A Rate-Based Process Modeling Study of CO2 Capture with Aqueous Amine

Solutions using aspenONE Process Engineering™

Chau-Chyun Chen, David Tremblay, Chai Bhat
Presented at the Clearwater Coal Conference, Clearwater Florida, June 4th 2008

ABSTRACT

Rising energy prices coupled with a higher environmental consciousness have generated
renewed interest in abundant fossil fuels such as coal, and ways to successfully capture and
store the Carbon Dioxide (CO2) produced during coal gasification. Mono Ethyl Amine (MEA),
Methyl Diethyl Amine (MDEA) and activated Tri Ethyl Amine (TEA) solutions are being
considered by the industry as a means of capturing CO2.

In this study we used Aspen RateSep to simulate the U. Texas-Austin experiments

(Dugas, 2006[1]) for CO2 capture with aqueous MEA solution. Aspen RateSep is a second
generation rate-based absorption and stripping unit operation model that works with Aspen Plus.
The model predictions against the MEA pilot plant data are presented. The superiority of rate-
based model predictions is shown. The impact of simulation results of various rate-based
modeling constructs, i.e., film discretization, flow mixing; interfacial area correlations, etc are
examined.

DESIGNING GASIFICATION PROCESSES USING aspenONE PROCESS ENGINEERING™

aspenONE Process Engineering enables engineers to model the entire gasification

process in one integrated environment. aspenONE Process Engineering has been successfully
utilized by plant owners/operators, engineering and construction companies, and technology
providers to improve yields, increase plant efficiency and quality, and reduce capital and
operating costs.

Designing a gasification facility can be challenging because of the different options

available such as gasifier type, feed type (different types of coal, cellulose, industrial waste,
biomass, petroleum coke, etc), end product demand (power, chemicals, fuel, etc). It is imperative
that each sub-process within a gasification facility, such as the sizing unit, the air separation unit,
the gasifier, gas cleaning unit (absorption and stripping of the acid gas), the CLAUS unit, etc be
modeled precisely so as to derive optimum conversion efficiency in the gasifier and clean out any
acid gas generated. Aspen Plus is used by many companies to design every sub-process in one
integrated environment; Aspen Plus is an integral part of aspenONE Process Engineering.

In fact, Aspen Plus was born out of the 1970’s energy crisis and the need for simulation
of unconventional solids such as coal. For over 25 years Aspen Plus has been used to model
advanced power processes, and all the major types of gasifiers used in the industry. Aspen Plus
has unique out-of-box capability of handling coal, while the equation oriented capability is ideal for
simulating large scale integrated coal plants.

Figure 1 illustrates the overall engineering workflow and life cycle process of designing a
gasification plant. Based on the process concept and business objective, one can establish the
performance of the concept and then improve the concept using conceptual design
methodologies in Aspen Plus. The base case and the improved case economic feasibility can be
compared using standard cost analysis environment such as Aspen Icarus Project Evaluator. It is
also important to establish a detailed performance model for critical equipment. This helps identify
a practical design option during the conceptual phase. The basis for these detailed equipment
models needs to be consistent between the base case and the improved case. Detailed models
of the gasifier can be developed using Aspen Custom Modeler.

After developing an improved process concept, Aspen Dynamics can then test the
process for safety, operability, and controllability issues; this defines the key control loops and the
instrumentation for the process. Once the process control strategy and key instrumentation is
defined, the definition of the process intent for the design is complete.

Aspen Zyqad can then be used to develop the FEED package, incorporating the PFD or
process P&ID for the improved concept, equipment designs, data sheets, summary sheets and
basic control loops and instrumentation. The process design information can then be further
transferred into detailed P&ID and instrumentation environments.

The performance models developed for the process can be re-used for operational
monitoring and improvement of the plant using Aspen Simulation Workbook. The performance
model can also be deployed to non-expert users who may not have background in simulation to
perform “what if analysis” studies over the web using Aspen Online Deployment.

Traditionally gas cleaning has been modeled using equilibrium stage models, which have
not provided the accuracy needed for real world industrial applications.

RATE BASED DISTILLATION

Aspen Rate Based Distillation (Aspen RateSep) is part of the aspenONE Process
Engineering solution, and extends the functionality of Aspen Plus RadFrac distillation model with
second-generation rate-based technology which accurately predicts simulation over a wide range
of operating conditions. Aspen Rate Based Distillation uses sate-of-the-art mass- and heat
transfer correlations to predict column performance, without the need of efficiency factors. This
added degree of rigor is especially critical for modeling gas scrubbers, sour water strippers,
azeotropic systems, reactive distillations, nitric acid absorption columns, narrow-boiling
separations, and other highly non-ideal separation processes.

The rate-based modeling approach is superior to the traditional equilibrium-stage

modeling approach that has been employed extensively in the process industries over the
decades. The rate-based models assume that separation is caused by mass transfer between the
contacting phases, and use the Maxwell-Stefan theory to calculate mass transfer rates[2].
Conversely, the equilibrium-stage models assume that the contacting phases are in equilibrium
with each other, which is an inherent approximation because the contacting phases are never in
equilibrium in a real column.

The rate-based modeling approach has many advantages over the equilibrium-stage
modeling approach. The rate-based models represent a higher fidelity, more realistic modeling
approach and the simulation results are more accurate than those attainable from the equilibrium-
stage models. The rate-based modeling approach can reduce the risk of inadequate designs or
off-spec operation because the rate-based models explicitly account for the actual column
configuration which affects column performance.

Designed to model reactive multistage separation problems rigorously and accurately,

Aspen RateSep balances gas and liquid phase separately and considers mass and heat transfer
resistances according to the film theory by explicit calculation of interfacial fluxes and film
discretization. The film model equations are combined with relevant diffusion and reaction kinetics
and include the specific features of electrolyte solution chemistry, electrolyte thermodynamics,
and electroneutrality where appropriate. The hydrodynamics of the column is accounted for via
correlations for interfacial area, hold-up, pressure drop, and mass transfer coefficients. Figure 2
illustrates the basic picture of CO2 transfer across the vapor and liquid films.

SIMULATION OF THE UNIVERSITY OF TEXAS - AUSTIN PILOT PLANT EXPERIMENTS

WITH ASPEN RATESEP

The pilot plant facility is a closed-looped absorption/stripping system for CO2 removal
from a flue gas by means of a 32.5% aqueous MEA solution. In this study the pilot plant absorber
was simulated using Aspen RateSep. Aspen RateSep automatically selects the correlations to
execute the various calculations. Aspen RateSep offers several options for modeling film
resistance, the film discretization option was chosen for this study. Aspen RateSep also provides
four different flow models to determine the bulk properties used to evaluate the mass and energy
fluxes and reaction rates of a stage. In this study the “Countercurrent” flow model was used as
the base calculation method.

The Aspen RateSep simulation results are summarized in Table 1, along with the
experimental performance data. The feed stream data is shown in the “Lean” and “Rich” columns.
“Lean” column contains values of CO2/MEA mole ratio of the lean stream, while the “Rich” column
contains the mole ratios of CO2/MEA mole ratio of the rich stream. These values indicate the
performance of the absorber. Note that the equations used to calculate the “Experimental” mole
ratio of CO2/MEA ignore the influence of MEA concentration; however in reality the solution
density is sensitive to MEA concentration especially for the rich stream with the high CO2 loading.

The CO2 loading was determined by taking sample solution density at five locations on
the absorber. Table 2 contains the MEA mass concentrations of the five samples. There is a
great deal of variability in this data, this confirms that the density of the liquid is sensitive to the
MEA concentration especially when the CO2 concentration is high. A correction can be applied to
the density so that the estimated CO2 loading absorber will decrease and the simulation results
will be much closer to the experimental results.

An absorber temperature profile was obtained by temperature sensors located on the

absorber. When CO2 reacts with MEA the heat of reaction produces a temperature bulge in the
column. This temperature bulge can significantly affect the absorption rates in the column since
the kinetics of the absorption reaction, the phase equilibrium composition of the system, and the
fluid transport properties depend on the temperature. This temperature bulge occurs at the top
section of the absorber until a pinch point where the temperature is the highest. In the section
below this point, the temperature will decrease.

Three distinct types of temperature profiles were evident in the shape of the temperature
bulge. All the cases in this study can be categorized in one of the three temperature profiles. It
was observed that the temperature profiles obtained from each case were related to the ratio of
gas flow rate to liquid flow rate.

When the ratio of gas flow rate to liquid flow rate was relatively high the absorption
reaction occurred at the top section of the absorber, in which case the temperature profile had a
pinch point near the top of the absorber.

When the liquid flow rate is high almost all the CO2 is absorbed at the bottom section of
the absorber, this leaves very little CO2 to react with the MEA in the top section and the pinch
point is near the bottom of the absorber.

When the CO2 absorption takes place throughout the absorber a very broad pinch is
visible in the temperature profile. The temperature changes sharply at both ends, one near the
top and the other near the bottom, and the temperature profile between the ends is relatively flat.
This is a transition type of temperature profile.

Both the vapor and the liquid phase temperature profiles are obtained from the Aspen
RateSep simulation. There was not much temperature difference between the two phases, this is
evident in Figure 3. For all other cases only the liquid phase temperature profile is shown.

As illustrated in Figure 4 the simulated temperature profile matches the absorber

experimental data very well, this was observed in all the cases simulated with Aspen RateSep.

CONCLUSION

In this study we established that the rate-based simulation results using Aspen RateSep
conform to the pilot plant absorber experimental data generated at U. T. – Austin. The Aspen
RateSep model accurately predicts the temperature profile in the pilot plant. The Aspen RateSep
model with proper model parameters provides excellent 1st principles-based predictive capability
and it should be very helpful for industrial process and plant design of the CO2 capture
processes.

With Aspen RateSep’s far superior rate-based modeling capabilities, ability to rigorously
model the liquid film with industry leading film discretization capability, and seamless integration
with aspenONE Process Engineering engineers can simulate plant performance accurately and
design plants with confidence, minimizing contingency factors, lowering capital and operating
costs, and avoid potential expensive start-up issues.

REFERENCES

[1] Dugas, R.E., Pilot Plant Study of Carbon Dioxide Capture by Aqueous Monoethylamine.
Master thesis, Chemical Engineering, the University of Texas at Austin, 2006.

[2] Taylor, R., R. Krishna, and H. Kooijman, “Real-World Modeling of Distillation,” Chem. Eng.
Prog., July 2003, 28-39.
FIGURES

Figure 1: Integrated Process Engineering Workflow Diagram

Reuse Process Models for Reuse Process Models for

Operations Decisions / OTS Planning Decisions

Aspen Aspe Aspe

Operations/ Simulation n n
Maintenance

Safety & Controllability Process Performance Modeling Analyze Economic

Analysis & Analysis Performance

Aspen Aspen Aspe

Dynamic Plus n
Conceptual
Design / R&D
Detailed Equipment
Design
Develop Basic Design Package Analyze Detailed
Aspen Costs
HTFS+ Aspe
Basic Aspe
n
Engineering n

Develop Detailed Plant Design

Detailed
Engineering

Figure 2: Discretized film concept is combined with the countercurrent flow configuration in Aspen
RateSep
Figure 3: Absorber temperature profile of Type A, Case 7: Experimental data from Dugas
(2006)[1], Liquid temperature calculated by Aspen RateSep, Vapor temperature calculated by
Aspen RateSep

200

180
Temperature, F

160

140

120

100

80
-1 1 3 5 7 9
Height from Bottom , m

Figure 4: Absorber temperature profile of Type A, Case 24: Experimental data from Dugas
(2006)[1], Liquid temperature calculated by Aspen RateSep

200

180
Temperature, F

160

140

120

100

80
-1 1 3 5 7 9
Height from Bottom , m
TABLES

Table 1: Performance of the absorber

Lean (molCO2/molMEA) Rich (molCO2/molMEA)

Case
Experimental Experimental Simulation
5 0.180 0.525 0.485
6 0.182 0.523 0.478
7 0.177 0.496 0.457
8 0.170 0.493 0.456
9 0.150 0.532 0.475
10 0.148 0.533 0.476
11 0.147 0.537 0.481
12 0.143 0.546 0.482
13 0.323 0.507 0.459
14 0.329 0.508 0.459
18 0.268 0.506 0.459
19 0.274 0.495 0.456
20 0.271 0.538 0.476
21 0.274 0.540 0.477
22 0.282 0.554 0.482
23 0.277 0.557 0.483
24 0.275 0.506 0.451
25 0.278 0.386 0.346
26 0.275 0.376 0.341
27 0.284 0.413 0.372
28 0.287 0.412 0.373
29 0.285 0.448 0.428
30 0.284 0.453 0.439
31 0.281 0.426 0.419
32 0.279 0.428 0.407
33 0.283 0.422 0.405
34 0.282 0.420 0.406
35 0.280 0.415 0.388
36 0.284 0.425 0.405
37 0.282 0.404 0.386
38 0.281 0.402 0.379
39 0.228 0.367 0.322
40 0.229 0.371 0.325
41 0.235 0.433 0.399
42 0.232 0.430 0.401
43 0.231 0.491 0.438
44 0.231 0.492 0.435
45 0.285 0.433 0.386
46 0.286 0.426 0.388
47 0.281 0.539 0.466
48 0.285 0.537 0.466
Table 2: Mass ratios of MEA/(H2O+MEA) of five samples for Case 22

Sample Mass ratios of MEA/(H2O+MEA)

Lean into the top of the absorber 0.325
Middle of the absorber 0.328
Rich out of the bottom of the absorber 0.334
Middle of the stripper 0.300
Lean out of the bottom of the stripper 0.399