Published on April 24, 2014
Vapour-Liquid and Solid-Vapour-Liquid Equilibria of the System (CO2 + H2) at Temperatures Between (218 and 303) K and at Pressures up to 15 MPa David Vega-Maza University of Aberdeen Martin Trusler Niall R McGlashan Imperial College London 1
2 Scope Impact of Phase behaviour Apparatus VLE results SVLE results Conclusions
3 Scope Post-combustion capture. Oxy-combustion capture Pre-combustion capture Natural gas reforming Coal gasification Integrated Gasification Combined Cycle Ca looping Chemical looping Adsorption • Physical Absorbents • Membranes • Cryogenic Separation SEPARATION
4 Scope Pre-combustion CO2 capture offers an attractive route to decarbonising coal-fired electricity production Low-temperature physical separation of the CO2 may offer significant cost savings compared with traditional amine-based absorption processes Costain’s Next Generation Capture Technology (NGCT) concept embodies these ideas in a practical process
6 Impact of Phase behaviour NGCT process modelling requires precise VLE data for CO2-rich synthesis gas at low temperatures and high pressures Also require SVLE data to determine the lower operating temperature locus to avoid solids formation VLE of CO2 + H2 + impurities moderately well known but much of the data are old and there are some significant gaps – hence this new study
7 Apparatus Static apparatus with on-line sampling and GC analysis Ranges: 193 ≤ T/K ≤ 473 and 0.5 ≤ p/MPa ≤ 20 Absolute calibration with pure gases by means of internal GSV with sample loops under temperature and pressure control Process safety considered carefully
8 Apparatus Static apparatus with on-line sampling and GC analysis Ranges: 193 ≤ T/K ≤ 473 and 0.5 ≤ p/MPa ≤ 20 Absolute calibration with pure gases by means of internal GSV with sample loops under temperature and pressure control Process safety considered carefully
11 Apparatus 193 K < T < 473 K p < 20 MPa V = 0.14 dm3
12 VLE results
13 p-x-y diagram on H2 + CO2 system at -55 ⁰C, where x represents the molar composition of H2 in the liquid phase and y represents the molar composition of H2 in the vapour phase. Symbols: y -this work-; x –this work-; Tsang et al.  ; Spano et al.  1. C.Y. Tsang, W.B. Streett. Chem. Eng. Sci. 36 (1981) 993-1000 2. J.O. Spano, C.K. Heck, P.L. Barrick. J. Chem. Eng. Data 13 (2) (1968) 168-171 p-x diagram on H2 + CO2 system at -55 ⁰C, where x represents the molar composition of H2 in the liquid. Symbols: x –this work-; – – Tsang et al.  ; – – Spano et al.  1. C.Y. Tsang, W.B. Streett. Chem. Eng. Sci. 36 (1981) 993-1000 2. J.O. Spano, C.K. Heck, P.L. Barrick. J. Chem. Eng. Data 13 (2) (1968) 168-171 0 40 80 120 160 0 0.2 0.4 0.6 0.8 1 p/bar x or y 0 40 80 120 160 0 0.01 0.02 0.03 0.04 p/bar x VLE results
14 VLE results
15 SVLE results
16 SVLE results SVLE locus determined from p-T behaviour during cooling ramps Allowance for sub-cooling prior to freezing SVLE locus modelled with EoS for pure solid CO2 + GERG-2008 EoS for (CO2 + H2) in the gas phase, evaluated at the experimental temperature and vapour-phase composition
17 Conclusions VLE and SVLE data measured for (CO2 + H2) VLE results in good agreement with the available Elementary modelling completed; GERG-2008 mixture model planned for CO2 with impurities Further measurement on (CO2 + CO), (CO2 + CH4) and (CO2 + H2 + 100 ppm H2S) Acknowledgement We are pleased to acknowledge financial support for this work provided by Costain Energy & Process and the Energy Technology Institute
VLE and SVLE of the System (CO2 + H2) at Temperatures Between (218 and 303) K and at Pressures up to 15 MPa Thank You David Vega-Maza University of Aberdeen Martin Trusler Niall R McGlashan Imperial College London 18
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