N O solubility at high amine concentration and validation of N O Analogy Ardi Hartono, Emmanuel, O. Mba and Hallvard F. Svendsen The 6 th Trondheim CO Capture, Transport and Storage Conference Trondheim, Norway, June 14-16, 011 1
Outline Introduction Drawbacks and Aims Experimental Section Chemicals Used Solubility Apparatus Results and Discussion N O Analogy with H O N O Analogy with Neutralized Amine system Conclusion and Future works
Introduction Physical CO solubility is important for detailed thermodynamic modeling and design Expressed as the Henry s law Constant Can not measure directly in Amine solution But can be inferred from the N O solubility via N O analogy HO H Am Am CO HCO = H NO HO H NO N O Analogy (Versteeg & van Swaiij, 1988) H H HO NO HO CO 40 = 3.04 exp T 3
Drawbacks : N O Analogy was challenged: Not valid over large range of concentrations (Pawlak and Zarzycki, 00) Valid for amine concentration less than 30 wt% (Hutenhius, et al.,008) Aims : to measure the N O solubility at high amine concentrations and to test the N O analogy 4
Experimental Section 5
Chemicals used CO gas (purity 99.999 mol %, from YARA-PRAXAIR) N O gas (purity 99.99 mol %, from YARA-PRAXAIR) N gas (purity 99.6 mol %, from YARA-PRAXAIR) H SO 4 (purity 95-97% from SIGMA-ALDRICH) MDEA (purity 99mass%, from SIGMA-ALDRICH) De-ionised water was used as solvent throughout the experiment 6
Apparatus used 1. Low Pressure Apparatus Up to bar (abs) Up to middle range of CO loading Up to 90C 7 Hartono, et al. (008)
. Moderate/High Pressure Apparatus Up to 6 bar Up to 00 C 8 Higher CO loading Up to 60 bar Up to 50 C
N O and CO solubility was measured: 1. Water. Neutralized amine system with equinormal amount of amine and H SO 4 MDEA 50wt% +. M H SO 4 MDEA 70wt% + 3.1 M H SO 4 9
Results and discussion 10
Comparing N O solubility in H O with literature H NO (kpa m 3 mol -1 ) 35 30 5 0 15 10 Versteeg & van Swaaij (1988) Yaghi & Houache (00) Jamal (00) Hartono et al (008) 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 New high pressure apparatus gave certainty at higher temperature 5 11 0.6.8 3 3. 3.4 3.6 1000/T (K -1 ) HO 14905.5 HNO = exp 700.65 16.4 log( T) 0.38 T + + T AARD = 4%
Comparing CO solubility in H O with literature H CO (kpa m 3 mol -1 ) 0 18 16 14 1 10 8 6 Versteeg & van Swaaij (1988) Jamal (00) Hartono, et al., (008) This work Versteeg & van Swaaij model Jamal model Mamun & Svendsen, 009 Edward, et al.,1978 This model +/-5% Very good agreement up to 70C within +/- 5% New data for higher temperature 4 1 0.6.8 3 3. 3.4 3.6 1000/T (K -1 ) HO 078. HCO = exp 1.73 40.9 log( T) 0.09 T + + T AARD = 3%
Comparing the obtained N O analogy for water with literature C 1 = [H NO-HO /H CO-HO ].5 1.5 Versteeg & van Swaaij (1988) Jamal (00) Ma`mun & Svendsen (009) This work +/-5% Very good agreement up to 70C within +/- 5% Discrepancy at higher temperature We provide a new correlation for N O Analogy for a wider range of temperature 1 0 0 40 60 80 100 10 140 Temperature ( C) 13
Comparing the obtained N O analogy from Neutralized Solution.5 Versteeg & van Swaaij (1988) Jamal (00) Ma`mun & Svendsen (009) Very good agreement up to 70C within +/- 5% C 1 = [H NO-HO /H CO-HO ] 1.5 MDEA 50%+.M H SO 4 MDEA 70%+3.1M H SO 4 MEA 30%+.55M H SO 4 (Hartono, 009) This work +/-5% The neutralized solution follows the the N O analogy from water reasonably well Still need to work more at higher temperature (High Pressure Apparatus!!) 1 0 0 40 60 80 100 10 140 Temperature ( C) 14
Conclusions The experimental procedure and apparatus was validated and the results obtained are consistent with literature data up to 70C NO Analogy was found to be valid even at high amine concentrations (50 wt% and 70 wt%) We provide a new correlation for the N O analogy Future Work More work needed to measure the Henry s law constant at higher concentrations of amine and higher temperatures 15
Acknowledgement The financial support from the CCERT project is greatly appreciated. The CCERT project is supported by: the Research Council of Norway (NFR 18607) Shell Technology Norway AS Metso Automation Det Norske Veritas (DNV) AS Statoil AS 16
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