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1.2 Selected Highlights of Clathrate Hydrate Science Research Up to the Present

In this section, we summarize selected highlights of clathrate hydrate research, emphasizing contributions to molecular science. Not all engineering and geological discoveries are covered in detail in this selection. Full author names and references for most of these highlights are given in the following chapters.

1810	Sir Humphrey Davy correctly identified a solid material, previously thought to be solid chlorine, as a compound of chlorine and water and called it “gas hydrate.”
1823	Faraday determined the composition of chlorine hydrate to be Cl₂·10H₂O.
1823	Faraday acting upon a suggestion by Davy, used decomposition of gas hydrates in confined vessels as a method of liquefying gases.
1828	Löwig prepared bromine hydrate and determined the formula Br₂·10H₂O for the compound.
1829	de la Rive prepared SO₂ hydrate, SO₂·14H₂O, and proposed that all common gases form hydrates.
1840	Wöhler prepared H₂S hydrate.
1843	Millon prepared chlorine dioxide hydrate, the first example of the preservation of an unstable chemical species, ClO₂, an explosive‐free radical.
1852	Loir prepared solid binary hydrates from water, H₂S, or H₂Se and halogenated hydrocarbons like chloroform, their composition remained unknown for some 30 years.
1856	Berthelot prepared the first pure hydrates of organic compounds, namely, those of methyl chloride and methyl bromide. He also claimed that CS₂ formed a hydrate, starting a controversy about its existence that lasted 40 years.
1863	Wurtz prepared ethylene oxide (EO) hydrate, the first example of a water‐soluble guest. Its composition and melting point diagram were not determined until 1922.
1878	Isambard showed that the equilibrium pressure of chlorine hydrate is univariant.
1878	Cailletet designed and built apparatus suitable for working at high pressure and low temperature. This was of great value for the preparation of new gas hydrates and the determination of phase equilibria. He illustrated this by preparing new hydrates of acetylene and phosphine.
1882	Wróblewski prepared CO₂ hydrate.
1882	de Forcrand prepared and characterized 33 double hydrates of H₂S with a variety of guests and established similarities of composition, M·2H₂S·23H₂O. Studies were extended to double hydrates with H₂Se as well as a simple hydrate of H₂Se.
1882	Cailletet and Bordet showed that mixed hydrates of CO₂ and PH₃ were not simply physical mixtures of simple CO₂ and PH₃ hydrates but hydrates with unique properties.
1883	de Forcrand applied calorimetry to gas hydrates and assigned most of the thermal effects to the dominant presence of water in the hydrate.
1883	de Forcrand observed that a number of double hydrates had well‐defined cubic, cubo‐octahedral, or truncated octahedral morphologies which were not acted on by polarized light.
1884–1885	Bakhuis Roozeboom provided hydration numbers for SO₂, Cl₂, and Br₂ hydrates and his phase equilibrium diagrams clearly showed the pressure–temperature fields of hydrate stability. Cailletet, Wróblewski, and Bakhuis Roozeboom observed a memory effect that increased the reformation rate of hydrate from solutions of decomposed hydrate.
1884	Le Châtelier used the Clausius–Clapeyron equation for the variation of vapor pressure of the hydrates with temperature and was the first to use the equation to determine gas hydrate compositions.
1885	Chancel and Parmentier reported a simple hydrate of chloroform. This was one of the first so‐called “liquid hydrates” whose guest components are liquids at ambient temperature.
1887–1888	Bakhuis Roozeboom applied the Gibbs phase rule to heterogeneous equilibria and systematically classified chemical and physical processes according to number and nature of the components and phases present. He published on the treatment of the invariant points at which equilibrium lines meet.
1888	Villard prepared hydrates of CH₄, C₂H₆, C₂H₄, N₂O, and propane (1890).
1890	Villard recognized the stabilizing effect of air on the decomposition of gas hydrates. In the search for other “help‐gases” he identified both hydrogen at 23 atm and oxygen at 2.5 atm as increasing the decomposition temperature of ethyl chloride.
1897	On the basis of careful measurements on the large number of hydrates then available, Villard presented a definition of the composition of gas hydrates (Villard's law).
1897	de Forcrand and Thomas discovered new help‐gases (CO₂, C₂H₄, C₂H₂, and SO₂).
1902	de Forcrand used calorimetric data and a generalization of Trouton's rule to calculate hydrate compositions for 15 hydrates. About half had compositions in agreement with Villard's law.
1923	Bouzat produced summary statements giving the then current definition of hydrates, their structure, and composition.
1926	Schroeder wrote an influential monograph summarizing the state of knowledge of gas hydrate to that date.
1934	Hammerschmidt, after reading Schroeder's book, showed that gas hydrates are more likely to form plugs in natural gas pipelines than ice.
1936–1937	Nikitin prepared mixed hydrates of noble gases and SO₂ and showed that the noble gases could be separated by partitioning between the solid hydrate and the gas. His observations were first consistent with the “solid solution” nature of hydrates.
1946	Deaton and Frost presented experimental data on hydrate phase equilibria of natural gas components and methods of hydrate prevention.
1946	Miller and Strong proposed natural gas storage in hydrate form.
1947	Powell coined the term “clathrate” for materials having a guest molecule residing in a cavity formed in a host lattice.
1949	von Stackelberg used X‐ray diffraction data to propose a structure for a gas hydrate of chloroform and H₂S. Although the structure, based on a lattice with holes for guests, was incorrect, it was a radical departure from the molecular structure current up until that time. von Stackelberg had studied the X‐ray diffraction of gas hydrates prior to this time, but his original photographic plates had been destroyed in aerial bombardment during World War II.
1951	Clausen introduced the pentagonal dodecahedron as a structural component of gas hydrates, and von Stackelberg and Muller's X‐ray diffraction data confirmed the crystal structure of the “structure II” (sII or CS‐II) hydrate proposed by Clausen.
1952	Clausen, von Stackelberg, and Pauling and Marsh provided a structure for “structure I” (sI or CS‐I) gas hydrates.
1952	Delsemme and Swings suggested the presence of gas hydrates in comets and interstellar grains. Delsemme later suggested that the outgassing of comets on approaching the sun could be due to decomposition of hydrates.
1957–1967	Barrer and coworkers studied hydrate thermodynamics, kinetics, and separation of gas mixtures with hydrate formation.
1959–1970	Jeffrey and coworkers used single‐crystal X‐ray diffraction to obtain structural data for clathrate hydrates, semi‐clathrates, and salt hydrates.
1959	van der Waals and Platteeuw presented the “solid solution” statistical thermodynamics model for clathrate hydrates.
1961	Miller and Pauling hypothesized hydrate formation as a mechanism for anesthesia arising from inert noble gases, in particular xenon.
1961	Miller suggested the presence of gas hydrates in the planets, planetary rings, and interstellar space in the solar system.
1963	Davidson used dielectric methods to study clathrate hydrates. He discovered new water‐soluble (polar) guests for clathrate hydrates, measured the dynamics of guest and host molecules, found that water molecule reorientation rates depend on the nature of the guest molecule, and postulated the presence of guest–host hydrogen bonding capable of generating Bjerrum defects.
1965	Makogon reported on natural gas hydrates found in the Siberian permafrost.
1965	Kobayashi and coworkers applied the Kihara intermolecular potential to van der Waals–Platteeuw theory to represent the guest–cage interactions.
1965	Davidson and coworkers started nuclear magnetic resonance (NMR) measurements on clathrate hydrates and demonstrated that the SF₆ guest in sII clathrate rotates isotropically even at 77 K.
1966	Glew and Rath showed that the equilibrium compositions of Cl₂ and EO clathrate hydrates are variable, in accordance with van der Waals–Platteeuw theory.
1968	Glew and Haggett studied EO hydrate growth kinetics and showed that the process is governed by heat transfer over a wide range of concentrations.
1969	Miller predicted air hydrates should be present in glacier ice, CO₂ hydrates on Mars, and CH₄ hydrates on the outer planets and moons.
1969	Ginsburg studied natural gas hydrates in geological settings.
1971	Stoll, Ewing, and Bryan found that anomalous wave velocities (bottom‐simulating reflectors) are associated with marine offshore natural gas hydrate deposits.
1972	Parrish and Prausnitz developed convenient computer code for applying the van der Waals–Platteeuw theory to the calculation of gas hydrate phase diagrams.
1972	Tester, Bivins, and Herrick performed the first Monte Carlo simulation of gas hydrates of noble gases, N₂, O₂, CO₂, and CH₄ to test some of the assumptions made regarding guest–cage interactions in using the van der Waals–Platteeuw approach.
1973–1983	Bertie and coworkers studied clathrate hydrates with infrared spectroscopy at low temperatures.
1974	Bily and Dick encountered gas hydrates below the permafrost in the Mackenzie Delta, Northwest Territories, Canada.
1974	Davidson, Garg, and Ripmeester reported broadline and pulsed NMR experiments on tetrahydrofuran (THF) hydrate from 4 to 270 K, showing regions of anisotropic and isotropic motions of the guest, relaxation minima for guest anisotropic rotation, water molecule reorientation, and diffusion.
1974	Davidson et al. showed that polar as well as non‐polar guests show reorientational guest motions that can be described by very broad distributions in reorientational correlation times at low temperatures. It led to a model for a guest–host potential determined by short range interactions between the guest and the disordered hydrogen atoms of the host water molecules.
1974	Dyadin was appointed to lead a research group that over some 40 years provided new information on structure, stoichiometry, and stability of clathrates and high‐pressure research on clathrate hydrates.
1975	Sloan and coworkers initiated work on two‐phase hydrate equilibria.
1976	Holder calculated that small guests are more likely to form sII (CS‐II) hydrate than sI (CS‐I).
1976–1987	Nakayama studied phase equilibria of salt hydrates.
1976	Peng and Robinson developed an accurate equation of state which is widely used to describe the vapor–liquid equilibria of hydrocarbons and small gases for hydrate equilibrium calculations.
1977	Ripmeester and Davidson reported 17 new clathrate guests mainly from NMR measurements.
1979–1993	Bishnoi and coworkers initiated a program of natural gas hydrate kinetic measurements and modeling and phase equilibrium modeling.
1981–1985	Cady measured hydrate compositions as a function of pressure, obtaining values which are in agreement with van der Waals–Platteeuw theory.
1981	Ross, Anderson, and Backström measured the anomalously low thermal conductivity of hydrates of clathrate hydrates.
1983	Tse, Klein, and coworkers initiated molecular dynamics simulations of clathrate hydrates.
1984	Handa prepared pure hydrocarbon hydrates under equilibrium conditions and obtained their thermodynamic properties from calorimetry.
1984	Davidson et al. experimentally showed very small guests form CS‐II rather than CS‐I.
1986	Davidson et al. provided the first laboratory analysis of recovered gas hydrate samples obtained from the Gulf of Mexico and identified both CS‐I and CS‐II hydrates.
1986	Davidson, Handa, and Ripmeester provided the first measurement of absolute cage occupancy of Xe hydrate.
1987	Ripmeester and coworkers discovered a new clathrate hydrate family, structure H (HS‐III).
1988	Whalley showed that octahedral melt figures are produced in THF clathrate hydrate crystals.
1988	Ripmeester and Ratcliffe introduced low‐temperature magic angle spinning ¹³C NMR spectroscopy to measure the relative occupancy of methane and methane/propane hydrate and used van der Waals–Platteeuw theory to obtain hydration numbers.
1988	Makogon and Kvenvolden independently provided estimates of the total volume of worldwide in situ hydrated natural gas at 10¹⁶ m³. Kvenvolden recognizes the decomposition of natural gas hydrates as potential contributor to global climate change.
1990	Collins, Ratcliffe, and Ripmeester used NMR spectral properties of several different nuclei, including ²H, ¹⁹F, ³¹P, and ⁷⁷Se to measure hydration numbers.
1990	Rodger studied hydrate stabilities with molecular dynamics simulations.
1990	Hallbrucker and Mayer formed clathrate hydrates by vapor deposition of amorphous solid water.
1990	Ripmeester and Ratcliffe discovered numerous new guests which form HS‐III and CS‐II using ¹²⁹Xe NMR of xenon co‐guest.
1991	Sloan proposed a molecular mechanism for hydrate formation with implications for inhibition.
1991	Handa et al. applied high pressure at 77 K to amorphize CS‐I and CS‐II clathrate hydrates, much as was observed for ice itself. Unlike, the amorphous ice phase, this amorphous phase recrystallized to the original hydrate phase when the applied pressure was reduced to ambient at 77 K.
1992	Handa and Stupin investigated hydrate phase equilibria in porous media.
1993	Inelastic incoherent neutron scattering (IINS) experiments on methane, Xe, and Kr hydrates were initiated at the NRC.
1993	Englezos and Hatzikiriakos used mathematical models to quantify how global temperature warming affects the stability of methane hydrates in the permafrost and in ocean sediments.
1993–2020	Tanaka and coworkers began a program of generalizing and improving on the assumptions of the van der Waals–Platteeuw theory.
1994	Edwards modeled winter flounder antifreeze peptide as a potential kinetic hydrate inhibitor.
1996	Sum measured clathrate hydration numbers with Raman spectroscopy.
1996	Koga and Tanaka studied the rearrangements of the water hydrogen bonding network in clathrate hydrates with polar guests using molecular dynamics simulation.
1997	Kuhs et al. reported double occupancy of large cages in CS‐II nitrogen hydrate.
1997	Udachin et al. reported HS‐III (sH) structure from single‐crystal X‐ray diffraction.
1997	Udachin et al. determined the tetragonal structure, TS1, of Br₂ hydrate from single‐crystal X‐ray diffraction.
1999	Dyadin et al. reported that H₂ forms a clathrate hydrate at high pressure.
1999	Moudrakovski et al. reported the first magnetic resonance imaging (MRI) of hydrate formation on ice particles.
2000	Huang, Walker, and Ripmeester showed that antifreeze proteins (AFPs) inhibit hydrate formation and, in some cases, eliminate the freezing memory effect for hydrate reformation.
2000–2001	Loveday et al., Hirai et al., Chou et al., and Manakov et al. prepared and characterized high‐pressure phases of water, including a high‐pressure HS‐III clathrate phase.
2001	Moudrakovski et al. used hyperpolarized ¹²⁹Xe NMR to observe the nucleation, growth, and decomposition of Xe hydrate in real time.
2001	Udachin et al. determined a new structural type for dimethyl ether clathrate hydrate.
2001	Moudrakovski et al. observed a metastable CS‐II Xe hydrate phase.
2001	Loveday et al. discovered a high‐pressure structure of CH₄ hydrate using diamond anvil diffraction methods.
2002	Ballard and Sloan developed CSMGem software for hydrate equilibrium prediction.
2002	Mao et al. synthesized the CS‐II hydrogen hydrate under high‐pressure and low‐temperature conditions to observe high H₂:H₂O storage ratios.
2002	Servio and Englezos accurately measure the temperature dependence of the solubility of CH₄ and CO₂ gases in the aqueous phase in equilibrium with the corresponding clathrate hydrate phases.
2004	The mechanism of self‐preservation of methane hydrate was studied with scanning electron microscope (SEM) imaging by Stern and coworkers. Falenty and Kuhs used SEM to study self‐preservation of CO₂ hydrate in 2009.
2005	Lee et al. developed a method for tuning the H₂ content of the mixed CS‐II hydrate with THF.
2005	Clarke and Bishnoi developed a focused beam reflectance method for in situ, time‐dependent hydrate particle size analysis under conditions of hydrate nucleation and growth.
2007–2016	Bačić and coworkers performed quantum mechanical calculations to determine discrete translation‐rotational states of H₂ and CH₄ in different CS‐I and CS‐II cages with single and multiple occupancies.
2007	Celli, Ulivi, and coworkers initiated IINS studies on H₂/D₂/HD dynamics in CS‐I and CS‐II clathrate hydrates
2007	Linga, Kumar, and Englezos provided the thermodynamic and kinetic basis for CO₂ capture from post‐combustion flue gas and pre‐combustion fuel gas.
2009	Detailed characterization of hydrogen bonding of hydrates was determined using molecular dynamics simulations by two groups: Buch et al. and at the NRC.
2009	Simulation work initiated by Jordan and coworkers determined the stepwise (layer by layer) decomposition mechanism for methane hydrate.
2010	Walsh et al. carried out millisecond molecular dynamics simulations of CH₄ hydrate nucleation and growth.
2010	Following an early proposal by McTurk and Waller, Mori, and coworkers formed ozone hydrate in an apparatus incorporating in situ ozone generation.
2012–2014	Shin et al. characterized clathrate hydrates incorporating NH₃ and CH₃OH synthesized using vapor deposition.
2013	Udachin et al. performed single‐crystal X‐ray diffraction and molecular dynamics simulations on halogen hydrates which indicated the possibility of halogen bonding between these guests and water molecules of the cages.
2014	Falenty, Hanssen, and Kuhs prepared a metastable ice phase (Ice XVI) with the structure of the empty CS‐II lattice.
2015	NMR spectroscopy gave direct evidence of cage‐to‐cage transfer of hydrate guests CO₂ in THF‐CO₂ CS‐II hydrate and for CH₄ and CH₃F in double hydrates of THF and tert‐butylmethylether.
2015	Molecular dynamics simulations performed at the NRC and University of British Columbia showed the formation of nanobubbles of methane upon decomposition of methane hydrate.

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