Thomsen, Kaj

Waseem Arshad, Muhammad

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Downloaded from orbit.dtu.dk on: Dec 18, 2017Freezing Point Depression of Aqueous Solutions of DEEA, MAPA and DEEA-MAPAwith and without CO2 LoadingArshad, Muhammad Waseem; Thomsen, KajPublication date:2011Link back to DTU OrbitCitation (APA):Waseem Arshad, M., & Thomsen, K. (2011). Freezing Point Depression of Aqueous Solutions of DEEA, MAPAand DEEA-MAPA with and without CO2 Loading [Sound/Visual production (digital)]. 2nd ICEPE : InternationalConference on Energy Process Engineering, Frankfurt am Main, 01/01/2011Freezing Point Depression of Aqueous Solutions of DEEA, MAPA and DEEA-MAPA with and without CO2 Loading Muhammad Waseem ArshadSupervisor: Assoc. Prof. Kaj Thomsen2nd ICEPE, 20-22 June, 2011PRESENTATION OUTLINE2nd ICEPE, 20-22 June, 2011 Introduction Materials Reaction Mechanism Experimental Method Results Conclusions Future Work2INTRODUCTION2nd ICEPE, 20-22 June, 2011 3Freezing Point Depression:The phenomenon in which the freezing point of a Liquid(Solvent) is depressed when another compound is added in it.This means that the solution has lower freezing than the puresolvent.Why we need Freezing Point Depression Data??? We want to model H2O-DEEA-MAPA-CO2 system Water activity is a key parameter for the amount of waterevaporated in the desorber Low water activity means less evaporation of water in thedesorber and low energy consumption during solventregeneration Water activity can be determined very accurately fromFreezing point dataMATERIALS2nd ICEPE, 20-22 June, 2011 2-(Diethylamino)-ethanol   OR   DEEA   (99%)Clear liquid with light yellow colourFreezing point = -70 oCBoiling point = 163 oC pH = 11.5 at 100 g/l at 20 oC Completely soluble in water 3-(Methylamino)propylamine   OR   MAPA   (97-98%)Clear and colourless liquidFreezing point = -72 oCBoiling point = 140 oCpH = 13.5 at 100 g/l at 20 oCCompletely soluble in water4REACTION MECHANISM2nd ICEPE, 20-22 June, 20112-(Diethylamino)-ethanol   OR   DEEA52 52 22           DEEA  R C HR CH CH OHR R N= −′ = −′∴ =( )2 2 2 2 3                   1R R N H O CO R R N H HCO+ −′ ′+ + → +( )( )2 32 2 3                                                   2                                           3CO OH HCOCO H O HCO H− −− ++ ↔+ ↔ +Following reactions may also take place simultaneouslyBase catalytic effect on hydration of CO2[Ref] Vaidya, P. D.; Kenig, E. Y. A Study on CO2 Absorption Kinetics by Aqueous Solutions of N,N-Diethylethanolamine and N-Ethylethanolamine. Chem. Eng. Technol. 2009, 32, No. 4, 556-563( )( )2 2 22 2 2 3                                     1                    1R R N CO R R NCOO aR R NCOO H O R R N H HCO b−− + −′ ′+ ↔′ ′+ → +Zwitterion mechanismREACTION MECHANISM2nd ICEPE, 20-22 June, 20113-(Methylamino)propylamine   OR   MAPA6( )( )2 2 22 32 3 2Protonation:                                           1                                           2  2                                H NRR NH H H NRR NHH NRR NH H H NRR NHH NRR NH H H NRR NH+ ++ ++ + ++ ↔′ ′+ ↔′ ′+ ↔′ ′ ( )( )( )( )2 2 22 22 22      3Carbamate:                            4                           5  2    2            6Protonated Carbamate:H NRR NH CO H NRR NCOO HH NRR NH CO OOCHNRR NH HH NRR NH CO OOCHNRR NCOO HH− +− +− − ++ ↔ +′ ′+ ↔ +′ ′+ ↔ +′ ′( )( )32                              7                            8NRR NCOO H H NRR NCOOOOCHNRR NH H OOCHNRR NH− + + −− + − ++ ↔′ ′+ ↔′ ′3 6 32     and        MAPA  R C H R CHH NRR NH′= − = −′∴ =8 Possible species of MAPAEXPERIMENTAL METHODA, Thermostatic bath with ethanol B, Cooling jacket C, Sample glass with magneticstirrer D, Rubber stopper with sampleglass lid E, Device for manual stirring F, Controlled temperature ethanolbath with magnetic stirrer G, Pt100 Thermometer H, Data acquisition unit 2nd ICEPE, 20-22 June, 2011Experimental Setup[Ref] Fosbøl, P. L.; Pedersen, M. G.; Thomsen, K. Freezing Point Depressions of Aqueous MEA, MDEA, and MEA-MDEA Measured with a New Apparatus. J. Chem. & Eng. Data 2010, Special Issue: John M. Prausnitz Festschrift7EXPERIMENTAL METHOD2nd ICEPE, 20-22 June, 2011[Ref] Fosbøl, P. L.; Pedersen, M. G.; Thomsen, K. Freezing Point Depressions of Aqueous MEA, MDEA, and MEA-MDEA Measured with a New Apparatus. J. Chem. & Eng. Data 2010, Special Issue: John M. Prausnitz FestschriftMeasured Freezing PointHeat of CrystallisationCrystallisation8RESULTS2nd ICEPE, 20-22 June, 20112452502552602652702750 2 4 6 8 10 12Freezing Temperature   (K)Solvent Molality   (mole / kg water)DEEAMAPAAqueous solutions of DEEA and MAPA9RESULTS2nd ICEPE, 20-22 June, 20112452502552602652702750 10 20 30 40 50 60Freezing Temperature   (K)Solvent Mass PercentDEEADEEA/MAPA 5:1DEEA/MAPA 3:1DEEA/MAPA 1:1DEEA/MAPA 1:3DEEA/MAPA 1:5MAPAAqueous solutions of DEEA-MAPA with different molar ratios10RESULTS2nd ICEPE, 20-22 June, 2011Aqueous solutions of MAPA loaded with CO2112562582602622642662682702720 0,2 0,4 0,6 0,8 1 1,2 1,4 1,6 1,8Freezing Temperature  (K)CO2 Loading   (mol CO2 / mol MAPA)10% MAPA20% MAPA27% MAPARESULTS2nd ICEPE, 20-22 June, 2011Aqueous solutions of DEEA loaded with CO2122652662672682692702712720 0,2 0,4 0,6 0,8 1Freezing Temperature  (K)CO2 Loading (mol CO2 / mol DEEA)12% DEEA20% DEEAWork in Progress for 30% and 35% DEEA solutions CONCLUSIONS2nd ICEPE, 20-22 June, 2011 Freezing point depression (FPD) are measured for H2O-DEEAand H2O-MAPA and also for H2O-DEEA-MAPA for different molarratios of DEEA/MAPA [Data point = 76] FPD are measured for H2O-DEEA-CO2 and H2O-MAPA-CO2systems at different CO2 loading [Data points = 57] Measured freezing point data illustrates that the MAPA-waterinteraction is stronger than DEEA-water interaction The measured data can be used for modeling CO2 absorption/desorption system when aqueous blend of DEEA/MAPA is used13FUTURE WORK2nd ICEPE, 20-22 June, 2011 Measurement of FPD for 30% and 35% DEEA solutions withdifferent CO2 loadings Measurement of freezing points For aqueous solutions of DEEA-MAPA with different molar ratios loaded with CO2 Development of correlations for the freezing points as afunction of the solution composition Thermodynamic modeling of H2O-DEEA-MAPA-CO2 system usingExtended UNIQUAC model14THANK YOU FOR YOUR ATTENTIONQUESTIONS ?????2nd ICEPE, 20-22 June, 2011 15

Freezing Point Depression of Aqueous Solutions of DEEA, MAPA and DEEA-MAPA with and without CO2 Loading

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Freezing Point Depression of Aqueous Solutions of DEEA, MAPA and DEEA-MAPA with and without CO2 Loading

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