vapor-liquid equilibrium of co 2 with aqueous solutions of deea, … pdfs/4b_4... · 2013. 9....
TRANSCRIPT
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
2
• Introduction • Measurement Techniques • Experimental Work • Results Heat of absorption (sample) VLE of CO2
• Main Conclusions
Amine-based Capture Solvents
3
• 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
4
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
5
CO2 lean phase
6
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
9
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
10
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)
11
Experimental Method
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
13
Sample Results: Heat of Absorption 30 mass % MEA
14
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
16
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.
17
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
18
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
20
Results: Phase change amine mixtures
5M DEEA + 2M MAPA (5D2M) 5M DEEA + 1M MAPA (5D1M)
PTotal and PCO2 VS CO2 loading
22
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
23
Acknowledgement
• This project is funded by European Commission under the 7th Framework Program (Grant no. 241393) through the iCap project
24