HiP CHiPerCap Hi hHigh PfPerformance CtCapture...HiP CHiPerCap‐Hi hHigh PfPerformance CtCapture FP7 Grant agreement n 608555 Sterically hindered alkanolamines as strong bicarbonate

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


[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


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


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


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.]


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]


(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


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 %


the velocity of flooding4. compression train is not included

Energy consumptionEnergy consumption

30% MEA

(HS#1/HS#2)


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


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)


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HiP CHiPerCap Hi hHigh PfPerformance CtCapture...HiP CHiPerCap‐Hi hHigh PfPerformance CtCapture FP7 Grant agreement n 608555 Sterically hindered alkanolamines as strong bicarbonate