Published on April 25, 2014
- Call 1 project - Determination of water solubility limits in CO2 mixtures: Ensuring the safety of CO2 transport Stéphanie Foltran Norhidayah Suleiman Matthew Vosper Ke Jie Martyn Poliakoff Mike George UKCCSRC Biannual meeting - CCS in the Bigger Picture - Cambridge on 2-3 April 2014
Aim of our research 2 To establish the solubility limit of water in impure CO2 to ensure the safety of pipelines • For this presentation: ▫ Water solubility in CO2 + 5% N2 or in CO2 + 10% N2 at T = 40°C and P = 8 – 18 MPa • Nobody has made such measurements before
Karl Fischer titration Can detect µg of water Low temperature FT-IR spectroscopy Water highly absorbing in infrared Long standing experience in the Group with high-pressure vessel coupled to infrared spectroscopy Research Strategy: 2 independent methods 3
Background • Literature data on water solubility in pure CO2; • The presence of impurities changes the physico- chemical properties of CO2! 4 0 5 10 15 20 25 0 200 400 600 800 Pure CO2 2 % H2 7.5% H2 10% H2 ρ(kg/m3 ) P (MPa) 50 o C SANCHEZ-VICENTE, Y., DRAGE, T.C., POLIAKOFF, M., KE, J., GEORGE, M.W., Int. J. Greenh Gas Con, Vol.13, 2013, p.78. 2% of H2 in CO2 can reduce the molar density up to 25% in the critical region
FT-IR spectroscopic set-up 5 N2 CO2 Gas mixer IP: ISCO Pump F: Fluid S: Sample HJ: Heating Jacket EC: Equilibrium Cell
FTIR spectrum of CO2 + H2O 8 0 0.5 1 1.5 2 2.5 3 10002000300040005000 Absorbance Wave number (cm-1) ν1 + 2ν2 + ν3 ν2 2ν1 + ν3 CO2 H2O CO2 CO2 ν3 CO2 4ν2 + ν3 (ν1 + ν3) +(2ν2 + ν3)
9 FT-IR spectrum of H2O in CO2 at 25°C, 9 MPa and with 0.2µl of H2O FTIR spectrum of CO2 + H2O
0.1µl Procedure 10 0.2 0.3 0.4 0.5 0.6 1.31.4 1.5 Bending mode of H2O for different concentrations at T and P fixed ν2(H2O) Saturation quantity
11 Z. Wang et al. Fluid Phase Equilibria 338 (2013) 155– 163 uncertainty Saturation data Calibration data Our work: less than 4% In the literature with a similar method: 10% ! Uncertainty challenge
12 H2O concentration decreases by up to 59% with the addition of N2 Concentration of water in CO2 mixtures At = 40°C and P = 8 - 18 MPa in pure CO2 and in CO2 + (5-10%) N2 mixtures 3% of error compared with the literature
13 10% N2 lowers the solubility of the water in CO2 by up to 26% At = 40°C and P = 8 - 18 MPa in pure CO2 and in CO2 + (5-10%) N2 mixtures Mole fraction of water in CO2 mixtures
EC: Equilibrium cell SC: Secondary cell Solubility of water in impure CO2 using Karl Fischer titration 14
Equilibrium part 15 1. Pre-heater 2. Equilibrium cell 3. Secondary equilibrium cell + Filter 4. Sample loop
Conclusions • Development of an FT-IR method to study the solubility of water CO2 + impurities; • The presence of N2 lowers significantly the water solubility in CO2; • Design of a high-pressure rig coupled to a Karl Fischer. 16
Outlooks • Solubility of water in ▫ CO2 + H2 ▫ CO2 + O2 ▫ and CO2 + H2 +N2 • Reproduction of the FT-IR results using the Karl Fischer titrator 17
Acknowledgements • Prof. Martyn Poliakoff and Prof. Mike George • Dr. Ke Jie • Matthew Vosper • Norhidayah Suleiman • Dr. Maria-José Tenorio • Mark Guyler • Workshop: ▫ Richard Wilson ▫ Peter Fields • All the group 18 • UKCCSRC for funding this project
Thank you for your attention!
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