基于Raman光谱技术的瓦斯混合气水合过程定量分析

瓦斯水合物微观晶体结构研究对水合分离技术具有重要理论意义。利用Raman光谱技术对三种含高浓度CO₂瓦斯混合气水合反应过程进行在线观测,并对水合物相Raman光谱图进行分析,获取了瓦斯水合物不同生长阶段大、小孔穴占有率,同时利用van der Waals与Platteeuw热力学统计模型间接获得水合指数等晶体结构信息。结果表明,瓦斯水合物孔穴占有率及水合指数在水合物不同生长阶段未发生较大变化,水合物相中大孔穴几乎被客体分子填满,CO₂与CH₄分子共同占据大孔穴,但CO₂占绝大多数,达到78.58%~94.09%,CH₄分子仅为4.52%~19.12%,这主要是由于两种分子间存在竞争关系且气样中CO₂浓度明显高于CH₄,大孔穴占有率维持在97.70%~98.68%;小孔穴占有率为17.93%~82.41%,占有率普遍偏低,且仅有CH₄分子;随气样中CH₄浓度增加,CH₄在大、小孔穴中的占有率均有所增加,且CH₄分子在大孔穴中的占有率均明显低于在小孔穴中占有率;水合物生长不同阶段水合指数为6.13~7.33,随气样中CH₄浓度的增加,小孔穴占有率有所增加,致使水合指数随之降低;由于瓦斯水合物生长分布不均匀,三种气样对应的不同生长阶段水合指数均呈不规则变化。     

Studies of catalytic process of complete oxidation of methane by SSITKA method

This paper presents the results obtained by means of the steady state isotopic transient kinetic analysis for complete methane oxidation over the Pd(PdO)Al₂O₃ catalyst. The average surface life-time and surface concentration of methane and carbon dioxide were determined. It was found out that on the palladium catalyst there are adsorbed small amounts of methane (which does not take part in the process of oxidation) only at the temperature corresponding to the starting point of methane oxidation. Additionally, in the steady state of methane oxidation on the palladium catalyst there are present two different kinds of carbon dioxide: short- and long-resided on the catalyst surface. The average surface life-time of both kinds of carbon dioxide decreases with temperature. The surface concentration of long-resided carbon dioxide increases with temperature whereas the small maximum at about 380 °C is noticed for the surface concentration of short-resided carbon dioxide.     

Using magnetic resonance imaging to monitor CH4 hydrate formation and spontaneous conversion of CH4 hydrate to CO2 hydrate in porous media

Magnetic resonance imaging was used to monitor and quantify methane hydrate formation and exchange in porous media. Conversion of methane hydrate to carbon dioxide hydrate, when exposed to liquid carbon dioxide at 8.27 MPa and ∼4°C, was experimentally demonstrated with MRI data and verified by mass balance calculations of consumed volumes of gases and liquids. No detectable dissociation of the hydrate was measured during the exchange process.     

Density functional theory study of structural stability for gas hydrate

Using the first-principles method based on the density functional theory(DFT),the structures and electronic properties of different gas hydrates(CO_2,CO,CH_4,and H_2) are investigated within the generalized gradient approximation.The structural stability of methane hydrate is studied in this paper.The results show that the carbon dioxide hydrate is more stable than the other three gas hydrates and its binding energy is-2.36 e V,and that the hydrogen hydrate is less stable and the binding energy is-0.36 e V.Water cages experience repulsion from inner gas molecules,which makes the hydrate structure more stable.Comparing the electronic properties of two kinds of water cages,the energy region of the hydrate with methane is low and the peak is close to the left,indicating that the existence of methane increases the stability of the hydrate structure.Comparing the methane molecule in water cages and a single methane molecule,the energy of electron distribution area of the former is low,showing that the filling of methane enhances the stability of hydrate structure.     

On injection of hydrate-forming gas into a gas-saturated snowy agglomerate while transition through the ice melting point

The paper considers the process of injection of hydrate-forming gas (methane) into a snowy agglomerate (ini-tially saturated with methane). The self-similar problem statement demonstrates that if the warm gas (T_e > 0 °C) is injected under a high pressure (p_e ≥ p_*, where the critical values are found from the initial temperature T₀, pressure p₀, volumetric snow saturation S_i0, and permeability of snow) into the filtration zone with phase transition, this produces four characteristic zones: the nearest zone with all snow transformed into hydrate, therefore, the aggregate filled only with gas and hydrate, the two intermediate zones where gas, snow or water and hydrate are in phase equilibrium state, and the distant zone filled only with gas and snow. The obtained analytical and numerical solutions give an analysis of the influence of key input parameters like initial state of the aggregate, gas injection rate, and its temperature, on the structure and the length of four filtration zones.     

Photoacoustic monitoring of gases using a novel laser source tunable around 2.5 μm

We present the first spectroscopic measurements using a tunable solid state Cr²+:ZnSe laser emitting at wavelengths between 2.2 μm and 2.8 μm. Photoacoustic measurements on various gases such as methane, carbon monoxide, carbon dioxide, water vapour, nitrous oxide, and ambient air were carried out. In this paper, we present measurements on methane, nitrous oxide, and ambient air. The deduced detection limits are in the low ppm or sub-ppm range, e.g., 0.2 ppm for carbon dioxide, 0.8 ppm for methane and 2.7 ppm for carbon monoxide.     

不同笼占据率Ⅰ型甲烷水合物结构和光学性质的第一性原理研究

本文基于第一性原理计算,对三种不同结构的Ⅰ型甲烷水合物进行弛豫,得到优化后的结构、电子态密度及光学性质,通过对结果的分析揭示不同笼子占据率对水合物的结构和相关性质的影响。这三种结构分别为:(cI)只有一个大笼未被占据;(cII)只有一个小笼未被占据;(cIII)每个笼子都被甲烷分子占据。结果显示,cIII是最稳定的,因为它有完美的晶体结构;cII和cI相对较不稳定,其中cI在缺失一个甲烷分子的情况下,结构出现了较大的变形,这导致它成为三种情况中最不稳定的结构;相反,同样缺失了一个甲烷分子的cII的结构变形就很小。cII和cI的体积变化分别是0.56%和2.1%,cII的电子态密度和能带几乎与cIII的一致,而cI的则与前两者差别很大。计算结果表明,相对于电子转移,质子无序对水合物的介电常数的影响更为主要;甲烷水合物只对紫外光有响应,无论结构和占据率差异如何,甲烷水合物都具有相近的光学性质。本文的结果证明,缺失一个甲烷分子,对cII造成的影响很小,其晶体结构、介电常数和光学性质与cIII的一致,然而同样缺失一个甲烷分子的cI的结构及性质却出现了巨大变化。这些结果可为水合物探测提供有价值的参考。     

The AC monitoring of a mixed conducting Li-Ni-Co-O catalyst during temperature programmed reactions

The temporal analysis of effluent species with temperature linearly increasing with time for two reactions, carbon dioxide hydrogenation (250° to 600°C) and the oxidative coupling of methane (400° to 800°C) have been studied. A non-stoichiometric, mixed-oxide catalyst, Li_0.9Ni_0.5Co_0.5O_2-δ, containing both mobile ions and electrons at elevated temperatures was investigated. The exit gas stream was monitored by using the multiple-ion monitoring facility of a quadrupole mass spectrometer. The AC electrical characteristics of the catalyst pellet between 100 Hz and 1 MHz were simultaneously monitored in-situ. A clear correlation between catalytic behaviour and electrical properties was obtained. Frequency-dependent AC losses due to surface dipole effects were dominant during phases of strong chemisorption and reaction, whilst reversion to thermally activated behaviour occurred during times of reduced chemical activity. In the case of carbon dioxide hydrogenation, the catalyst becomes partially reduced as a result of the chemical reaction, as shown by the changes in conductance-temperature-frequency characteristics. The original oxidised state could be recovered by re-oxidation at 700°C for 1 hour in air. For the partial oxidation of methane, mobile lattice oxygen participates in the reaction. The temporary changes in the state of oxidation of the catalyst during this reaction are correlated with changes in the electrical characteristics of the material. Paper presented at the 3rd Euroconference on Solid State Ionics, Teulada, Sardinia, Italy     

Theoretical investigation of structures and compositions of double neon-methane clathrate hydrates,depending on gas phase composition and pressure

The region of existence of neon clathrate hydrates is an actual problem of hydrate chemistry. The current work presents theoretical study of the equilibrium formation conditions of pure neon clathrate hydrates and double clathrate hydrates of neon-methane mixture. The structures and properties of double clathrate hydrates were described within the scope of the previously developed molecular clathrate hydrate model that takes into account the influence of guest molecules on the host lattice, interaction of guest molecules between themselves, and the possibility of multiple filling of host lattice cages by guest molecules. The model makes it possible to find an equilibrium state and thermodynamic properties of clathrate hydrates at given values of p and T. In the present work, we considered the properties of double clathrate hydrates in the range of pressures from 0 to 4 kbar at 250 K. The results of modeling have shown that the mass fraction of neon in double clathrate hydrate of Ne and CH₄ mixture of cubic structure I (sI) can reach 26%, and 22.5% in double hydrate of cubic structure II (sII) even at a low methane concentration (1%) in gas phase, at high pressure. It is shown that in double clathrate hydrates of the Ne and CH₄ mixture at high pressures, phase transition sII-sI can occur.     

Interaction induced Raman light scattering as a probe of the local density structure of binary supercritical solutions

Interaction induced Raman light scattering is presented as a unique tool for the understanding of solvation processes from the solute's point of view in weakly interacting solute-solvent systems. A review of pertinent literature shows that this technique should be useful at least in single-phase binary mixtures such as supercritical solutions. Methane is used here as a probe molecule at 10mol% concentration (as the solute) and 90mol% CO and CO₂ are the solvents. The light scattering results, i.e., the dependence of the anisotropic intensities divided by density (I/d) on the density, are interpreted by use of the Duh-Haymet-Henderson closure (bridge) function of the Ornstein-Zernike integral equation. These data, together, are examined in the context of known supercritical solution thermodynamics and statistical mechanical results. It is shown that the light scattering I/d data versus density yield maxima in both attractive and repulsive solute-solvent systems. The local number density maxima were found near these same densities by the integral equation calculations for both methane + carbon monoxide or carbon dioxide using only Lennard-Jones single-centre parameters as input. The methane + carbon monoxide system is identified as weakly attractive (augmenting), whereas the methane + carbon dioxide system is identified as repulsive (avoidance).     

Processes of dissolution and hydrate formation behind a shock wave in a liquid with carbon dioxide bubbles

The processes of dissolution and hydrate formation behind the front of a shock wave of moderate amplitude in water with carbon dioxide bubbles are studied experimentally at various initial static pressures. The influence of a surface-active substance (SAS) in the medium on the processes of dissolution and hydrate formation behind the shock wave is investigated. It is demonstrated that behind a shock wave of moderate amplitude in a liquid with carbon dioxide bubbles an intensive process of dissolution and hydrate formation takes place, resulting in complete disappearance of the gas phase in a matter of a few milliseconds. The presence of an SAS in the medium does not significantly influence the processes of dissolution and hydrate formation within the investigated periods of time.     

Experimental study of incomplete oxidation of methane in a ring channel

Chemical transformations at incomplete methane oxidation in the air medium were studied experimentally at reaction activation on the wall of an annular microchannel. Methane was oxidized incompletely on a rhodium catalyst deposited on an inner wall of the channel. Concentrations of the products of chemical transformations were measured in the outlet gas mixture for different reactor temperatures and stay times. We have determined the range of channel wall temperatures and stay times of the mixture corresponding to an increase in the portion of hydrogen and carbon dioxide indicating transition from predominant methane combustion to cascade chemical reactions with activation of steam and carbon dioxide methane conversions. It is shown that the kinetic model of chemical transformations of methane in the air medium depends significantly on the temperature of channel walls and stay time of the mixture. The effect of outer diffusion deceleration on the rate of chemical transformations at incomplete methane oxidation under the strained conditions is determined. The work was financially supported by the Russian Foundation for Basic Research (Grant No. 05-08-65526).     

Structural and Parametric Optimization of S–CO2 Nuclear Power Plants

The transition to the use of supercritical carbon dioxide as a working fluid for power generation units will significantly reduce the equipment′s overall dimensions while increasing fuel efficiency and environmental safety. Structural and parametric optimization of S–CO₂ nuclear power plants was carried out to ensure the maximum efficiency of electricity production. Based on the results of mathematical modeling, it was found that the transition to a carbon dioxide working fluid for the nuclear power plant with the BREST–OD–300 reactor leads to an increase of efficiency from 39.8 to 43.1%. Nuclear power plant transition from the Rankine water cycle to the carbon dioxide Brayton cycle with recompression is reasonable at a working fluid temperature above 455 °C due to the carbon dioxide cycle′s more effective regeneration system.     

Molecular dynamics simulations of carbon dioxide hydrate growth in electrolyte solutions of NaCl and MgCl2

Molecular dynamics simulations are performed to study the growth of carbon dioxide (CO₂) hydrate in electrolyte solutions of NaCl and MgCl₂. The kinetic behaviour of the hydrate growth is examined in terms of cage content, density profile, and mobility of ions and water molecules, and how these properties are influenced by added NaCl and MgCl₂. Our simulation results show that both NaCl and MgCl₂ inhibit the CO₂ hydrate growth. With a same mole concentration or ion density, MgCl₂ exhibits stronger inhibition on the growth of CO₂ hydrate than NaCl does. The growth rate of the CO₂ hydrate in NaCl and MgCl₂ solutions decreases slightly with increasing pressure. During the simulations, the Na⁺, Mg²⁺, and Cl^? ions are mostly excluded by the growing interface front. We find that these ions decrease the mobility of their surrounding water molecules, and thus reduce the opportunity for these water molecules to form cage-like clusters toward hydrate formation. We also note that during the growth processes, several 5¹²6³ cages appear at the hydrate/solution interface, although they are finally transformed to tetrakaidecahedral (5¹²6²) cages. Structural defects consisting of one water molecule trapped in a cage with its hydrogen atoms being attracted by two Cl^? ions have also been observed.     

Frontal polymerization of styrene under the conditions corresponding to the transition of the initial styrene-carbon dioxide to the supercritical state

The possibility and conditions of realization of the frontal polymerization of styrene-carbon dioxide mixtures with transition to the supercritical (SC) state are examined. A method for experimental determination of the conditions of transition of the mixture to the supercritical state is developed. The critical temperatures for various initial monomer-to-CO₂ ratios are determined. Numerical simulation of the thermal polymerization of styrene in a tubular reactor is performed. The temperature and concentration profiles along the length of the reactor corresponding to the transition of the styrene-carbon dioxide mixture to the SC state are calculated.     

Precursor radical recombination and its attendant effects on the surface of solids in a dissociated carbon dioxide medium

The atomic-hydrogen-initiated ejections of materials from the surface of solids (ZnS, Ni) preliminary treated with dissociated carbon dioxide are revealed. The glow of a crystalline phosphor and the dynamic effect of the reaction are observed in the dissociated carbon dioxide medium. It is found that the observed variations in the dynamic effect of the reaction are unrelated to changes in the reaction rate. These effects are used to elucidate the mechanism of heterogeneous radical recombination on the surface of solids (Al₂O₃, ZnS, Ni) in dissociated carbon dioxide. It is revealed that, under the experimental conditions, the reaction rate is independent of the chemisorbed radical concentration, because the reaction involves radicals entrapped into the precursor state with a short lifetime at the surface.     

Some thermodynamic processes of anthracite–carbon dioxide mixture in supercritical fluid state

In the context of the development of the catalyst regeneration procedure via supercritical fluid CO₂ extraction, some thermodynamic properties of the anthracene–carbon dioxide mixture in supercritical fluid state have been studied. Data on anthracene solubility in pure and modified (dimethyl sulfoxide, 5 wt %) supercritical carbon dioxide (SC–CO₂), the heat capacity of anthracene and its mixtures with carbon dioxide, and the heat of solution of anthracene in SC–CO₂ are presented. Anthracene solubility in SC–CO₂ is described satisfactorily using the Peng–Robinson equation of state.     

Fuel quality and operational issues for polymer electrolyte membrane (PEM) fuel cells

Polymer electrolyte membrane (PEM) fuel cells are susceptible to degradation due to the catalyst poisoning caused by CO present in the fuel above certain limits. Although the amount of CO in the fuel may be within the permissible limit, the fuel composition (% CO₂, CH₄, CO and H₂O) and the operating conditions of the cell (level of gas humidification, cell temperature and pressure) can be such that the equilibrium CO content inside the cell may exceed the permissible limit leading to a degradation of the fuel cell performance. In this study, 50 cm² active area PEM fuel cells were operated at 55–60 °C for periods up to 250 hours to study the effect of methane, carbon dioxide and water in the hydrogen fuel mix on the cell performance (stability of voltage and power output). Furthermore, the stability of fuel cells was also studied during operation of cells in a cyclic dead end / flow through configuration, both with and without the presence of carbon dioxide in the hydrogen stream. The presence of methane up to 10% in the hydrogen stream showed a negligible degradation in the cell performance. The presence of carbon dioxide in the hydrogen stream even at 1–2% level was found to degrade the cell performance. However, this degradation was found to disappear by bleeding only about 0.2% oxygen into the fuel stream.     

Desorption of carbon dioxide from small potassium niobate particles induced by the particles’ ferroelectric transition

The aim of this work is to understand surface properties of ferroelectric crystals related to gas adsorption. Various ferroelectric crystals involved in these studies readily adsorb carbon dioxide, thus our studies were centered on adsorption studies of this molecule. It has been claimed that a dipole moment is induced on carbon dioxide molecules that are near an oxide surface. Our experiments explored the possibility of a dipole-dipole interaction between the gas molecule and the ferroelectric oxide surface in order to explain its adsorption. We characterized the samples with scanning electron microscopy, X-ray diffraction and Raman spectroscopy. We determined the ferroelectric nature of the particles and studied the temperature-dependent phase transitions in small particles of KNbO₃ using Raman spectroscopy. We were able to correlate desorption of CO₂ from one surface state of KNbO₃ with the occurrence of the orthorhombic to tetragonal transition in KNbO₃ in particles of 1 μm size. This CO₂ surface site was not observed in KTaO₃, which does not show ferroelectricity at room temperature.     

Solution and hydrate formation behind a shock wave in liquid with nitrogen — carbon dioxide bubbles in a presence of surfactant

The processes of solution and hydrate formation behind a shock wave of moderate amplitude were studied experimentally in water with bubbles of nitrogen — carbon dioxide mixture at different initial static pressures in the medium and surfactant concentrations. It is shown that these bubbles do not affect significantly the processes of solution and hydrate formation behind a shock wave during the considered periods. The hypothesis about partial hydration of nitrogen from the gas mixture at intense formation of carbon dioxide hydrate was suggested for the conditions, when the pressure behind the wave is less than the equilibrium pressure of nitrogen hydrate formation at a given temperature. The work was financially supported by the President of RF (NSh-3417.2008.8) and Russian Foundation for Basic Research (Grant No. 06-08-00657).