Imaging Biologically-Based Clathrate Hydrate Inhibitors

IMAGING BIOLOGICALLY-BASED CLATHRATE HYDRATE INHIBITORS by Raimond Gordienko A thesis submitted to the Department of Biology in conformity with the requirements for the degree of Master of Science Queen’s University Kingston, Ontario, Canada August, 2009 Copyright © Raimond Gordienko, 2009 Abstract The unscheduled formation of gas hydrate plugs in oil and gas pipelines, which can lead to serious mechanical and personnel damage, is a problematic issue in the petroleum industry. Traditionally, thermodynamic inhibitors such as methanol have been used to control the formation of gas hydrates, but due to the large expenses and ecological risks associated with its use there is increased interest in the use of alternative hydrate inhibitors. They include kinetic inhibitors (KIs) and antiagglomerants (AAs) and as their names imply, function by interfering with the kinetics of hydrate formation and hydrate agglomeration. Recently, antifreeze proteins (AFPs) have shown to inhibit hydrates and have been proposed as hydrate inhibitors. Normally, AFPs function to protect the tissues of various organisms during freezing conditions. Initially they were found in polar fish, and were later recognized in insects, plants and microorganisms. AFPs are thought to function by lowering the freezing point of water through an adsorption-inhibition mechanism. This thesis has shown that antifreeze proteins (AFPs) are able to modify the crystal morphologies of structure II (sII) tetrahydrofuran (THF) similarly to the KI poly-N- vinylpyrrolidone (PVP) by adhering to the hydrate surface and inhibiting crystal growth. The AFPs were also tested on a high-pressure sII methane/ethane/propane hydrate and proved to have superior hydrate inhibition to PVP. Yet, the expense of purifying AFPs makes them impractical for industrial purposes, thus investigations into the use of cold-adapted bacteria as hydrate inhibitors proved that isolates capable of adsorbing to THF hydrate showed the most effective THF hydrate inhibition. These findings suggest a potential for the future development of biologically-based hydrate inhibitors. ii Acknowledgements Virginia K. Walker, your unparalleled enthusiasm, cheerfulness and knowledge as a supervisor and friend has been a source of inspiration throughout this thesis and my time at Queen’s, I sincerely thank you. I thank my committee members Ken Ko, Heather Jamieson and John Ripmeester for their time and advice throughout the progression of my thesis. Members of the Walker Lab, former and current; Julie Choi, Emily Huva, Niraj Kumar, Shaun Nowickyj, Nikki Philbrook, Tara Vanderveer, Sandra Wilson and Suzy Wu, additionally, department members; Linda Cameron, Josh Powles, Grace Tharmarajah, Matt Vankoughnett and Tara Zamin, my thanks to all your assistance and friendship, you have made every day at work and out enjoyable and memorable. I also thank NRC faculty Dr. Hiroshi Ohno, Rajneesh Kumar and Robin Susilo as well Sherry Gauthier and Adam Middleton from Queen’s Biochemistry for their kind assistance and advice throughout my thesis. I thank my friends Andrew Palombella, Scott Robson and Andrew Seniuk for their shared conversation and experiences here in Kingston, I will never forget our times together. To my family, for all their care and support throughout all the years of life and to my mother, who has been my guiding light. iii Co-Authorship Chapters 2 and 3. Dr. Hiroshi Ohno assisted with the high-pressure gas mix hydrate work. Appendix A. Dr. Robin Susilo assisted with the high-pressure methane hydrate work. iv Table of Contents Abstract ........................................................................................................................................... ii Acknowledgements ........................................................................................................................ iii Co-Authorship................................................................................................................................ iv Table of Contents ............................................................................................................................ v List of Figures .............................................................................................................................. viii List of Tables ............................................................................................................................... viii List of Abbreviations ..................................................................................................................... ix Chapter 1 Introduction and Literature Review Clathrate Hydrates ........................................................................................................ 1 Properties and Varieties ................................................................................................ 1 Hydrates in Industry ...................................................................................................... 2 Hydrate Plugs ................................................................................................................ 3 Preventing Hydrate Growth .......................................................................................... 4 Thermodynamic Inhibitors............................................................................................ 4 Chemical Kinetic Inhibitors .......................................................................................... 5 Antifreeze Proteins........................................................................................................ 6 AFP Diversity ............................................................................................................... 7 AFP Activities ............................................................................................................. 11 Applications of AFPs .................................................................................................. 11 Cold-Adapted and Freeze-Tolerant Bacteria .............................................................. 12 Bacterial AFPs ............................................................................................................ 13 Biotechnological Applications .................................................................................... 14 Research Objectives .................................................................................................... 15 References ................................................................................................................... 16 v Chapter 2 Towards A Green Hydrate Inhibitor: Imaging AFPs on Clathrate Hydrates Abstract ....................................................................................................................... 26 Introduction ................................................................................................................. 27 Materials and Methods ................................................................................................ 28 Results ......................................................................................................................... 33 Discussion ................................................................................................................... 36 References ................................................................................................................... 46 Chapter 3 Tetrahydrofuran Hydrate Inhibition using Cold-Adapted Bacteria Abstract ....................................................................................................................... 48 Introduction ................................................................................................................. 49 Materials and Methods ................................................................................................ 50 Results and Discussion ............................................................................................... 52 References ................................................................................................................... 56 Chapter 4 General Discussion 4.1. AFP binding and hydrate inhibition ..................................................................... 62 4.2. Cold-adapted bacteria and hydrate inhibition ...................................................... 67 4.3. Concluding comments ......................................................................................... 68 References ................................................................................................................... 70 Summary ..................................................................................................................... 73 Appendix A AFPs and sI Methane Hydrate Abstract ....................................................................................................................... 74 Introduction ................................................................................................................. 74 Methods and Results ................................................................................................... 75 Discussion ................................................................................................................... 76 References ................................................................................................................... 77 vi Appendix B AFP Adsorption studies with Amorphous Silica and Quartz Abstract ......................................................................................................................

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