Trondheim CCS Conference (TCCS-6)

June 14-16, 2011, Trondheim, Norway

A general column model in CO2SIM for transient

modeling of CO2 absorption processes
Programming methods and code development

Andrew Tobiesena

Magne Hillestadb, Hanne M. Kvamsdala, Actor Chikukwaa

aSINTEF Materials and Chemistry, Postbox 4760 Sluppen,7494, Trondheim, Norway

bNorwegian University of Science and Technology, NTNU, Sem Sælandsvei 4, Trondheim, 7491, Norway

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 Dynamic modeling of CO2 absorption systems
Project description
Validation
Simulation studies

Rationale Summary

• The objective of this work task is to implement a dynamic absorber in CO2SIM

– The model should be a ‘multipurpose’ packing model

• Focus is placed on competence building through use of simulation models that

can be:
– verified against experimental and plant data where feedback to the work is
done ‘fairly quickly’ (validation/verification through established routines)

– by developing dynamic simulation models based on already established

computer architecture (efficient development)

• To assist in understanding CO2 capture processes (or any chemical process), we

believe process simulation is beneficial to all phases in a projects lifetime

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 Dynamic modeling of CO2 absorption systems
Reasons for developing a dynamic simulator Project description
Validation

We are now moving towards building full scale Simulation studies

Summary

plants
• Large and frequent load changes of the power plant requires understanding of dynamic
operation
– How shall the capture plant be operated and controlled?
– What are the real consequences of varying loads at the CO2 removal plant?
– How do we handle unsteady behavior, shut down, start up?
Condenser
– Or changes in load due to fluctuations in energy demand? N2, 1.9 bar
O2, CO2 to
Exhaust: H2 O compression
CO2,N2, O2 ,H2O Amine 45 °C
Pressurized NG absorption
HRSG Amine stripper
40 °C

CO2-rich 30 Re-
wt % boiler
ST
MEA/H2O
GT Generator
Air
CO2-lean 30 wt %
MEA/H2O
LP steam (3.8 bar, 140 °C)

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 Dynamic modeling of CO2 absorption systems

Development Strategy: Project description

Validation
Simulation studies
Summary

• Task 1: Implement a dynamic column model

– Development of the model for absorption and desorption
– Test model and validate towards pilot plant data (steady state and dynamic)
• Task 2: Develop the connected unit operations, flash tanks, mixers, storage tanks and
heat exchangers
– Definition of unit operations built into CO2SIM
• Task3: Develop the dynamic Network solver
– Flowsheet model
– Programming techniques: information handling
– Information structure
• relationship between an event (the cause) and a second event ( the effect) -> causality

This work is extensive...

Our first requirement is therefore: We must have a platform for development

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Development platform Dynamic modeling of CO2 absorption systems
Project description
Validation

CO2SIM programming techniques Simulation studies

Summary

• Fundamental problem: Exponential

increase in complexity as code
becomes larger
• Requires focus on structural planning
and architectural patterns
– Design patterns can speed up the
development process
– Provides fundamental development
methods related to
• program organization
• and common data structures (classes)
– In other words; the basic code
elements at each layer are reusable
– The code design should be general Such design patterns provide general solutions,
enough to address future requirements documented in a format that does not require
also specific ties to a particular problem

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Development platform CO2SIM@SteadyState Dynamic modeling of CO2 absorption systems

Example: Use of ‘Design patterns’ does

Project description
Validation
Simulation studies

generalize code development Summary

Routine that minimizes the need

for manually processing data
1. Obtain plant data for the full
campaign
2. Duplicate plant flow sheet in the
simulator
3. Simulate the complete campaign
(one execution)
4. Evaluate statistics for the full
campaign
5. Further use: optimization etc.
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Development platform CO2SIM@SteadyState Dynamic modeling of CO2 absorption systems
Project description
Validation
Simulation studies
Summary

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 Dynamic modeling of CO2 absorption systems
Project description
Validation
Simulation studies

Development Strategy Summary

• Task 1: Implement a dynamic CO2SIM column model

– Model description and numerical methods
– Test model and validate towards pilot plant data (steady state and dynamic)
• Task 2: Develop the connected unit operations, flash tanks, mixers, storage tanks and
heat exchangers
– Definition of unit operations built into CO2SIM
• Task3: Develop the dynamic Network solver
– Flowsheet model
– Programming techniques: information handling
– Information structure:
• relationship between an event (the cause) and a second event ( the effect) -> causality

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 Dynamic modeling of CO2 absorption systems
Project description
Validation
Simulation studies

Task 1: The transient column model Summary

• Based on first principle conservation laws

for energy and mass
• Adaptability of the code for different
chemical systems and process
configurations have been emphasized

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 Dynamic modeling of CO2 absorption systems

The transient column model Project description

Validation
Simulation studies
Cleaned gas

Transport equations n n g,i,out

Hg,i,out
Summary l,i,out
Hl,i,out
P1 P0
Lean amine
1
Tg,out Tl,out

Gas phase normalized

height (h) dr

ε GCtot ,G
∂yi
∂t
−ntot ,G
=
1 ∂yi
L ∂zn
(
− N i a − yi ∑ j N j a ) Flue gas
0
ng,i,in nl,i,in
Top view

Hg,i,in Hl,i,in
dntot ,G d(ε GCG ) P0 P0

−∑ j N j a +
= Rich amine
Tg,in Tl,in

dz dt
∂T 1 ∂TG a Bondary conditions
εG G = −uG − ⋅ hG / L ( TL − TG )
∂t L ∂zn ∑i (CiC p ,i )G
yi ( zn ,0 ) = yi ,feed xi ( zn ,1 ) = xi ,feed
Liquid phase ntot ,G ( zn ,0 ) = ntot ,G , feed ntot ,G ( zn ,1 ) = ntot , feed
∂x
ε LC L =i
∂t
ntot ,L
1 ∂xi
L ∂zn
(
+ N i a − xi ∑ j N j a ) TG ( zn ,0 ) = TG , feed TL ( zn ,1 ) = TL , feed
dntot ,L
= −∑ j N j a
dz CG = P / ( RTG ) Ideal gas or SRK model
ε
dTL
l dt
=−uL
1 ∂TL
−
a
L ∂zn ∑i (CiC p ,i ) L
(
hL /G (TL − TG ) − ∑ j ∆H j N j − H wall (TL - Tout ) ) ntot = mol / m 2 / s
zn = z / L normalized column lenth

An extension of the model presented in: Kvamsdal, Jakobsen and Hoff, Chemical Engineering and Processing:, Volume 48, Issue 1, January 2009

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 Dynamic modeling of CO2 absorption systems

The transient column: numerics Project description

Validation
Simulation studies
Numerical solution to stiff DAE’s Summary

• Two point differential algebraic problem

Cleaned gas

ng,i,out nl,i,out

(DAE) in a single dimension Lean amine

Hg,i,out
P1
Tg,out
Hl,i,out
P0
Tl,out
1

• Discretization
– Time normalized
dr
height (h)

• Higher order integrator

– Space Flue gas
0
Top view

ng,i,in nl,i,in
• Static collocation derivatives Hg,i,in Hl,i,in
P0 P0

•
Tg,in Tl,in
To increase robustness we need Rich amine

• Stabilizing methods
1. Normalization
2. Dynamic relaxation (gives initial steadystate
slopes)

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 Dynamic modeling of CO2 absorption systems
Project description
Validation
Simulation studies

Outline Summary

• Dynamic modeling of CO2 absorption plants

• Project description
• Simulator requirements/capabilities
• Short description of simulation model

• Verification/Validation (Preliminary)
• Experimental validation using pilot plant data
• Simulation studies
• Ramp behavior
• Robustness of code
• Summary
• Further work
• Acknowledgements

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 Dynamic modeling of CO2 absorption systems
Project description
Validation
Simulation studies
Experimental validation of dynamic column model Summary

• Tested against the “VOCC rig”

• Two time series cases (case A and B)
• 30wt%MEA
• Logging of input and output data every 5
seconds
– The cases give about 500 updates
during simulation
• CO2SIM handles all these “events”
automatically during integration to
reflect process changes.
Absorber: – The events are collected and
Packing height = 5.4m systematically handled from log files
ID = 0.5m (excel).

Validation of CO2 Capture - The VOCC-project (2007)

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 Dynamic modeling of CO2 absorption systems

VOCC test case Project description

Validation
Simulation studies
Summary

• Case B: Stepwise variations in CO2 Property logging of inputs (only at events): molfracCO2vap and phase:vap
0.055
gas concentration
• Inlet gas concentration of 0.05

CO2 increased in two single 0.045

Property: molfracCO2vap
step-changes
0.04
• then decreased in a large
reverse single step-change 0.035

0.03

• All other process variables 0.025

kept constant
 Stable liquid and gas flow over 0.02
1000 1500 2000 2500 3000 3500
the experiment. time [s]

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 Comparing data from VOCC test with simulation
Dynamic modeling of CO2 absorption systems
Project description
Validation
Simulation studies
Simulated and measured:
Summary
Rich loading

Red line – PILOT data

Blue line – SIMULATION

Simulation time increased 30 times

20-30 times faster than real-time

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 Comparing data from VOCC test with simulation
Dynamic modeling of CO2 absorption systems
Project description
Validation
Simulation studies
Simulated and measured: Simulated and measured: Summary
Rich loading Outlet Liquid Solvent temperature
Property logging of outlets (only at events): loading and phase:liq Property logging of outlets (only at events): temp and phase:liq
0.42 321

320
0.4
319

0.38 318
Property: loading

Property: temp
317
0.36
316

0.34 315

314
0.32 Blue– SIMULATION
Red - PILOT 313

0.3 312
1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000
time [s] time [s]

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 Dynamic modeling of CO2 absorption systems

Simulation example
Project description
Validation
Simulation studies
Case A: Increasing gas load Summary

Property logging of inputs (only at events): flow and phase:vap

• Increasing molar ratio between the 125

gas and liquid flowrate 120

– Varying the liquid and vapor input
115
flow rates by ~50%?
• In a time frame of 50 seconds 110

Property: flow
– Initially running at steady state 105
then increase gas flow with 50%
100
over a short time interval
– Observe the transients, then run 95

end situation to steady state 90

again
85

80
• 20 meter packing, identical inlet 0 500 1000 1500 2000
time [s]
2500 3000 3500 4000

concentrations , only vary flow rate

Blue: gas flowrate (kmol/h)
Green: liquid flow rate (kmol/h)

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Case A: Increasing the flue gas load Dynamic modeling of CO2 absorption systems
Project description
Effect on loading Validation
Simulation studies
Property logging of outputs (only at events): loading and phase:liq
Summary
Property: loading 0.43

0.42

0.41

0.4

0.39
0 500 1000 1500 2000 2500 3000 3500 4000
time [s]
Effect on percent CO2 removed
Property logging of inputs (only at events): gasremoved and phase:vap
0.85

0.8
Property: gasremoved

0.75

0.7

0.65

0 500 1000 1500 2000 2500 3000 3500 4000

time [s]
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 Dynamic modeling of CO2 absorption systems
Case B: Varying flue gas load Project description
Validation
Simulation studies
Summary

Property logging of inputs (only at events): flow and phase:vap

• Varying the molar ratio between 130
the gas and liquid flow rate 125
– In a time frame of ~300 seconds 120
– Initially running at steady state 115
then increase/reduce gas flow 110
with 50%

Property: flow
105
– Observe the transients, then run
100
end situation to steady state
95
again
90
• 20 meter packing, identical inlet
85
concentrations , only vary flow rate
80

75

0 50 100 150 200 250 300 350 400

time [s]
Blue: gas flow rate (kmol/h)
Green: liquid flow rate (kmol/h)

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Case B: Varying the flue gas load Dynamic modeling of CO2 absorption systems
Project description
Effect on loading Validation
Simulation studies
Property logging of outputs (only at events): loading and phase:liq Summary
0.42
Property: loading

0.41

0.4

0.39
0 500 1000 1500 2000 2500 3000 3500 4000
Effect on percent CO2 removed time [s]
Property logging of inputs (only at events): gasremoved and phase:vap
0.84

0.83
Property: gasremoved

0.82

0.81

0.8

0.79

0.78

0.77

0.76
0 500 1000 1500 2000 2500 3000 3500 4000
time [s]
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 Dynamic modeling of CO2 absorption systems
Project description
Validation
Simulation studies

Summary Summary

• At this stage in the project a robust codebase is developed for dynamic simulation
– Absorber, desorber packing model (this presentation)
• Verified numerics
• Validated towards plant data (preliminary)
• The event updating procedures facilitates rapid simulation using plant data for validation
• Current model gives acceptable match towards data for MEA
– Both at dynamic and steady state operation
• The implementation methodology allows for efficient simulation of the units’ transient
behavior for continuously changes in input conditions or design parameters, part load
operation, varying input conditions and ramping behavior

Further work
• A few units implemented: Storage tank, dynamic flash, mixer tank and the
column model
• Network solver to handle sequential dynamic integration

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 Dynamic modeling of CO2 absorption systems
Project description
Validation
Simulation studies
Summary

Acknowledgement
This presentation forms a part of the BIGCO2 project, performed under the
strategic Norwegian research program Climit. The authors acknowledge the
partners: StatoilHydro, GE Global Research, Statkraft, Aker Clean Carbon, Shell,
TOTAL, ConocoPhillips, ALSTOM, the Research Council of Norway (178004/I30
and 176059/I30) and Gassnova (182070) for their support.

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