Effect of rapidly depressurizing and rising temperature on methane hydrate dissociation

Two methods, rapidly depressurizing to 0.1 MPa at a constant temperature and rising temperature under equilibrium P, T conditions, were used to study the dissociation of pure CH4 hydrate formed below the ice point. At a constant temperature with rapidly depressurizing to 0.1 MPa, CH4 hydrate dissociated rapidly at initial dissociation and then the dissociation rate gradually decreased. However, the dissociation of CH4 hydrate at temperatures of 261 to 266 K was much faster than that at temperatures of 269 to 272 K, indicating its anomalous preservation. Under an equilibrium P, T conditions, rising temperature had extensively controlling impact on dissociation of CH4 hydrate at equilibrium pressures of 2.31, 2.16 and 1.96 MPa. In this study, we report the effect of pressure on CH4 hydrate dissociation, especially the effect of equilibrium pressure on dissociation at various melting temperatures. And we find that the ice particles size of CH4 hydrate formed may dominant the CH4 hydrate dissociation. Dissociation of CH4 hydrate formed from ice particles of smaller than 250 μm may not have an anomalous preservation below the ice point, while particles larger than 250 μm may have more extensive anomalous preservation.     

Stabilization of methane hydrate by pressurization with He or N2 gas

The behavior of methane hydrate was investigated after it was pressurized with helium or nitrogen gas in a test system by monitoring the gas compositions. The results obtained indicate that even when the partial pressure of methane gas in such a system is lower than the equilibrium pressure at a certain temperature, the dissociation rate of methane hydrate is greatly depressed by pressurization with helium or nitrogen gas. This phenomenon is only observed when the total pressure of methane and helium (or nitrogen) gas in the system is greater than the equilibrium pressure required to stabilize methane hydrate with just methane gas. The following model has been proposed to explain the observed phenomenon: (1) Gas bubbles develop at the hydrate surface during hydrate dissociation, and there is a pressure balance between the methane gas inside the gas bubbles and the external pressurizing gas (methane and helium or nitrogen), as transmitted through the water film; as a result the methane gas in the gas bubbles stabilizes the hydrate surface covered with bubbles when the total gas pressure is greater than the equilibrium pressure of the methane hydrate at that temperature; this situation persists until the gas in the bubbles becomes sufficiently dilute in methane or until the surface becomes bubble-free. (2) In case of direct contact of methane hydrate with water, the water surrounding the hydrate is supersaturated with methane released upon hydrate dissociation; consequently, methane hydrate is stabilized when the hydrostatic pressure is above the equilibrium pressure of methane hydrate at a certain temperature, again until the dissolved gas at the surface becomes sufficiently dilute in methane. In essence, the phenomenon is due to the presence of a nonequilibrium state where there is a chemical potential gradient from the solid hydrate particles to the bulk solution that exists as long as solid hydrate remains.     

Gas hydrates of argon and methane synthesized at high pressures: composition, thermal expansion, and self-preservation

For the first time, the compositions of argon and methane high-pressure gas hydrates have been directly determined. The studied samples of the gas hydrates were prepared under high-pressure conditions and quenched at 77 K. The composition of the argon hydrate (structure H, stable at 460-770 MPa) was found to be Ar.(3.27 +/- 0.17)H(2)O. This result shows a good agreement with the refinement of the argon hydrate structure using neutron powder diffraction data and helps to rationalize the evolution of hydrate structures in the Ar-H(2)O system at high pressures. The quenched argon hydrate was found to dissociate in two steps. The first step (170-190 K) corresponds to a partial dissociation of the hydrate and the self-preservation of a residual part of the hydrate with an ice cover. Presumably, significant amounts of ice Ic form at this stage. The second step (210-230 K) corresponds to the dissociation of the residual part of the hydrate. The composition of the methane hydrate (cubic structure I, stable up to 620 MPa) was found to be CH(4).5.76H(2)O. Temperature dependence of the unit cell parameters for both hydrates has been also studied. Calculated from these results, the thermal expansivities for the structure H argon hydrate are alpha(a) = 76.6 K(-1) and alpha(c) = 77.4 K(-1) (in the 100-250 K temperature range) and for the cubic structure I methane hydrate are alpha(a) = 32.2 K(-1), alpha(a) = 53.0 K(-1), and alpha(a) = 73.5 K(-1) at 100, 150, and 200 K, respectively.     

Dissociation behavior of “dry water” C_3H_8 hydrate below ice point:Effect of phase state of unreacted residual water on a mechanism of gas hydrates dissociation

The results on a dissociation behavior of propane hydrates prepared from "dry water" and contained unreacted residual water in the form of ice inclusions or supercooled liquid water(water solution of gas) were presented for temperatures below 273 K.The temperature ramping or pressure release method was used for the dissociation of propane hydrate samples.It was found that the mechanism of gas hydrate dissociation at temperatures below 273 K depended on the phase state of unreacted water in the hydrate sample.Gas hydrates dissociated into ice and gas if the ice inclusions were in the hydrate sample.The samples of propane hydrates with inclusions of unreacted supercooled water only(without ice inclusions) dissociated into supercooled water and gas below the pressure of the supercooled water-hydrate-gas metastable equilibrium.     

Rates and mechanisms of conversion of ice nanocrystals to ether clathrate hydrates: guest-molecule catalytic effects at approximately 120 k

A Fourier transform infrared investigation of the rates and energetics of conversion of ice nanocrystals within 3-D arrays to ether clathrate-hydrate (CH) particles at approximately 120 K is reported. After an induction period, apparently necessitated by relatively slow nucleation of the CH phase, the well-established shrinking-core model of particle-adsorbate reaction applies to these conversions in the presence of an abundance of adsorbed ether. This implies that the transport of the ether adsorbate through the product crust encasing a reacting particle core (a necessary aspect of a particle reaction mechanism) is the rate-controlling factor. Diffusion moves adsorbed reactant molecules to the reaction zone at the interface of the ice core with the product (CH) crust. The results indicate that ether hydrate formation rates near 120 K resemble rates for gas hydrates measured near 260 K, implying rates greater by many orders of magnitude for comparable temperatures. A surprising secondary enhancement of ether CH-formation rates by the simultaneous incorporation of simple small gas molecules (N2, CO2, CH4, CO, and N2O) has also been quantified in this study. The rapid CH formation at low temperatures is conjectured to derive from defect-facilitated transport of reactants to an interfacial reaction zone, with the defect populations enhanced through transient H bonding of guest-ether proton-acceptor groups with O-H groups of the hydrate cage walls.     

Dissociation behavior of C2H6 hydrate at temperatures below the ice point: melting to liquid water followed by ice nucleation

The dissociation of C(2)H(6) hydrate particles by slow depressurization at temperatures slightly below the ice melting point was studied using optical microscopy and Raman spectroscopy. Visual observations and Raman measurements revealed that ethane hydrates can be present as a metastable state at pressures lower than the dissociation pressures of the three components: ice, hydrate, and free gas. However, they decompose into liquid water and gas phases once the system pressure drops to the equilibrium boundary for supercooled water, hydrate, and free gas. Structural analyses of obtained Raman spectra indicate that structures of the metastable hydrates and liquid water from the hydrate decay are fundamentally identical to those of the stable hydrates and supercooled water without experience of the hydration. These results imply a considerably high energy barrier for the direct hydrate-to-ice transition. Water solidification, probably induced by dynamic nucleation, was also observed during melting.     

Time-resolved in situ neutron diffraction studies of gas hydrate: transformation of structure II (sII) to structure I (sI).

We report the in situ observation from diffraction data of the conversion of a gas hydrate with the structure II (sII) lattice to one with the structure I (sI) lattice. Initially, the in situ formation, dissociation, and reactivity of argon gas clathrate hydrate was investigated by time-of-flight neutron powder diffraction at temperatures ranging from 230 to 263 K and pressures up to 5000 psi (34.5 MPa). These samples were prepared from deuterated ice crystals and transformed to hydrate by pressurizing the system with argon gas. Complete transformation from D(2)O ice to sII Ar hydrate was observed as the sample temperature was slowly increased through the D(2)O ice melting point. The transformation of sII argon hydrate to sI hydrate was achieved by removing excess Ar gas and exposing the hydrate to liquid CO(2) by pressurizing the Ar hydrate with CO(2). Results suggest the sI hydrate formed from CO(2) exchange in argon sII hydrate is a mixed Ar/CO(2) hydrate. The proposed exchange mechanism is consistent with clathrate hydrate being an equilibrium system in which guest molecules are exchanging between encapsulated molecules in the solid hydrate and free molecules in the surrounding gas or liquid phase.     

Methane hydrate dissociation above 0 °C and below 0 °C

The kinetic data of methane hydrate dissociation at various temperatures and pressures were measured in a sapphire cell apparatus by depressurizing method. When the temperature was higher than 0 °C, the experimental results showed that the hydrate dissociation rate was controlled by intrinsic dissociation reaction. When the temperature was lower than 0 °C, water generated from the hydrate dissociation would transform into ice rapidly at the surface of hydrate crystal. The released gas diffused from the hydrate and ice mixture to the bulk of gas phase. With the hydrate continuous dissociation, the boundary of ice–hydrate moved toward water/ice phase. The hydrate dissociation was controlled by gas diffusion, and the hydrate dissociation process was treated as a moving boundary problem. Corresponding kinetic models for hydrate dissociation were established and good agreements with experimental data were achieved.     

Formation of methane hydrate from polydisperse ice powders

Neutron diffraction runs and gas-consumption experiments based on pressure-volume-temperature measurements are conducted to study the kinetics of methane hydrate formation from hydrogenated and deuterated ice powder samples in the temperature range of 245-270 K up to high degrees of transformation. An improved theory of the hydrate growth in a polydisperse ensemble of randomly packed ice spheres is developed to provide a quantitative interpretation of the data in terms of kinetic model parameters. This paper continues the research line of our earlier study which was limited to the monodisperse case and shorter reaction times (Staykova et al., 2003). As before, we distinguish the process of initial hydrate film spreading over the ice particle surface (stage I) and the subsequent hydrate shell growth (stage II) which includes two steps, i.e., an interfacial clathration reaction and the gas and water transport (diffusion) through the hydrate layer surrounding the shrinking ice cores. Although kinetics of hydrate formation at stage II is clearly dominated by the diffusion mechanism which becomes the limiting step at temperatures above 263 K, both steps are shown to be essential at lower temperatures. The permeation coefficient D is estimated as (1.46 +/- 0.44) x 10(-12) m2/h at 263 K with an activation energy Q(D) approximately 52.1 kJ/mol. This value is close to the energy of breaking hydrogen bonds in ice Ih and suggests that this process is the rate-limiting step in hydrate formation from ice in the slower diffusion-controlled part of the reaction.     

多孔介质中甲烷水合物的分解特性

利用定容降压方法测定了在不同多孔介质中甲烷水合物的分解实验数据, 所使用的多孔介质平均孔径分别为9.03, 12.95, 17.96和33.20 nm, 其中孔径为12.95 nm的多孔介质采用了3个粒径范围, 分别为0.105～0.150, 0.150～0.200和0.300～0.450 mm; 其它孔径的多孔介质的粒径范围为0.105～0.150 mm. 在封闭的条件下测定了不同温度与不同初始生成压力下甲烷水合物的分解实验数据(实验温度范围为269.15～278.15 K, 初始生成压力范围为4.1～11.0 MPa), 结果表明, 水合物的分解速度随着初始生成压力的增加和水浴温度的降低而升高, 也随孔径的增加而升高, 但随多孔介质粒径的增大而降低. 在孔径较大和分解温度较低时, 多孔介质中水合物分解引起的温度降低会使水结冰, 从而减缓水合物的分解速度.     

Effective control of gas hydrate dissociation above the melting point of ice

Direct measurements of the dissociation behaviors of pure methane and ethane hydrates trapped in sintered tetrahydrofuran hydrate through a temperature ramping method showed that the tetrahydrofuran hydrate controls dissociation of the gas hydrates under thermodynamic instability at temperatures above the melting point of ice.     

Tetrahydrofuran hydrate decomposition characteristics in porous media

Many tetrahydrofuran (THF) hydrate properties are similar to those of gas hydrates. In the present work THF hydrate dissociation in four types of porous media is studied. THF solution was cooled to 275.15 K with formation of the hydrate under ambient pressure, and then it dissociated under ambient conditions. THF hydrate dissociation experiments in each porous medium were conducted three times. Magnetic resonance imaging (MRI) was used to obtain images. Decomposition time, THF hydrate saturation and MRI mean intensity (MI) were measured and analyzed. The experimental results showed that the hydrate decomposition time in BZ-4 and BZ-3 was similar and longer than that in BZ-02. In each dissociation process, the hydrate decomposition time of the second and third cycles was shorter than that of the first cycle in BZ-4, BZ-3, and BZ-02. The relationship between THF hydrate saturation and time is almost linear.     

The role of tropospheric ice surfaces in the elimination of the CFC substitute, trifluoroethanol

This work provides uptake results of CF(3)CH(2)OH on ice over the temperature range 203-223 K using a coated wall flow tube coupled to mass spectrometric detection. For experiments over pure ice, the adsorption was fully reversible and the data could be described in terms of the Langmuir isotherm for the range of concentrations and temperatures studied. For this temperature range, ΔH°(ads) = -46 ± 16 kJ mol(-1) was obtained (error is 2σ + 5%). For experiments on doped ice with nitric acid over the temperature range 203-223 K, the number of adsorbed molecules was slightly lower than over pure ice. At temperatures above 231 K, the extent of the reversible uptake of CF(3)CH(2)OH is enhanced in the presence of nitric acid due to coexistence of a liquid solution phase. Under such conditions the obtained solubility data follow Henry's law. Although pure ice and acid doped water surfaces do not permanently scavenge CF(3)CH(2)OH, the partitioning of CF(3)CH(2)OH between the gas phase and aqueous condensed phases may play a role as reservoirs or as a means of transport in the troposphere.     

Methane clathrate: CH(4) quantum rotor state dependent rattling potential

In methane hydrate the dominant peak in the density of states above 3 meV represents a rattling mode of the guest molecule CH(4) in the large ice cages. This mode shifts from 6.7 meV at T=4.5 K to T=30 K to 7.14 meV with conversion of CH(4) guest molecules into the tunneling ground state. The less symmetric angular density distribution PsiPsi(*) in the excited rotational state compared to the ground state allows the methane to fit better in the orientation dependent cage potential surface. This leads to a larger average distance to the cage-forming molecules with a weaker potential and a reduced rattling energy. A two state single particle model with characteristic rattling energies of 5.20 meV for pure T-methane and 7.3 meV for pure A-methane weighted by the population factors can fit the data.     

Natural gas pyrolysis in double-walled reactor tubes using thermal plasma or concentrated solar radiation as external heating source

The thermal pyrolysis of natural gas as a clean hydrogen production route is examined.The concept of a double-walled reactor tube is proposed and implemented.Preliminary experiments using an external plasma heating source are carded out to validate this concept.The results point out the efficient CH4 dissociation above 1850 K (CH4 conversion over 90%) and the key influence of the gas residence time.Simulations are performed to predict the conversion rate of CH4 at the reactor outlet,and are consistent with experimental tendencies.A solar reactor prototype featuring four independent double-walled tubes is then developed.The heat in high temperature process required for the endothermic reaction of natural gas pyrolysis is supplied by concentrated solar energy.The tubes are heated uniformly by radiation using the blackbody effect of a cavity-receiver absorbing the concentrated solar irradiation through a quartz window.The gas composition at the reactor outlet,the chemical conversion of CH4,and the yield to H2 are determined with respect to reaction temperature,inlet gas flow-rates,and feed gas composition.The longer the gas residence time,the higher the CH4 conversion and H2 yield,whereas the lower the amount of acetylene.A CH4 conversion of 99% and H2 yield of about 85% are measured at 1880 K with 30% CH4 in the feed gas (6 L/min injected and residence time of 18 ms).A temperature increase from 1870 K to 1970 K does not improve the H2 yield.     

Reanalysis and New Measurements of N(2) and CH(4) Adsorption on Ice and Snow

Numerous literature data indicate that the mean heat of adsorption of a monolayer of N(2) (DeltaQ(N(2))) on ice or snow at 77.15 K, determined by volumetric methods, is highly variable, suggesting that ice surface properties strongly depend on its mode of formation and its thermal history. Less numerous data on CH(4) adsorption show smaller variations of DeltaQ(CH(4)). If such variations are real, the extrapolation to atmospheric chemistry models of adsorption parameters measured on laboratory-made ice may be unwarranted. We have measured CH(4) adsorption on variable amounts of a crushed ice sample, to show that when the total surface area of the sample is below a threshold value, DeltaQ(CH(4)) decreases. We identify the cause of this artifact as an error in the molar budget, because the temperature gradient in the tube connecting the introduction and expansion volumes is not taken into account. Performing an adequate molar budget suppresses this artifact, except for ice samples with very small total surface areas, where the resolution of the manometer becomes a limiting factor and a further decrease in DeltaQ(CH(4)) is observed. Error in DeltaQ(gas) results in large errors in surface area, and we suggest that the value of DeltaQ(gas) obtained can be used to test the reliability of the surface area measurement. Copyright 2000 Academic Press.     

Hydrate kinetics study in the presence of nonaqueous liquid by nuclear magnetic resonance spectroscopy and imaging

The dynamics of methane hydrate growth and decomposition were studied by nuclear magnetic resonance (NMR) spectroscopy and imaging (MRI). Three well-known large molecule guest substances (LMGS) were used as structure H hydrate formers: 2,2-dimethylbutane (NH), methylcyclohexane (MCH), tert-butyl methyl ether (TBME). In addition, the impact of a non-hydrate former (n-heptane/nC7) was studied. The methane diffusion and hydrate growth were monitored by recording the 2H NMR spectra at 253 K and approximately 4.5 MPa for 20 h. The results revealed that methane diffuses faster in TBME and NH, slower in nC7, and slowest in MCH. The TBME system gives the fastest hydrate formation kinetics followed by NH, MCH, and nC7. The conversion of water into hydrate was also observed. The imaging study showed that TBME has a strong affinity toward ice, which is not the case for the NH and MCH systems. The degree of ice packing was also found to affect the LMGS distribution between ice particles. Highly packed ice increases the mass transfer resistance and hence limits the contact between LMGS and ice. It was also found that "temperature ramping" above the ice point improves the conversion significantly. Finally, hydrates were found to dissociate quickly within the first hour at atmospheric pressure and subsequently at a much slower rate. Methane dissolved in LMGS was also seen. The residual methane in hydrate phase and dissolved in LMGS phase explain the faster kinetics during hydrate re-formation.     

Hydrate film growth on the surface of a gas bubble suspended in water

The lateral film growth rate of CH4, C2H4, CO2, CH4 + C2H4, and CH4 + C3H8 hydrates in pure water were measured at four fixed temperatures of 273.4, 275.4, 277.4, and 279.4 K by means of suspending a single gas bubble in water. The results showed that the lateral growth rates of mixed-gas CH4 + C2H4 hydrate films were slower than that of pure gas (CH4 or C2H4) for the same driving force and that of mixed-gas CH4 + C3H8 hydrate film growth was the slowest. The dependence of the thickness of hydrate film on the driving force was investigated, and it was demonstrated that the thickness of hydrate film was inversely proportional to the driving force. It was found that the convective heat transfer control model reported in the literature could be used to formulate the lateral film growth rate v(f) with the driving force DeltaT perfectly for all systems after introduction of the assumption that the thickness of hydrate films is inversely proportional to the driving force DeltaT; i.e., v(f) = psiDeltaT(5/2) is correct and independent of the composition of gas and the type of hydrate. The thicknesses of different gas hydrate films were estimated, and it is demonstrated that the thicknesses of mixed-gas hydrate films were thicker than those of pure gases, which was qualitatively consistent with the experimental result.     

Photodissociation and photoisomerization of alpha-fluorotoluene and 4-fluorotoluene in a molecular beam

The photodissociation of jet-cooled alpha-fluorotoluene and 4-fluorotoluene at 193 and 248 nm was studied using vacuum ultraviolet (vuv) photoionization/multimass ion imaging techniques as well as electron impact ionization/photofragment translational spectroscopy. Four dissociation channels were observed for alpha-fluorotoluene at both 193 and 248 nm, including two major channels C6H5CH2F-->C6H5CH2 (or C7H7)+F and C6H5CH2F-->C6H5CH (or C7H6)+HF and two minor channels C6H5CH2F-->C6H5CHF+H and C6H5CH2F-->C6H5+CH2F. The vuv wavelength dependence of the C7H7 fragment photoionization spectra indicates that at least part of the F atom elimination channel results from the isomerization of alpha-fluorotoluene to a seven-membered ring prior to dissociation. Dissociation channels of 4-fluorotoluene at 193 nm include two major channels C6H4FCH3-->C6H4FCH2+H and C6H4FCH3-->C6H4F+CH3 and two minor channels C6H4FCH3-->C6H5CH2 (or C7H7)+F and C6H4FCH3-->C6H5CH (or C7H6)+HF. The dissociation rates for alpha-fluorotoluene at 193 and 248 nm are 3.3 x 10(7) and 5.6 x 10(5) s(-1), respectively. The dissociation rate for 4-fluorotoluene at 193 nm is 1.0 x 10(6) s(-1). An ab initio calculation demonstrates that the barrier height for isomerization from alpha-fluorotoluene to a seven-membered ring isomer is much lower than that from 4-fluorotoluene to a seven-membered ring isomer. The experimental observed differences of dissociation rates and relative branching ratios between alpha-fluorotoluene and 4-fluorotoluene may be explained by the differences in the six-membered ring to seven-membered ring isomerization barrier heights, F atom elimination threshold, and HF elimination threshold between alpha-fluorotoluene and 4-fluorotoluene.     

The conversion process of hydrocarbon hydrates into CO2 hydrates and vice versa: thermodynamic considerations

Microscopy, confocal Raman spectroscopy and powder X-ray diffraction (PXRD) were used for in situ investigations of the CO(2)-hydrocarbon exchange process in gas hydrates and its driving forces. The study comprises the exposure of simple structure I CH(4) hydrate and mixed structure II CH(4)-C(2)H(6) and CH(4)-C(3)H(8) hydrates to gaseous CO(2) as well as the reverse reaction, i.e., the conversion of CO(2)-rich structure I hydrate into structure II mixed hydrate. In the case of CH(4)-C(3)H(8) hydrates, a conversion in the presence of gaseous CO(2) from a supposedly more stable structure II hydrate to a less stable structure I CO(2)-rich hydrate was observed. PXRD data show that the reverse process requires longer initiation times, and structural changes seem to be less complete. Generally, the exchange process can be described as a decomposition and reformation process, in terms of a rearrangement of molecules, and is primarily induced by the chemical potential gradient between hydrate phase and the provided gas phase. The results show furthermore the dependency of the conversion rate on the surface area of the hydrate phase, the thermodynamic stability of the original and resulting hydrate phase, as well as the mobility of guest molecules and formation kinetics of the resulting hydrate phase.