Impacts of impurities on thermophysical properties and dehydration requirements of CO2-rich systems in CCS - Luis Pereira at UKCCSRC Biannual Meeting, Cambridge, April 2014

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Technology

Published on April 24, 2014

Author: UKCCSRC

Source: slideshare.net

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Presentation given by Luis Pereira (on behalf of Antonin Chapoy) from Heriot-Watt University on "Impacts of impurities on thermophysical properties and dehydration requirements of CO2-rich systems in CCS" in the Effects of Impurities Technical Session at the UKCCSRC Biannual Meeting - CCS in the Bigger Picture - held in Cambridge on 2-3 April 2014

1 Impact of impurities on thermophysical properties and dehydration requirements of CO2-rich systems in CCS L. Pereira, M. Kapateh, A. Chapoy Centre for Gas Hydrate Research, Institute of Petroleum Engineering, Heriot-Watt University, Edinburgh EH14 4AS, UK UKCCSRC Biannual, 2-3 April, Cambridge

Outline • Introduction / Background • VLE / Phase Equilibria • Hydrate / dehydration • Viscosity / density • Frost Points • Conclusions / Future Work 2 UKCCSRC Biannual, 2-3 April, Cambridge

Background • 3 years project in collaboration with ENSMP started in 2012 • Main objective: developing a reliable thermodynamic package for CCS fluids • CO2 originating from capture processes is generally not pure and can contain impurities such as: – H2O, CH4, N2, H2, NyOx, H2S, SO2… • The main aim of the proposed project is to investigate the phase behaviour and properties of CO2-rich stream containing impurities • Phase behaviour of saline water and CO2-rich streams • Impurities in this project: – H2O, CH4, C2H6,C3H8, N2, H2, O2, Ar, CO, NyOx, H2S, SO2… 3 UKCCSRC Biannual, 2-3 April, Cambridge

Research Topics • Phase Equilibria (VLE, Phase Envelope) • Hydrates – Saturated (free brine) or dehydration • Solubility, water content, pH • Phase behaviour with glycols • Transport properties – Density, viscosity, speed of sound • Frost/ dry Ice • Interfacial Properties • Mercury content 4 UKCCSRC Biannual, 2-3 April, Cambridge

Type of Fluids investigated • From binary to multicomponent systems 5 Comp. MIX 1 MIX 2 MIX 3 MIX 4 MIX 5 MIX 6 CO2 95.64 89.83 69.99 49.93 95.97 69.99 Methane 0.6261 0 20.02 39.99 0 7.901 Ethane 0 0 6.612 3.510 0 7.015 Propane 0 0 2.58 1.530 0 4.968 n-Butane 0 0 0.3998 0.501 0 2.067 i-Butane 0 0 0.3997 0.499 0 2.049 n-Pentane 0 0 0 0.513 0 0 Nitrogen 1.41 5.05 0 3.524 2.028 6.009 Hydrogen 0.8175 0 0 0 0.605 0 Oxygen 0.08 3.07 0 0 0.783 0 Argon 1.21 2.05 0 0 0.611 0 CO 0.2127 0 0 0 0 0 Total 100 100 100 100 100 100 UKCCSRC Biannual, 2-3 April, Cambridge

Phase Equilibria – Vapour Liquid Equilibria • Between CO2 and contaminant and between contaminants • Data needed for EoS model ----> Engineering calculations • Saturation pressure of “typical” CCS stream for validation 6 UKCCSRC Biannual, 2-3 April, Cambridge

Why Measure VLE? • Lack of data for components expected in CCS stream -- > especially for toxic gases 7 CO2 CO N2 O2 Ar H2 NO CH4 C2H6 C3H8 NO2 SO2 H2S N2O CO2 CO N2 O2 Ar H2 NO CH4 C2H6 C3H8 NO2 SO2 H2S UKCCSRC Biannual, 2-3 April, Cambridge

What we have covered so far 8 CO2 CO N2 O2 Ar H2 NO CH4 C2H6 C3H8 NO2 SO2 H2S N2O CO2 NEW NEW NEW NEW NEW NEW [19- 36] [37 - 49] [47,50- 61] CD [62- 64]+CD NEW [141] CO [65- 70]+CD CR [67] [82- 83] NEW [79- 82] [84- 85] [84-88] ND NEW [89] NEW N2 [90- 93] [90] [94- 97] NEW DWA ND [99- 109] [100- 102] NEW O2 [90] ND ND CRYO CD [107- 108] ND [106- 109] ND [104- 105] Ar CRYO NEW CRYO [140] NEW ND NEW ND NEW H2 ND [110- 119] [111- 112, 120] [121- 123] ND NEW ND ND NO [124] ND ND [29] NEW ND ND CH4 DWA ND [99] [126- 131] NEW C2H6 DWA ND NEW [132- 134] NEW C3H8 ND [125] [136- 139] NEW NO2 CR ND ND SO2 ND ND H2S ND N2O UKCCSRC Biannual, 2-3 April, Cambridge

VLE Apparatus 9 Specifications – Ti Rig – 200 ml – Maximum working pressure: 200 bar – -30 °C < T < 120 °C Accuracy T : ± 0.1 °C P: ± 0.05 bar Phase samplings: ROLSI™ Schematic illustration of the cell used for VLE studies Magnetic Motor Temperature Probe PressureTransducer Capillary Sampler 2-wayvalve Cooling Jacket Cooling Fluid in/out Equilibrium Cell Window UKCCSRC Biannual, 2-3 April, Cambridge

0 1 2 3 4 5 6 7 0 0.2 0.4 0.6 0.8 1 P/MPa x1, y1 Typical Experimental / Modelling Results 10 kij =0 Tuned kij Vapour – Liquid Equilibria in the H2S + CO2 Binary System 0°C -15°C UKCCSRC Biannual, 2-3 April, Cambridge

Validation: Phase Envelope 11 Exp. and predicted Phase Envelope (Blue and Red Lines: PR-EoS with tuned kij; Dotted lines: PR-EoS with kij=0). UKCCSRC Biannual, 2-3 April, Cambridge

• Knowledge of the maximum allowable water content in CO2- rich fluids is critical for a safe transport of CO2 to storage sites – Hydrates, corrosion • Limited data are available on the phase behavior of CO2 in presence of hydrates – GPA RR80 and RR99 (also published in SPE) – Unfortunately the reliability of these studies has been recently questioned in a few papers (ex BRE: Hendrick et al., 2010) – Gap in data at low temperature (T<-20°C, Statoil: de Koeijer, 2010) – Effect of contaminants not evaluated 12 Dehydration Requirement UKCCSRC Biannual, 2-3 April, Cambridge

Dehydration – Lab Apparatus 13 -33.0 C NITROGEN CYLINDER CHILLED MIRROR HYGROMETER T PROBE P TRANSDUCER FLOW METER HEATED LINE EdgeTech DewMaster : - Can measure dew/frost point from -75 to 100 °C and up to 20 bar - Resolution 0.1 °C - Accuracy ±0.2 °C UKCCSRC Biannual, 2-3 April, Cambridge

Apparatus: Schematic TDLAS Set-up 14 UKCCSRC Biannual, 2-3 April, Cambridge

Dehydration Requirement • Typical Results for a saturated system (free water) 15 Exp. and predicted hydrate (sI) dissociation conditions for MIX 2 UKCCSRC Biannual, 2-3 April, Cambridge

Typical Experimental / Modelling Results 16 Water Content in pure CO2 and MIX 2 at 150 bar UKCCSRC Biannual, 2-3 April, Cambridge 0 500 1000 1500 2000 2500 -50 -40 -30 -20 -10 0 10 20 yw/ppm T/ °C CO2 (Chilled Mirror) CO2 (TDLAS) MIX 2 10% impurities (no H2S or SO2) ~ 20% reduction in water content (to pure CO2)

Density / Viscosity – Exp. Equipment 17 A schematic view of the viscosity and density experiments setup High temperature and pressure oscillating U-tube densitometer: Anton Paar DMA-HPM Cell: Working Pressure: Up to 20,000 psia (1400 bar) Working Temperature: -10 °C to 200 °C Material: U-shaped Hastelloy C-276 tube Temperature Variation: ±0.01 °C Oven: BINDER GmbH Working Temperature: -70 °C to 200 °C mPDS 2000V3 evaluation unit UKCCSRC Biannual, 2-3 April, Cambridge

Viscosity Results 18 0 50 100 150 200 250 300 350 0 25 50 75 100 125 150 Viscosity,η/µPa.s P / MPa 0 5 10 15 20 25 30 35 0 2 4 6 8 10 Viscosity,η/µPa.s P / MPa MIX 2 Viscosity – Modelling using modified CO2 1-fluid CSP model (), T = 243.15 K (), T = 253.15 K (), T = 273.15 K (), T = 283.15 K (), T = 298.15 K (), T = 323.15 K (), T = 373.15 K (), T = 423.15 K UKCCSRC Biannual, 2-3 April, Cambridge

Density Results 19 MIX 2 Density – Modelling using modified EoS with CO2 volume correction (), T = 273.26 K (), T = 283.31 K (), T = 298.39 K (), T = 323.48 K (), T = 373.54 K (), T = 423.43 K UKCCSRC Biannual, 2-3 April, Cambridge 0 250 500 750 1000 1250 0 25 50 75 100 125 150 Density,ρ/kg.m-3 P / MPa 0 10 20 30 40 50 60 70 80 90 100 110 1 2 3 4 Density,ρ/kg.m-3 P / MPa

Density 20 Density difference between pure CO2 and MIX 2 in the supercritical region (50°C) -200 -150 -100 -50 0 0 25 50 75 100 125 150 ρ/kg.m-3 P / MPa >35% reduction in density UKCCSRC Biannual, 2-3 April, Cambridge

Frost Point/ Dry ice • VSE of CO2-mixtures important issue – safety assessment of CO2 pipelines – possibility of solid or ‘dry ice’ discharge during an accidental release or rapid decompression • Removal of CO2 – A technique has been suggested based on frosting CO2 at low temperature and separating the CO2 solid from natural gas • No data were found for systems of interest in CCS. 21 UKCCSRC Biannual, 2-3 April, Cambridge

Frost Point/ Dry ice - Equipment 22 UKCCSRC Biannual, 2-3 April, Cambridge Cross-sectional view of the SETARAM BT 2.15 BT 2.15 Calorimeter Internal Block

Frost Point/ Dry ice - Results 23 UKCCSRC Biannual, 2-3 April, Cambridge Predicted (PR-EoS) and experimental phase diagram of CO2 1 10 100 1000 -80 -60 -40 -20 0 P/bar T/ °C Vapour Liquid Solid Ttr=-56.76 ± 0.1°C Ptr=5.12 ± 0.005 bar Span and Wagner Tt=-56.558 °C and Pt= 5.1795 bar

Frost Point/ Dry ice - Results 24 UKCCSRC Biannual, 2-3 April, Cambridge 0 20 40 60 80 100 120 140 160 180 200 -75 -55 -35 -15 5 25 P/bar T / °C Calorimeter measurements Isochoric measurements Bubble points Experimental and predicted frost points of MIX 2

Other Properties • CO2 solubility in brine and water in CO2 – Effect of impurities, water chemistry – Halite formation – IFT • CO2 – Glycols/aqueous glycol solution phase equilibria, i.e. Optimisation of glycol dehydration • Calorific properties (heat capacity) • Mercury 25

Conclusions • Filling the knowledge gaps • Practical implementations of results (parameters, tuned EoS)/models in a modelling package 26

Conclusions • New/unique range of experimental data – VLE for toxic gases – Hydrates in low water content (dehydration) – Transport Properties.... – Frost Point • Phase II of the project starting in October 2014 27

Acknowledgements 28

2929 Thank you for your attention Questions?

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Comments

Yelisa | 09/03/15
Well done to think of someihtng like that
Yelisa | 09/03/15
Well done to think of someihtng like that

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