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Fluid Phase Measurement Using Optical, Microfluidic and Nanofluidic Methods

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Fluid Phase Measurement Using Optical, Microfluidic and Nanofluidic Methods Fluid Phase Measurement using Optical, Microfluidic and Nanofluidic Methods by Bo Bao A thesis submitted in conformity with the requirements for the degree of Doctor of Philosophy Mechanical & Industrial Engineering University of Toronto © Copyright by Bo Bao 2016 Fluid Phase Measurement using Optical, Microfluidic and Nanofluidic Methods Bo Bao Doctor of Philosophy Mechanical & Industrial Engineering University of Toronto 2016 Abstract Understanding fluid phase behavior is essential to a wide range of applications, including oil and gas recovery, chemical reactor engineering, transport and storage of natural gas and carbon dioxide, and supercritical fluid processing and extraction. In this thesis, novel experimental methods – optical, microfluidic and nanofluidic - are developed to measure and understand fluid phase behaviors for carbon dioxide transport/storage and shale gas/oil production. (i) Optical thin-film interference based bubble and dew point sensor probe: The sensor probe within a small pressure-volume-temperature (PVT) system offers accurate (< 5% error) and responsive measurement (1-to-2 orders faster than the conventional method) of bubble and dew point of both pure fluids and mixtures up to 80 oC and 10 MPa. This approach also allows in situ measurement of the thickness of condensed liquid film to 1 µm accuracy. (ii) Refractive index based optical fiber sensor: This approach takes advantage of the sharp refractive index difference between different phases. The optical fiber successfully distinguishes supercritical CO2 and brine at sequestration pressure and temperature conditions. In addition, the CO2-saturated brine is detectable relative to unsaturated brine – a minute refractive index difference. (iii) Multiplexed microfluidic-based phase diagram mapping: Demonstrated here is the direct measurement of the ii full Pressure-Temperature phase diagram with 10,000 microwells. The method is tested with a pure fluid and a fluid mixture. Liquid, vapor and supercritical regions are clearly differentiated, and the critical point is measured within 1.2% error on a single chip. This method provides 100- fold improvement in measurement speed over conventional methods. (iv) Nanofluidics-based measurement of bubble nucleation and growth in nanochannels: A nanofluidic platform is developed to investigate vapor bubble nucleation and growth in a pure hydrocarbon confined in sub-100-nm channels. Measured nucleation conditions in the nanochannels are compared with those predicted from the nucleation theory. In addition, different types of bubble growth dynamics are observed and analyzed. Collectively these contributions leverage optics and microfluidics to develop fast and accurate fluid phase measurement methods, and leverage nanofluidics to study the unique effects of nanoconfinement on fluid phase behavior. iii Acknowledgments It is a great joy for me to express my appreciation to all of you who have supported me academically or spiritually during my PhD journey. Foremost, I would like to express my deep and sincere gratitude to my academic supervisor Professor David Sinton for his incalculable guidance and support to my PhD study and research. It is his intelligence, enthusiasm, patience, encouragement and profound knowledge that helped me achieving the honorable degree. Thank you to my supervisor. Also, I would like to thank all my thesis committee: Professor Anthony Sinclair, Professor Markus Bussmann and Professor Nikos Varotsis, for their insightful comments and suggestions to my PhD thesis. And, I would like to thank Professor Peter Wild from University of Victoria for his co-supervision on the work in Chapter 4 and Dr. Farshid Mostowfi from Schlumberger Doll-Research Center (moved from Schlumberger DBR Edmonton) for the collaboration on the work in Chapter 6. Moreover, I would express my thanks to all my colleagues for their help to my PhD work. Specially, thanks to Dr. Hossein Fadaei for his expertise in petroleum and his help to my research in first two years. My sincere thanks also go to Dr. Jason Riordon, Dr. Huawei Li and Dr. Hadi Zandavi who worked closely with me and supported my research work in last two years. In addition, thanks to three summer students who assisted my work, Haiyi Wang, Japinder Nijjer and Yi Xu. Finally and importantly, I would like to express my deep appreciation to my parents, Pingyuan Bao and Junqing Shi, for their endless and invaluable support throughout my PhD journey and my life. I could not make the achievement without them. Thank you to my parents. iv Table of Contents Contents Acknowledgments.......................................................................................................................... iv Table of Contents .............................................................................................................................v List of Tables ............................................................................................................................... viii List of Figures ................................................................................................................................ ix List of Appendices ..................................................................................................................... xviii 1 Thesis Overview .........................................................................................................................1 1.1 Research motivation .............................................................................................................1 1.1.1 Carbon transport and sequestration ..........................................................................1 1.1.2 Shale gas/oil production ...........................................................................................4 1.2 Thesis structure ....................................................................................................................6 2 Introduction .................................................................................................................................8 2.1 Fluid phases .........................................................................................................................8 2.2 Experimental methods to measure fluid phase ..................................................................12 2.2.1 PVT experiments ...................................................................................................14 2.2.2 Optical methods .....................................................................................................17 2.2.3 Electrical and acoustic methods .............................................................................19 2.2.4 Microfluidic methods .............................................................................................20 2.2.5 Nanofluidic methods ..............................................................................................23 3 Detection of Bubble and Dew Point using Optical Thin-film interference ..............................29 3.1 Introduction ........................................................................................................................29 3.2 Experimental ......................................................................................................................31 3.2.1 Experimental setup.................................................................................................31 v 3.2.2 Sensing mechanism: thin-film interference ...........................................................32 3.2.3 Experimental procedure .........................................................................................35 3.3 Results and discussion .......................................................................................................35 3.3.1 Method validation with pure CO2 ..........................................................................35 3.3.2 Application to industrial CO2 mixtures containing impurities ..............................40 3.3.3 Comparison with existing methods of gas mixture properties ...............................43 3.3.4 Film thickness determination .................................................................................45 3.3.5 Resolution ..............................................................................................................45 3.3.6 Repeatability ..........................................................................................................46 3.4 Conclusion .........................................................................................................................46 3.5 Supplemental material .......................................................................................................47 4 Detecting Supercritical CO2 in Brine at Sequestration Pressure with an Optical Fiber Sensor ........................................................................................................................................50 4.1 Introduction ........................................................................................................................50 4.2 Experimental ......................................................................................................................52 4.2.1 Optical fiber sensor ................................................................................................52 4.2.2 High-pressure apparatus.........................................................................................54
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