Technology for a better society [628925]

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ECRA -Cemcap Workshop
José -Francisco Pérez -Calvo
Daniel Sutter
Matteo Gazzani
Marco Mazzotti Chilled ammonia process for CO2 capture 1

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1.Introduction to Chilled Ammonia Capture Process (CAP)
2.Research topics in the CAP
3.Criticalities for CAP application to cement plant conditions Presentation layout

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The Chilled Ammonia Process
1
Flue gas
cooling 2
CO2 removal 3
NH3 slip
abatement 4
CO2
purification Cleaned fluegas CO2
Fluegas Post -combustion CO2 capture
Aqueous ammonia as solvent
Main advantages :
globally available , low cost
no toxic degradation products
highly competitive energy penalty

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The Chilled Ammonia Process
Flue gas
in CO2 depleted
flue gas
Absorber
pumparound CO2 lean
solution
CO2 rich solution CO2 CO2
storage
Cooled flue
gas CO2
Absorber CO2
Desorber Flue gas to the stack NH3 water wash (NH3 + CO2+H2O) to
CO2 capture section
Makeup
H2O DCC NH3 slip
abatement
CO2 removal
Fluegas
cooling CO2
purification

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Hype cycle for NH3-based CO2 capture
[7] Bollinger et al. Alstom Technical Report, Paper No. 72
[8] Darde et al. Int J Greenh Gas Control , 10 (2012) 74 -87
[9] Black et al. (2013) Patent No. US 2013/0028807 A1
[10] Darde et al. Ind Eng Chem Res. 49 (2010) 12663 -12674)
[11] Que and Chen. Ind Eng Chem Res . 50 (2011) 11406 -11421
[12] Baburao et al. Presentation at TCCS -8, Trondheim, Norway [1] Bai and Yeh. Ind Eng Chem Sc. 36 (1997) 2490 -2493
[2] Bai and Yeh. Sci Total Environ. 228 (1999) 121-133
[3] Gal . (2006) Patent No. WO2006/022885A1
[4] Mathias et al. Energy Procedia 1 (2009) 1227 -1234
[5] Mathias et al. Int J Greenh Gas Con 4 (2010) 174-179
[6] Yu et al. Chem Eng Res and Des. 89 (2011) 1204 -1215 • understand
• control
• Exploit solid formation in the CAP .
• new process synthesis
• optimization
• piloting

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Features of an efficient Chilled Ammonia Process
OPTIMAL
CAP plant Low
chilling
duty Low
reboiler
duty
Avoiding
solid
formation Low
ammonia
slip
High
absorption
mass transfer Energy and
environmental
performance
Plant operation
and design

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CAP research topics
Thermo –
dynamics Kinetics Process
Synthesis Process
Optimization Process
Integration

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Thermo –
dynamics Kinetics Process
Synthesis Process
Optimization Process
Integration

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9 Understanding the system thermodynamics

VLE
SLE

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Understanding the system thermodynamics

adapted from :
Darde et al., Ind Eng Chem Res 49 (2010) 12663 -74

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Phase diagram construction
wt. frac.

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Phase diagram construction
10°C
1 bar Thermodynamic model:
Thomsen and Rasmussen. Chem Eng Sci. 54 (1999)1787 -1802
Darde et al., Ind Eng Chem Res. 49 (2010) 12663 -74
Solid properties:
Jänecke , Z Elektrochem. 35 (1929) 9:716 -28

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1 bar Phase diagram construction

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1 bar Phase diagram construction

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1 bar Phase diagram construction

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1 bar Phase diagram construction

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The Chilled Ammonia Process
Flue gas
in CO2 depleted
flue gas
Absorber
pumparound CO2 lean
solution
CO2 rich solution CO2 CO2
storage
Cooled flue
gas CO2
Absorber CO2
Desorber Flue gas to the stack NH3 water wash (NH3 + CO2+H2O) to
CO2 capture section
Makeup
H2O DCC NH3 slip
abatement
CO2 removal
Fluegas
cooling CO2
purification

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18 CO2 depleted
flue gas
Pump –
around
CO2-lean
solution
CO2-rich solution Cooled
flue gas
CO2 absorber

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19 CO2 depleted
flue gas
Pump –
around
CO2-lean
solution
CO2-rich solution Cooled
flue gas
CO2 absorber
Feed

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Thermo –
dynamics Kinetics Process
Synthesis Process
Optimization Process
Integration

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Kinetics – equilibrium and rate-controlled reactions
(1) Self-ionization of water
(2) Dissociation of bicarbonate
(3) Protonation of ammonia
(4) Bicarbonate ion formation 𝐇𝟐𝐎𝐊𝟏 𝐎𝐇−+𝐇+
𝐇𝐂𝐎𝟑−𝐊𝟐 𝐂𝐎𝟑𝟐−+𝐇+
𝐍𝐇𝟑+𝐇𝟐𝐎𝐊𝟑 𝐍𝐇𝟒++𝐎𝐇−
𝐂𝐎𝟐+𝐎𝐇−𝐤𝟒,𝐤−𝟒,𝐊𝟒𝐇𝐂𝐎𝟑−
(5) Carbamate ion formation Equilibrium
reactions Diffusion and rate
controlled reactions
𝐂𝐎𝟐+𝐍𝐇𝟑𝐤𝟓,𝐤−𝟓,𝐊𝟓𝐍𝐇𝟐𝐂𝐎𝐎−+𝐇+

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Kinetics – chemical reaction mechanisms
Bicarbonate ion formation
carbonic acid dissociation CO2+H2O HCO3−+H+ negligible contribution for pH>8 [4]
reaction with hydroxide ion CO2+OH− HCO3−
Carbamate ion formation
Zwitterion mechanism[5,6]
Zwitterion formation CO2+NH3 NH3+COO−
deprotonation NH3+COO−+B NH2COO−+BH+ often considered non -rate-
limiting[1-3]
Termolecular mechanism[7,8] CO2+NH3+B NH2COO−+B
Elementary reactions
mechanism[9] CO2+NH3 NH2COO−+H+
[1] Pinsent et al. Trans Faraday Soc. 52 (1956) 1594 -1598.
[2] Pinsent et al. Trans Faraday Soc. 52 (1956) 1512 -1520.
[3] Puxty et al. Chem Eng Sci. 65 (2009) 915 -922.
[4] Blauwhoff et al., Chem Eng Sci. 39 (1984) 207 -225.
[5] Caplow . J Am Chem Soc. 90 (1968) 6795 -6803 . [6] Danckwerts . Chem Eng Sci. 34 (1979) 443 -446.
[7] Crooks and Donellan . J Chem Soc Perkin Trans II. 4 (1989) 331.
[8] da Silva and Svendsen . Ind Eng Chem Res. 43 (2004) 3413 -3418.
[9] Wang et al. J Phys Chem . 115 (2011) 6405 -6412.

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Thermo –
dynamics Kinetics Process
Synthesis Process
Optimization Process
Integration

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Integrate solid formation into a next generation CAP
•Solid formation in the crystallizer
•No solids in the columns
The chilled ammonia process with solid formation
2
4 Cooled
flue gas CO2 depleted
flue gas
Pumparound CO2 lean
solution
CO2 rich solution CO2

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The chilled ammonia process with solids formation
2
5 CO2
Absorber CO2 Desorber NH3 water wash
Direct
contact
cooler

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0 0.5 1Column stages
Solubility index Absorber profile: standard vs crystallizer CAP
2
6 standard CAP crystallizer CAP
CO2 depleted
flue gas
Pumparound CO2 lean solution
CO2 rich solution Cooled
flue gas Cooled
flue gas CO2 depleted
flue gas
Pumparound CO2 lean solution
CO2 rich solution Crystallizer CAP
Standard CAP
•Lower working temperature
•Better ammonia slip control bottom top
•Higher solubility index
•Higher CO2 loading (lower flow rate)

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Thermo –
dynamics Kinetics Process
Synthesis Process
Optimization Process
Integration

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Definition of the CAP operating conditions
2
8 Process optimization
First Stage
Exploit the user sensitivity and knowledge of the
process by visualizing the conditions on a CO2-
NH3-H2O ternary phase diagram

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Definition of the CAP operating conditions
2
9 Process optimization
First Stage Second Stage
Exploit the user sensitivity and knowledge of the
process by visualizing the conditions on a CO2-
NH3-H2O ternary phase diagram Optimization of the CAP in a limited feasible
region of the operating variables
MATLAB overarching structure
Input parameters :
•NH3 fraction in water
•CO2 loading lean stream
•Absorber loading
•L/G
•Reboiler Duty Sensitivity analysis – CO2
capture section
Minimized function :
•Specific reboiler duty
Input variables:
•L/G
•Reboiler duty
Constraints :
•NH3 removal
•CO2 capture Rigorous optimization –
NH3 removal section
Final operating
conditions Matlab+Aspen
Aspen

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ECRA -Cemcap Workshop
Criticalities for CAP application to cement
plant conditions

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Outline
Increment in the content of CO2 in the flue gas
Power plant 2 – 16%mol
Cement plant up to 30%mol
Modifications of absorber conditions

Cement -like CO2 content leads to different operating conditions of
CAP and/or process modifications To reach 90% of CO2 recovery in the flue gas from the
cement plant:
(i) Increase the liquid -to-vapor flowrate
(ii) Increase the ammonia content in the CO2-lean stream
and/or
(iii) Decrease the CO2 loading of the CO2-lean solution Multiple combinations:
(i) L/G
(ii) Pumparound /Rich
(iii) [NH3]CO2-lean
(iv) (CO2 load)CO2-lean Flue
gas in CO2
depleted
flue gas
Absorber
pumparound CO2
lean
solution
CO2 rich solution CO2
Absorber L
G Pumparound
Rich [NH3]
CO2 load

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Absorber simulations – Exemplary cases
Flue
gas inCO2
depleted
flue gas
Absorber
pumparoundCO2lean
solution
CO2rich solutionCooled flue
gasCO2
Absorber
Makeup
H2ODCC3
124
56
yair = 0.84
yCO2 = 0.16
yH2O = 0
T = 140 °C Power Plant – Base case
Cement Plant cases
yair = 0.70
yCO2 = 0.30
yH2O = 0
T = 110 °C ~ 90% CO2 recovery

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Absorber simulations – Exemplary cases
2 4 6 8 10 12
L/G (wt)
0.0 0.1 0.2 0.3 0.4
V-phase comp (mass frac)CO2
NH3
1
6
11
16
21
26
31
10152025303540455055Stage
Temperature ( °C)
Power Plant
Two differenciated regions in the
absorber separated by the CO2-
lean stream:
(i)NH3-uptake
(ii)CO2-uptake Inlet flue gas yCO2 = 0.16
CO2-lean stream CO2load = 0.35 molCO2/molNH3
[NH3] = 14 % wt (binary )
Absorption process L/G = 3.7 kg/kg
Pumparound /Rich = 0.36
CO2 capture ≈ 90 %
NH3 slip ≈ 10000 ppmv
35

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Modelling
Thermodynamic
model
Simplified kinetics Power Plant

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Modelling
Thermodynamic
model
Process simulation
RATE -BASED Simplified kinetics
Pilot Plant Tests
2 – 16 %mol CO2 Power Plant

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Modelling
Process simulation
EQUILIBRIUM -BASED
Murphree efficiencies Power Plant
Process Integration Process simulation
RATE -BASED Murphree
efficiencies Power Plant

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Modelling
Process simulation
EQUILIBRIUM -BASED
Murphree efficiencies Cement Plant
Process simulation
RATE -BASED Power Plant
Murphree
efficiencies

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Modelling
Murphree
efficiencies ???
Process Integration Thermodynamic
model
Process simulation
RATE -BASED Simplified kinetics
Pilot Plant Tests
2 – 16 %mol CO2 Cement Plant
Power Plant

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CEMCAP approach
Murphree
efficiencies Thermodynamic
model
Modelling & Simulation
RATE -BASED Extended kinetics
Pilot Plant Tests
up to 30 %mol CO2
Process Integration Process simulation
EQUILIBRIUM -BASED
Murphree efficiencies

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Acknowledgements
This project has received funding from the European Union's Horizon 2020
research and innovation programme under grant agreement no 641185

This work was supported by the Swiss State Secretariat for Education, Research
and Innovation (SERI) under contract number 15.0160

www.sintef.no/cemcap
Twitter: @CEMCAP_CO2