of the Optimized 2.34
intercooling stage is capable of reducing packing height by 15%.

58 58
-0.16 -0.16
Intercooling
Liquid T
56 56

CO2 Absorption rate (kmol/s)

CO2 Absorption rate (kmol/s)

54 54
-0.12 -0.12
Liquid T
T (oC)

52 52
50 50
-0.08 -0.08
48 48
CO2 absorption rate
46 46 CO2 absorption rate
44 -0.04
44 -0.04

42 42
40 40
0 0
0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 1
Z/Ztotal Z/Ztotal
Figure 7: Temperature and absorption rate profiles Figure 8: Temperature and absorption rate
of an absorber column with no intercooling. 15 m profiles of an intercooled column with 5.16 m of
packing 84.7% CO2 removal, rich loading = 0.489. packing. 90% removal.

6 Conclusions

Reconciled pilot plant data show the proposed absorber model is capable of simulating operation of the absorber.
Loadings and removal were around 1% off the measured value. Temperature profiles are 2 to 8 oC off the reported
values. This may correspond to the unaccounted heat losses.

The stripper pilot plant data was matched with an average deviation of 3.8% by specifying heat duties to account
for heat loss.

The three-stage flash was developed as an alternate stripper configuration which efficiently utilizes solar energy,
improving stripper performance by 6%.

Intercooling increased the performance of the absorber allowing 90% removal. Optimum placement of the
intercooled stage can reduce packing height by 13%.
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7 Acknowledgements

This work was supported by the Luminant Carbon Management Program. AspenTech provided Aspen Plus®
with RateSepTM. Special assistance was provided by Chau-Chyun Chen of AspenTech.

8 References

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