2nd Post Combustion Capture Conference (PCCC2) 17-20 September, 2013, Bergen, Norway

Muhammad Waseem Arshad

Assoc. Prof. Kaj Thomsen (DTU) Assoc. Prof. Nicolas von Solms (DTU)

Asst. Prof. Philip L. Fosbøl (DTU) Prof. Hallvard Fjøsne Svendsen (NTNU)

Vapor-Liquid Equilibrium of CO2 with Aqueous Solutions of DEEA, MAPA and Their Mixtures

Outline

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• Introduction • Measurement Techniques • Experimental Work • Results Heat of absorption (sample) VLE of CO2

• Main Conclusions

Amine-based Capture Solvents

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• Alkanolamines/ Amines Primary (e.g. MEA) Secondary (e.g. DEA) Tertiary (e.g. TEA, MDEA)

• Sterically hindered amines (e.g. AMP)

• Cyclic Amines (e.g. Piperazine)

• Mixed Amines

Phase Change Liquid-Liquid Solvents

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DMXTM Process (demixing solvents) IFPEN France

Raynal, L.; Pascal, A.; Bouillon, P.-A.; Gomez, A.; le Febvre de Nailly, M.; Jacquin, M.; Kittel, J.; di Lella, A.; Mougin, P.; Trapy, J. Energy Procedia 2011, 4, 779-786

Upper light phase lean in CO2

Lower heavy phase rich in CO2

Low liquid circulation rate in the stripper

Reboiler duty 2.1 GJ/ ton CO2 compared to 3.7 GJ/ ton CO2

for 30 mass % MEA

Introduction

2-(diethylamino)ethanol (DEEA)

• Low heat of absorption/ reaction (bicarbonate) • Low heat requirement for regeneration • High loading capacity • Low reaction kinetics

3-(methylamino)propylamine (MAPA)

• Fast reaction kinetics • High heat of absorption/ reaction (carbamate) • High heat requirement for regeneration

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CO2 lean phase

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CO2 rich phase

Phase change solvent

DEEA-MAPA-CO2-H2O system give liquid-liquid split with lower phase rich in CO2 and upper phase lean in CO2

- Phase change solvents has potetial for:

• Low circulation rate in the desorber

• Smaller size of desorber (low capital cost)

• Improved energy efficiency

Introduction

Introduction

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Process Flow Diagram Conventional

Introduction

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Process Flow Diagram Phase Change Solvents

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Xu, Q.; Rochelle, G. T. Energy Procedia 2011, 4, 117-124

• Equilibrium Cells (EC) Static method Dynamic (circulation) method

• Calorimeter and Autoclave as EC

Measurement Techniques

1, 2L jacketed reactor 2a & 2b, CO2 storage cylinders 3, CO2 mass flow controller 4, Amine solution feed bottle 5, Vaccuum pump

Calorimeter Model CPA-122 ChemiSens AB, Sweden

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4

2b

1

CO2

2a

Control DeviceVRC200

FCO2

PP

P

P

P

5

T

Control Device

Thermostat

WP TN

T TP

n

3

To air

Vacuum

Experimental Setup

Arshad, M. W.; Fosbøl, P. L.; von Solms, N.; Svendsen, H. F.; Thomsen, K. J. Chem. Eng. Data. 2013, 58, 1974-1988

• Moles of CO2 (Peng-Robinson EOS) • Power curve (Integration) • Amine concentration (known)

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Experimental Method

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Experimental Method

Complete log for 1 M MAPA at 80 oC For a given CO2 feeding

Tested Concentrations

• 30 mass % MEA

• 5M DEEA

• 2M and 1M MAPA

• 5M DEEA + 2M MAPA (phase split)

• 5M DEEA + 1M MAPA (phase split) Temperature = 40 oC (absorption), 80 oC and 120 oC (desorption) Total Pressure = ~6 bar

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Sample Results: Heat of Absorption 30 mass % MEA

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Kim, I. Heat of reaction and VLE of post combustion CO2 absorbents. PhD Thesis. Norwegian University of Science and Technology, Trondheim, Norway, 2009 Arshad, M. W.; Fosbøl, P. L.; von Solms, N.; Svendsen, H. F.; Thomsen, K. J. Chem. Eng. Data. 2013, 58, 1974-1988

Sample Results: Heat of Absorption

Overall comparison of all systems at Absorption & Desorption conditions

15 Arshad, M. W.; Fosbøl, P. L.; von Solms, N.; Svendsen, H. F.; Thomsen, K. J. Chem. Eng. Data. 2013, 58, 1974-1988

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Results: VLE of CO2 in 30 mass % MEA

Lee, J. I.; Otto, F. D.; Mather A. E. J. appl. Chem. Biotechnol. 1976, 26, 541-549. Shen, K.-P.; Li, M.-H. J. Chem. Eng. Data 1992, 37, 96-100. Jou, F.-Y.; Mather, A. E.; Otto, F. D. Can. J. Chem. Eng. 1995, 73, 140-147. Ma’mun, S.; Nilsen, R.; Svendsen, H. F. J. Chem. Eng. Data 2005, 50, 630-634. Aronu, U. E.; Gondal, S.; Hessen, E. T.; Haug-Warberg, T.; Hartono, A.; Hoff, K. A.; Svendsen, H. F. Chem. Eng. Sci. 2011, 66, 6393-6406. Xu, Q.; Rochelle, G. T. Energy Procedia 2011, 4, 117-124.

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Results: VLE of CO2 in 5M DEEA

PCO2 vs CO2 loading PTotal vs CO2 loading

Monteiro, J.G.M.-S., Pinto, D.D.D., Hartono, A., Svendsen, H.F. Final report on liquid/ liquid solvents characterization. EU FP-7, iCap project. Deliverable number D 1.3.2, 2011

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Results: VLE of CO2 in 2M MAPA

Monteiro, J.G.M.-S., Pinto, D.D.D., Hartono, A., Svendsen, H.F. Final report on liquid/ liquid solvents characterization. EU FP-7, iCap project. Deliverable number D 1.3.2, 2011

PCO2 vs CO2 loading PTotal vs CO2 loading

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Results: VLE of CO2 in 1M MAPA

PTotal and PCO2 VS CO2 loading

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Results: Phase change amine mixtures

5M DEEA + 2M MAPA (5D2M) 5M DEEA + 1M MAPA (5D1M)

PTotal and PCO2 VS CO2 loading

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Results: Overall Comparison

Absorption conditions Desorption conditions

PCO2 VS CO2 loading

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Results: Phase change amine mixtures

Two liquid phases only in certain CO2 loading range

Arshad, M. W.; Fosbøl, P. L.; von Solms, N.; Svendsen, H. F.; Thomsen, K. J. Chem. Eng. Data. 2013, 58, 1974-1988

Main Conclusions • Experimental method is validated – 30 mass % MEA

• Total pressure and CO2 solubility were measured in the temperature range 40-120 oC

• Experimental setup and method is very useful in measuring both heat of absorption and VLE at the time

• The measured data is of good quality

• Measured data is useful in thermodynamic modelling

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Acknowledgement

• This project is funded by European Commission under the 7th Framework Program (Grant no. 241393) through the iCap project

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Thank You!