Prediction of N O solubilities in alkanolamine solutions from density data 1 Ardi Hartono and Hallvard F. Svendsen 1 st Post Combustion Capture Conference Abu Dhabi, UAE, May 17-19, 011
Outline Introduction Experimental Part Density Measurement N O Solubility Measurement Excess Properties Molar Volume Henry s law constant Result and Modeling Conclusion and Future works
Introduction Physical CO solubility is important for a detailed thermodynamic modeling and design Expressed as the Henry law Constant Can not measure directly in Amine solution But can be inferred from the N O solubility via N O analogy 3 Kinetic Study 1 H H 1 = = k = k' E k k C D k' k g µ H CO CO CO freeam Thermodynamic MEA H NO = =γ H MEA w MEA * w HCO H CO H w CO CO H CO NO A g k' g HCO CfreeAm DA
Experimental Part Density Measurement Pycnometer Simple and easy Quite accurate (+/- 0.000 g) Can be used for elevated temperature Disadvantage : for viscous liquid Commercial (e.g. DMA 500) Simple and easy Very accurate (+/- 0.0000 g) Can be used for elevated temperature Compensate of liquid viscosity
N O Solubility Measurement Pressure Drop Measurement P vap measured as initial pressure Flexible in the Pressure Range H=P/C* Tounsi, et al. (005) Volume Drop Measurement Control the Mercury level Limited up to Atmospheric condition P vap as an ideal (Raoult s Law) H=P/C* 5 Hani, et al. (199)
N O Solubility Apparatus at NTNU laboratory Low Pressure Apparatus Hartono, et al. (00) Up to 0. MPa (abs) Up to middle range of CO loading Up to 90C
N O Solubility Apparatuses at NTNU laboratory () Moderate to High Pressure Up to 0 MPa Up to 150 C For very high loading of CO 7
Excess Properties Excess Molar Volume E V = V x1 V1 x V ( ) V E x M + x M x M x M = ρ ρ ρ 1 1 1 1 m 1 0 Excess Molar Volume of Aqueous MEA Solution 1.0 Density of Aqueous Solution of MEA -0.1 1.03-0. 1.0 R (mol cm -3 ) -0.3-0. ρ (g cm -3 ) 1.01 1 0 C -0.5 30 C 0 C -0. 50 C 0 C 70 C -0.7 0 0.1 0. 0.3 0. 0.5 0. 0.7 0. 0.9 1 Mass fraction, xw MEA (-) 0 C 0.99 30 C 0 C 50 C 0.9 0 C 70 C 0.97 0 0.1 0. 0.3 0. 0.5 0. 0.7 0. 0.9 1 Mass fraction, x MEA (-) Solid lines are developed from Maham, et al. (199)
Excess Henry s Law Constant E H = ln( H ) Φ ln( H ) Φ ln( H ) v i Φ i = vi m v 1 1 i = x i M ρ i i Nitta, et al. (1973) 9 Wang, et al. (199)
Results and Modeling H NO (kpa m 3 mol -1 ) 35 30 5 0 15 5 N O Solubility into pure H O Versteeg & van Swaaij (19) Yaghi & Houache (00) Jamal (00) Hartono et al (00) This work Versteeg & van Swaaij model Jamal model Mamun & Svendsen, 009 This model +/-5% Very good agreement up to 70C within +/- 5% Discrepancy at higher temperature Need to focus at higher temperature (High Pressure Apparatus!!) HO 3.3 HNO = exp 1. 197.5 log( T) 0.35 T + + T 0.5 3 3.5 00/T (K -1 )
N O Solubility into pure MEA H NO (kpa m 3 mol -1 ) 5.5 5.5 3.5 Wang, et al (199) Yaghi & Houache (00) Jiru & Eimer (0) Hartono (009) This work best fitted +/-5% Pure MEA H NO Our result showed consistently higher up to % However the best fitted gave +/-5% 59.9 = exp 3.95 ( T 99.0) 3.5.7..9 3 3.1 3. 3.3 3. 3.5 00/T (K -1 ) 11
N O Solubility into 30% MEA Solution 13 H NO (kpa m 3 mol -1 ) 1 11 9 7 Yaghi & Houache (00) Jiru & Eimer (0) Jamal (00) Li & Lai (1995) Hartono (009) This work best fitted +/-5% Our result from HP and LP seems to be in very good agreement However compared to the literature the discrepancy are bigger (up to +/-%) Only a few data for higher concentration 5 3.5..7..9 3 3.1 3. 3.3 3. 3.5 00/T (K -1 ) 1
N O Solubility into MEA Solution H NO (kpa m 3 mol -1 ) 1 1 0 C 5 C 30 C 0 C 50 C 0 C 70 C 0 C Black Blue Red Green Magenta Cyan Yellow Black (unfilled) The agreement among the data are reasonably good up to 30% But only data of Jiru & Eimer (0) behave differently At x MEA > 30% Only a few data were found and very big in discrepancy 0 0.1 0. 0.3 0. 0.5 0. 0.7 0. 0.9 1 Mass fraction, x MEA (-) Yaghi & Houache, 00 Jiru & Eimer, 0 Jamal, 00 + Li & Lai, 1995 13 Hartono, et al., 00 This work
Modeling Wang Model (Wang, et al., 199) E H = ln( H ) Φ ln( H ) Φ ln( H ) H E m 1 1 α ij i j ij = ( k + k t+ k t + k Φ ) j= i= i j = 0.5 α Φ Φ Λ 0.7 0. 0.5 0. Excess Henry Constant of Aqueous MEA Solution Wang, et al. (199) Yaghi & Houache (00) Tsai, et al. (000) No agreement among those authors due to the availability of the regressed experimental data 1 H E 0.3 0. 0.1 0 0 0.1 0. 0.3 0. 0.5 0. 0.7 0. 0.9 1 Φ i To calculate accurately, we need a full set of experimental data for the whole range of concentrations at different temperatures
Original of Wang Model (Wang, et al., 199) N O Solubility into MEA Solution (Wang Model (199)) H NO (kpa m 3 mol -1 ) 1 1 0 C 5 C 30 C 0 C 50 C 0 C 70 C 0 C Failure of Original Wang Model due to the limitation of the data that were regressed, i.e. only regressed up to 5 o C The Model can only predict up to 30 o C 0 0 0.1 0. 0.3 0. 0.5 0. 0.7 0. 0.9 1 Mass fraction, x MEA (-) 15
H NO (kpa m 3 mol -1 ) N O Solubility into MEA Solution (Yaghi & Houache (00)) 1 0 C 5 C 1 30 C 0 C 50 C 0 C 70 C 0 C The model were regressed with their own data up to 30% and 0C The given parameter showed the model overpredicted H NO Failed to model the whole range 0 0 0.1 0. 0.3 0. 0.5 0. 0.7 0. 0.9 1 Mass fraction, x MEA (-) 1
N O Solubility into MEA Solution (Tsai et al. (000)) H NO (kpa m 3 mol -1 ) 1 1 0 C 5 C 30 C 0 C 50 C 0 C 70 C 0 C Surprisingly this model gave the best estimation even thought the model was regressed only up to 3% and 0 C 0 0 0.1 0. 0.3 0. 0.5 0. 0.7 0. 0.9 1 Mass fraction, x MEA (-) 17
H NO model (kpa m 3 mol -1 ) 1 1 + Parity plot of N O Solubility into MEA Solution Yaghi & Houache, 00 Jiru & Eimer, 0 Jamal, 00 Li & Lai, 1995 Hartono, et al., 00 This work 0 C 5 C 30 C 0 C 50 C 0 C 70 C 0 C 1 1 H NO data (kpa m 3 mol -1 ) Black Blue Red Green Magenta Cyan Yellow Black (unfilled) 1
FACTS: The parameter of Tsai, et al., (00) gave the best representation of Wang Model for MEA But it still needs a laborious experiments of N O Solubility for different temperatures and concentrations The disagreement of among the data from different researchers of the N O solubility can go up to more than % We developed an empirical model based on an excess molar volume (i.e. density) Suggested new model: E H = ln( H ) Φ ln( H ) Φ ln( H ) H E m E ψ ( V ) 1 1 E V = ( k + k T + k x + k x ) x (1- x ) 1 3 19
H E E ψ ( V ) 0-0.1-0. Excess Molar Volume of Aqueous MEA Solution 0.7 0. 0.5 Excess Henry Constant of Aqueous MEA Solution Wang, et al. (199) Tsai, et al. (000) ψ=1 ψ=(1-φ i ) 0.5 R (mol cm -3 ) -0.3-0. H E 0. 0.3 0 0 C -0.5 30 C 0 C -0. 50 C 0 C 70 C -0.7 0 0.1 0. 0.3 0. 0.5 0. 0.7 0. 0.9 1 Mass fraction, xw MEA (-) Advantages : 0. 0.1 0 0 0.1 0. 0.3 0. 0.5 0. 0.7 0. 0.9 1 Φ i The availability of density data and the agreement among the researchers are very good Only Need N O Solubility data at pure solvents (less laborious works)
H E E ψ ( V ) ψ = 1 N O Solubility into MEA Solution H NO (kpa m 3 mol -1 ) 1 1 0 C 5 C 30 C 0 C 50 C 0 C 70 C 0 C The model represents the data well up up to 5% But it over predicted at higher concentrations and temperatures Indicates that it needs correction at higher (T,C) 0 0.1 0. 0.3 0. 0.5 0. 0.7 0. 0.9 1 Mass fraction, x MEA (-) 1
H E E ψ ( V ) ψ = 1 Φ N O Solubility into MEA Solution H NO (kpa m 3 mol -1 ) 1 1 0 C 5 C 30 C 0 C 50 C 0 C 70 C 0 C The model is in very good agreement with the data But to validate the model H NO at very high concentration is needed 0 0.1 0. 0.3 0. 0.5 0. 0.7 0. 0.9 1 Mass fraction, x MEA (-)
H NO model (kpa m 3 mol -1 ) Parity plot of N O Solubility into MEA Solution 1 Yaghi & Houache, 00 Jiru & Eimer, 0 1 Jamal, 00 + Li & Lai, 1995 Hartono, et al., 00 This work 0 C Black 5 C Blue 30 C Red 0 C Green 50 C Magenta 0 C Cyan 70 C Yellow 0 C Black (unfilled) 1 1 H NO data (kpa m 3 mol -1 ) 3
DEA+H O N O Solubility into Aqueous DEA Solution Parity plot of N O Solubility into DEA Solution H NO (kpa m 3 mol -1 ) 9 7 5 0 C 5 C 30 C 0 C 50 C 0 C H NO model (kpa m 3 mol -1 ) 9 7 5 3 0 0.1 0. 0.3 0. 0.5 0. 0.7 0. 0.9 1 Mass fraction, x DEA (-) Versteeg & Oyevar (199) Yaghi & Houache (00) +/-5% 3 3 5 7 9 H NO data (kpa m 3 mol -1 )
MDEA+H O H NO (kpa m 3 mol -1 ) N O Solubility into Aqueous MDEA Solution 0 C 9 5 C 35 C 5 C 7 0 C 5 3 1 0 0 0.1 0. 0.3 0. 0.5 0. 0.7 0. 0.9 1 Mass fraction, x MDEA (-) H NO model (kpa m 3 mol -1 ) 9 7 5 3 Parity plot of N O Solubility into MDEA Solution 5 C 0 C +/-5% 1 1 3 5 7 9 H NO data (kpa m 3 mol -1 ) 0 C 5 C 35 C 5
DIPA+H O H NO (kpa m 3 mol -1 ) N O Solubility into Aqueous DIPA Solution 1 19.9 C 1.9 C 3.9 C.9 C 59.9 C 0 0 0.1 0. 0.3 0. 0.5 0. 0.7 0. 0.9 1 Mass fraction, x DIPA (-) H NO model (kpa m 3 mol -1 ) Parity plot of N O Solubility into DIPA Solution 9 7 5 19.9 C.9 C 3.9 C.9 C 59.9 C 3 3 5 7 9 H NO data (kpa m 3 mol -1 )
AEEA+H O N O Solubility into Aqueous AEEA Solution Parity plot of N O Solubility into AEEA Solution H NO (kpa m 3 mol -1 ) 1 5 C 1 30 C 0 C 1 50 C 0 C 70 C 0 0 0.1 0. 0.3 0. 0.5 0. 0.7 0. 0.9 1 Mass fraction, x AEEA (-) H NO model (kpa m 3 mol -1 ) 1 1 1 1 H NO data (kpa m 3 mol -1 ) 5 C 30 C 0 C 50 C 0 C 70 C +/-5% 7
MEA+MDEA+H O From the binary data of MEA+H O and MDEA+H O, the ternary (MEA+MDEA+H O) system can be predicted : H NO (kpa m 3 mol -1 ) 7.5 7.5 5.5 5.5 3.5 N O Solubility into ternary system (MEA+MDEA+H O) 3 3.05 3.1 3.15 3. 3.5 3.3 3.35 3. 3.5 00/T (K -1 ) 30%MEA+0%MDEA %MEA+%MDEA 1%MEA+1%MDEA 1%MEA+1%MDEA %MEA+%MDEA 0%MEA+30%MDEA H NO model (kpa m 3 mol -1 ) Parity plot of N O Solubility into ternary system (MEA+MDEA+HO) 7.5 7.5 5.5 5.5 %MEA+%MDEA 0%MEA+30%MDEA +/-5%.5 5 5.5.5 7 7.5 H NO data (kpa m 3 mol -1 ) 30%MEA+0%MDEA %MEA+%MDEA 1%MEA+1%MDEA 1%MEA+1%MDEA
Conclusions The developed new model represented the data very well for alkanolamines Only needs density data and solubility of N O for pure solvent The correction factor ψ (may) need to be adjusted when data for higher concentrations are available Future Works More data to validate for the ternary amine system Model ability to predict loaded system Expand the model for amine+h O system 9
Acknowledgement The financial support from the CCERT project is greatly appreciated. The CCERT project is supported by: the Research Council of Norway (NFR 7) Shell Technology Norway AS Metso Automation Det Norske Veritas (DNV) AS Statoil AS 30
Thank you for your attention 31