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HiP C Hi h P f C tHiPerCap ‐ High Performance CaptureFP7 Grant agreement n° 608555
Sterically hindered alkanolamines as strong bicarbonate forming solvents for post combustion captureforming solvents for post‐combustion capture
Ardi Hartono1, Rune Rennemo1, Solrun J Vevelstad2, Inna Kim2, Hanna Knuutila1, Odd‐Gunnar Brakstad2, Andrew Tobiesen2, Geir Haugen2
Source CO2 capture Transport Storage
1Norwegian University of Science and Technology (NTNU) and 2SINTEF Materials & Chemistry
2 p p StorageNatural gas
Oil
Bio‐fuel
Coal
PCCC‐3, Regina, Canada, 8th ‐11th September 2015 1
BackgroundBackgroundObjective: proof‐of‐concept enabling 25% reduction in efficiency penalty compared to a demonstrated state of the art capture process in the EU project CESAR
Solvent selection( TCCS 8 A2 A di H t htt // f i /? i 569 b16 5 l5# )
a demonstrated state‐of‐the‐art capture process in the EU project CESAR
(see TCCS‐8, A2, Ardi Hartono, https://conference.preseria.com/?session=r569cmb16uu5cl5# )
Input for technology accessement Solvent properties:
Phase equilibrium and ∆Habs
Solvent degradation Environmental propertiesEnvironmental properties
Energy consumption(see TCCS‐8, B3, Hanne Kvamsdal, https://conference.preseria.com/?session=7hryq7psuthhodo#
PCCC3 2C Hanne Kvamsdal http://www ieaghg org/member/52 conferences/pccc/557 pccc3 ts2 )PCCC3, 2C, Hanne Kvamsdal http://www.ieaghg.org/member/52‐conferences/pccc/557‐pccc3‐ts2 )
PCCC‐3, Regina, Canada, 8th ‐11th September 2015
Scope of the assessment in HiPerCap projectScope of the assessment in HiPerCap project
Overall comparison
Scope 5
Treated Overall comparison
On level of key Capture Process
ConditioningPre‐
treatmentCompression
ReferencePower Plant(modified)
flue gas
flue gas
Coal
Capture technology
treatedflue gas
steam
CapturedCO2
indicators the following performance can be
determined:Power(kWe)
condensate
CoolingWater
Indicator EnergyReference Coal fired power plant
Indicator EnvironmentalReferencePower Plant
Reference Coal fired power plant
flue gasCoal
Indicator Cost
[TCCS 8 B3 H K d l htt // f i /? i 7h 7 thh d #]
Power (kWe)
Cooling Water
PCCC‐3, Regina, Canada, 8th ‐11th September 2015 3
[TCCS‐8, B3, Hanne Kvamsdal, https://conference.preseria.com/?session=7hryq7psuthhodo#]
Solvent selection
Chemical structure (steric hindrance) and pKa (literature)
Solvent selection
Chemical structure (steric hindrance) and pKa (literature) Physical properties (Volatility, solubility in water) Toxicity Absorption rate and cyclic capacity (experimental test) Absorption rate and cyclic capacity (experimental test)
6 solvents show cyclic 6 solvents show cyclic capacity comparable to MEA 30 mass%
3 solvents have foaming issue (Red arrows)
1 solvent has high a melting 1 solvent has high a melting point (Black arrow)
2 solvents selected(Greenarrows)
[TCCS 8 A2 Ardi Hartono https://conference preseria com/?session r569cmb16uu5cl5# ]
PCCC‐3, Regina, Canada, 8th ‐11th September 2015
[TCCS‐8, A2, Ardi Hartono, https://conference.preseria.com/?session=r569cmb16uu5cl5# ]
Phase equilibriummeasurementsPhase equilibriummeasurements
Empirical ("soft") model:Empirical ( soft ) model:
pCO2 , T=40‐80 oC, Ptot = ambient
Buffer Tank
Feed Line
Vacuum Pump
TI PI
TG
Cooling out
Cooling in
Reactor (VR)
N2 CO2
Sample Line
TLCPI
TG
Heating in
Heating Out
Total P, T= 80‐120 oC, Ptot = max 6 bar
PCCC‐3, Regina, Canada, 8th ‐11th September 2015 5
Phase equilibriummeasurementsPhase equilibriummeasurements103
104
104
HS#1
10-1
100
101
102
PC
O2 (k
Pa) 10
3
(b)HS#2
10-4
10-3
10-2
10 1
40C60C80C100C120C
HS#1, AARD = 15%10
1
102
PC
O2 (k
Pa)
102
103
104
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 110
(mol CO2/mol Amine)
10-2
10-1
100
10-1
100
10-1
100
101
10
PC
O2 (k
Pa)
10 10 10 (mol CO2/ mol Amine)
‐‐‐‐‐‐MEA‐‐‐‐‐‐ CESAR 1
HS#1 and HS#2
0 0 1 0 2 0 3 0 4 0 5 0 6 0 7 0 8 0 9 110-4
10-3
10-2
40C60C80C100C120C
HS#2, AARD = 13% [30% MEA: U.E. Aronu et al., 2011. Chem.Eng.Sci 66, 6369‐6406 (40 oC),S. Ma'mun et al., 2005. J.Chem.Eng.Data 50, 630‐634 (120 oC)
CESAR 1: internal data]
‐‐‐‐‐‐ HS#1 and HS#2
PCCC‐3, Regina, Canada, 8th ‐11th September 2015 6
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 (mol CO2/mol Amine)
Heat of absorption, ∆Habs (differential in loading, 40oC)
R i l i CPA 122Reaction calorimeter CPA 122T= up to 150 oC, P = up to 40 bar
PCCC‐3, Regina, Canada, 8th ‐11th September 2015 7
Thermal degradationThermal degradation
• 30 mL cell (316SS stainless steel) • 15 ml of loaded amine solution • 135 oC, 5 weeks• Liquid analysis :
Amine, CO2
Metal (Fe, Cr, Ni)
% Degr t=5:• HS#1 : 18% loss, Fe < 3 mg/L• HS#2 : < 6% loss Fe < 18 mg/LHS#2 : < 6% loss, Fe < 18 mg/L
30% MEA ‐ 56 % loss, 600‐900 mg/L Fe concentration [I. Eide‐Haugmo, 2011. PhD thesis]
(3.5m AMP+1.5m Pz) – 6 % loss AMP, 9% loss piperazine [Tielin, 2013. PhD thesis.]
PCCC‐3, Regina, Canada, 8th ‐11th September 2015 8
Oxidative degradationOxidative degradation
• 1 5 L jacketed glass reactor• 1.5 L jacketed glass reactor• 1L of loaded amine solution• 0.35 L/min Air + 7.5 mL/min CO2
• 55 oC, 21 days• Liquid analysis
Alkalinity CO2
% Degr t=21:• HS#1: 57.6% loss• HS#2: < 10% lossHS#2: < 10% loss
30% MEA after 21 days: 10 % loss [S.J. Vevelstad et al., 2013. Int Journal of Greenhouse gas control, 28, 156‐167]
(3 5m AMP+1 5m Pz) after 38 days at 80 oC: 7 % loss AMP 30% loss piperazine [Tielin 2013 PhD thesis]
PCCC‐3, Regina, Canada, 8th ‐11th September 2015 9
(3.5m AMP+1.5m Pz) after 38 days at 80 C: 7 % loss AMP, 30% loss piperazine [Tielin, 2013. PhD thesis]
Environmental properties
Ecotoxicity• Algal cultures added to amine solutions of
different concentration and incubated at 20 oCfor 72 hr
• Inhibition of algal growth measured (EC‐concentrations)
• EC‐50 ‐ concentration inhibiting algae growth
Amine Ecotoxicity(EC50; mg/L)
Biodegradability(% BOD of ThOD)
Colourcode*
g g gby 50%
Biodegradation (in water)• Amines diluted in water (2 mg/L) and incubated
20 C f 28 d HS#2 14.8 38.6HS#1 43.8 71.0MEA 198 68AMP 119 3Pi i 472 1
> 10 > 60
> 20
at 20 oC for 5‐28 days• Oxygen consumption determined from the
difference between dissolved oxygen in water with and without chemicals (biological oxygen
Piperazine 472 1
*Adopted from OSPAR convention [HELCOM 29/2008]MEA, AMP, Pz data [I. Eide‐Haugmo, 2011, PhD thesis]
demand – BOD)• Biodegradation determined as % of a
theoretical oxygen demand (ThOD) for the studied chemical
PCCC‐3, Regina, Canada, 8th ‐11th September 2015 10
Input for technology assessment and benchmarkingInput for technology assessment and benchmarking
Flue gas (kg/h) 3073567( k l/h)
Assumptions(105,361 kmol/h)
Flue gas Temp. [C] 47.0 1. specified removal rate of 90 %(mol) CO2 from the inlet flue gas (90% approach to equilibrium in the absorber)
2. 5oC heat approach defined on the cold side for the heat exchangers3. absorber diameter was set so that the column never surpassed 70% of
the velocity of flooding
Flue gas Pressure [kPa] 105.0CO2 at inlet (mol %wet) 13.6 %H2O at inlet (mol %wet) 10.6 %
PCCC‐3, Regina, Canada, 8th ‐11th September 2015 11
the velocity of flooding4. compression train is not included
Energy consumptionEnergy consumption
30% MEA
(HS#1/HS#2)
PCCC‐3, Regina, Canada, 8th ‐11th September 2015 12
Summary comparison of the solventsSummary comparison of the solvents
Opt HIP1 Opt HIP2 Opt MEA CESAR 1
Solvent Lean flow rate (kg/s) 1395.41 1705.64 2624.19
Solvent Lean Temp. [C] 40 40 40
Solvent Rich Temp. [C] 108 108 113
Solvent Lean CO2 loading 0.02 0.01 0.19 0.14
Solvent Rich CO2 loading 0.69 0.52 0.48 0.56Solvent Rich CO2 loading 0.69 0.52 0.48 0.56
Approach to equilibrium based on loading (abs bottom) 91 74 92
Flue gas (Nm3/h) 2369025 2369025 2369025
b l [k ]Reboiler Duty [kW] 436420 359133 571224
CO2 recovery (%) 90 % 75 % 90 %
Spesific Reboiler duty [GJ/tonn CO2] 2.77 2.73 3.62 3.02/2.72
* CESAR 1 from [H. Kvamsdal et al., 2011. Energy Procedia 4, 1644‐1651] – to be estimated at conditions specified in HiPerCap
Specific solvent requirement [kg Amine/kg removed] 8.85 12.99 16.65
PCCC‐3, Regina, Canada, 8th ‐11th September 2015 13
CESAR 1 from [H. Kvamsdal et al., 2011. Energy Procedia 4, 1644 1651] to be estimated at conditions specified in HiPerCap
AcknowledgementsAcknowledgements
This work was performed within the HiPerCap project The project receivesThis work was performed within the HiPerCap project. The project receives funding from the European Union Seventh Framework Programme (FP7/2007‐2013) under grant agreement no. 608555. The industrial partners who also financially support the project are gratefully acknowledgedfinancially support the project are gratefully acknowledged.
Ardi Hartono (NTNU) Rune Rennemo (NTNU) Solrun J Vevelstad (SINTEF MC) Inna Kim
ContributorsArdi Hartono (NTNU), Rune Rennemo (NTNU), Solrun J Vevelstad (SINTEF MC), Inna Kim(SINTEF MC), Hanna Knuutila (NTNU), Odd‐Gunnar Brakstad (SINTEF MC), Andrew Tobiesen (SINTEF MC), Geir Haugen (SINTEF MC)
PCCC‐3, Regina, Canada, 8th ‐11th September 2015 14
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