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This book introduces readers to experimental techniques of general utility that can be used to practically and reliably determine nucleation rates. It also covers the basics of gas hydrates, phase equilibria, nucleation theory, crystal growth, and interfacial gaseous states. Given its scope, the book will be of interest to graduate students and researchers in the field of hydrate nucleation. The formation of gas hydrates is a first-order phase transition that begins with nucleation. Understanding nucleation is of interest to many working in the chemical and petroleum industry, since nucleation, while beneficial in many chemical processes, is also a concern in terms of flow assurance for oil and natural gas pipelines. A primary difficulty in the investigation of gas hydrate nucleation has been researchers’ inability to determine and compare the nucleation rates of gas hydrates across systems with different scales and levels of complexity, which in turn has limited their ability to study the nucleation process itself. This book introduces readers to experimental techniques that can be used to practically and reliably determine the nucleation rates of gas hydrate systems. It also covers the basics of gas hydrates, phase equilibria, nucleation theory, crystal growth, and interfacial gaseous states. Given its scope, the book will be of interest to graduate students and researchers in the field of hydrate nucleation.
This book introduces readers to experimental techniques of general utility that can be used to practically and reliably determine nucleation rates. It also covers the basics of gas hydrates, phase equilibria, nucleation theory, crystal growth, and interfacial gaseous states. Given its scope, the book will be of interest to graduate students and researchers in the field of hydrate nucleation. The formation of gas hydrates is a first-order phase transition that begins with nucleation. Understanding nucleation is of interest to many working in the chemical and petroleum industry, since nucleation, while beneficial in many chemical processes, is also a concern in terms of flow assurance for oil and natural gas pipelines. A primary difficulty in the investigation of gas hydrate nucleation has been researchers’ inability to determine and compare the nucleation rates of gas hydrates across systems with different scales and levels of complexity, which in turn has limited their ability to study the nucleation process itself. This book introduces readers to experimental techniques that can be used to practically and reliably determine the nucleation rates of gas hydrate systems. It also covers the basics of gas hydrates, phase equilibria, nucleation theory, crystal growth, and interfacial gaseous states. Given its scope, the book will be of interest to graduate students and researchers in the field of hydrate nucleation.
Gas hydrates, or clathrate hydrates, are crystalline solids resembling ice, in which small (guest) molecules, typically gases, are trapped inside cavities formed by hydrogen-bonded water (host) molecules. They form and remain stable under low temperatures – often well below ambient conditions – and high pressures ranging from a few bar to hundreds of bar, depending on the guest molecule. Their presence is ubiquitous on Earth, in deep-marine sediments and in permafrost regions, as well as in outer space, on planets or comets. In addition to water, they can be synthesized with organic species as host molecules, resulting in milder stability conditions: these are referred to as semi-clathrate hydrates. Clathrate and semi-clathrate hydrates are being considered for applications as diverse as gas storage and separation, cold storage and transport and water treatment. This book is the first of two edited volumes, with chapters on the experimental and modeling tools used for characterizing and predicting the unique molecular, thermodynamic and kinetic properties of gas hydrates (Volume 1) and on gas hydrates in their natural environment and for potential industrial applications (Volume 2).
This book had its genesis in a symposium on gas hydrates presented at the 2003 Spring National Meeting of the American Institute of Chemical Engineers. The symposium consisted of twenty papers presented in four sessions over two days. Additional guest authors were invited to provide continuity and cover topics not addressed during the symposium. Gas hydrates are a unique class of chemical compounds where molecules of one compound (the guest material) are enclosed, without bonding chemically, within an open solid lattice composed of another compound (the host material). These types of configurations are known as clathrates. The guest molecules, u- ally gases, are of an appropriate size such that they fit within the cage formed by the host material. Commonexamples of gas hydrates are carbon dioxide/water and methane/water clathrates. At standard pressure and temperature, methane hydrate contains by volume 180 times as much methane as hydrate. The United States Geological Survey (USGS) has estimated that there is more organic carbon c- tained as methane hydrate than all other forms of fossil fuels combined. In fact, methane hydrates could provide a clean source of energy for several centuries. Clathrate compounds were first discovered in the early 1800s when Humphrey Davy and Michael Faraday were experimenting with chlorine-water mixtures.
Hydrate research has expanded substantially over the past decade, resulting in more than 4,000 hydrate-related publications. Collating this vast amount of information into one source, Clathrate Hydrates of Natural Gases, Third Edition presents a thoroughly updated, authoritative, and comprehensive description of all major aspects of natural gas cla
"Natural gas-hydrates are crystalline inclusion compounds with gas molecules (guest compounds) trapped within a host lattice formed by water molecules in an ice-like hydrogen-bonded framework. Natural gas-hydrates have the potential to become an important carbon-based resource addressing the increasing energy demand, and they pose a risk in terms of climate change. Accurate estimates of gas-hydrates global inventory, understanding of formation and dissociation processes of gas-hydrates, and evaluation of their environmental impact require models that accurately describe gas-hydrate stability in sediments and predict gas-hydrate kinetic nucleation processes. The hypothesis driving this work is that incorporation of selected sediment properties, i.e., surface energies and pore diameter, can lead to more accurate predictions of hydrate equilibrium, stability and nucleation in porous media. In this work, a model for gas-hydrate equilibrium in porous media was developed from basic thermodynamic principles and tested against available experimental data published in the scientific literature. The proposed model predicts reported experimental data with high accuracy for the range of pore sizes (3.4 ~ 24.75 nm) of different materials reported in the literature. It was found that the wettability of the pore surface affects the shape of the hydrate phase inside the pore and consequently influences the equilibrium pressures of gas-hydrates formed in porous media. A predictive macroscopic mathematical model describing the kinetic nucleation of gas-hydrates was developed based on Classical Nucleation Theory (CNT) in order to formulate correction factors for three types of interfaces mostly encountered in natural sediments (gas-liquid interface, liquid-solid interface and three-phase boundary lines). This approach, which incorporates the interfacial properties of sediments, can efficiently provide a fundamental understanding on the dependence of the formation mechanism of gas hydrates on a wide range of interfacial properties (wettability, substrate size, interfacial tension). The model predicts that hydrate nucleation is energetically favorable on confined surfaces with smaller contact-angle values, i.e., hydrophilic surfaces. Comparison between different types of interfaces leads to the conclusion that the nucleation of gas hydrates preferentially occurs in larger sediment pores. At the beginning of methane hydrate formation, for example, hydrate will preferentially nucleate at the gas-liquid interface. With the increase of hydrate volume or growth of the hydrate phase, the center of crystal growth moves towards the liquid-solid interface. In natural systems, gas hydrates form first on the concave liquid/solid interface and gas/liquid interface in sandstone sediments, gas/liquid interface and gas/liquid/solid triple boundary line in clay sediments and gas/liquid interface in pipeline with oil droplets. The inclusion of sediment properties in the model for gas-hydrate equilibrium in sediments predict experimental data within a margin of %AAD lower than 2%, a significant improvement upon previous modeling attempts. Additionally, the inclusion of sediment properties in the models for kinetic nucleation of gas hydrates result in mathematical models that capture the qualitative information obtained from examination of gas-hydrate core samples. Therefore, the hypothesis of the present work was proven."--Abstract.
Striking a balance between theoretical and experimental perspectives, this book presents a historical overview of clathrate hydrates and examines future trends, reviews crystal structures and properties, reveals industrial applications of clathrate hydrates in the production and processing of natural gas, discusses hydrate kinetics and elucidates the current status of hydrate time dependence, analyzes time-independent phase equilibria, and more. With nearly 300 tables and illustrations, the book is a practical guide for chemical, design, process, petroleum, and mechanical engineers; chemists and geochemists; geologists; geophysicists; and graduate-level students in these disciplines.
Gas hydrates in their natural environment and for potential industrial applications (Volume 2).
“Natural Gas Hydrates: Experimental Techniques and Their Applications” attempts to broadly integrate the most recent knowledge in the fields of hydrate experimental techniques in the laboratory. The book examines various experimental techniques in order to provide useful parameters for gas hydrate exploration and exploitation. It provides experimental techniques for gas hydrates, including the detection techniques, the thermo-physical properties, permeability and mechanical properties, geochemical abnormalities, stability and dissociation kinetics, exploitation conditions, as well as modern measurement technologies etc. This book will be of interest to experimental scientists who engage in gas hydrate experiments in the laboratory, and is also intended as a reference work for students concerned with gas hydrate research. Yuguang Ye is a distinguished professor of Experimental Geology at Qingdao Institute of Marine Geology, China Geological Survey, China. Professor Changling Liu works at the Qingdao Institute of Marine Geology, China Geological Survey, China.
Carbon in Earth's fluid envelopes - the atmosphere, biosphere, and hydrosphere, plays a fundamental role in our planet's climate system and a central role in biology, the environment, and the economy of earth system. The source and original quantity of carbon in our planet is uncertain, as are the identities and relative importance of early chemical processes associated with planetary differentiation. Numerous lines of evidence point to the early and continuing exchange of substantial carbon between Earth's surface and its interior, including diamonds, carbon-rich mantle-derived magmas, carbonate rocks in subduction zones and springs carrying deeply sourced carbon-bearing gases. Thus, there is little doubt that a substantial amount of carbon resides in our planet's interior. Yet, while we know it must be present, carbon's forms, transformations and movements at conditions relevant to the interiors of Earth and other planets remain uncertain and untapped. Volume highlights include: - Reviews key, general topics, such as carbonate minerals, the deep carbon cycle, and carbon in magmas or fluids - Describes new results at the frontiers of the field with presenting results on carbon in minerals, melts, and fluids at extreme conditions of planetary interiors - Brings together emerging insights into carbon's forms, transformations and movements through study of the dynamics, structure, stability and reactivity of carbon-based natural materials - Reviews emerging new insights into the properties of allied substances that carry carbon, into the rates of chemical and physical transformations, and into the complex interactions between moving fluids, magmas, and rocks to the interiors of Earth and other planets - Spans the various chemical redox states of carbon, from reduced hydrocarbons to zero-valent diamond and graphite to oxidized CO2 and carbonates - Captures and synthesizes the exciting results of recent, focused efforts in an emerging scientific discipline - Reports advances over the last decade that have led to a major leap forward in our understanding of carbon science - Compiles the range of methods that can be tapped tap from the deep carbon community, which includes experimentalists, first principles theorists, thermodynamic modelers and geodynamicists - Represents a reference point for future deep carbon science research Carbon in Planetary Interiors will be a valuable resource for researchers and students who study the Earth's interior. The topics of this volume are interdisciplinary, and therefore will be useful to professionals from a wide variety of fields in the Earth Sciences, such as mineral physics, petrology, geochemistry, experimentalists, first principles theorists, thermodynamics, material science, chemistry, geophysics and geodynamics.