STUDY ON OXID TIVE COUPLING OF METHANE Ⅱ.CATALY TIC PERFORMANCE AND CHARACTERIZATION OF TiO_2-BASED CATALYSTS

The catalytic performance of Mn/TiO_2,La-Mn/TiO_2,Li-La-Mn/TiO_2 etc for the oxidetive coupling of methane(OCM)was investignted.Thecatalysta were cheracterised with X-ray diffraction(XRD)and X-rayphotoelectron spectroscopy(XPS).The results reveal that catalyst Li-La-Mn/TiO_2 exhibits high activity and C_2 selectivity;Ti in this catalyst exists asTi~( 4) state;Li can promote the formation of lanthanum tituate via theinteraction between La and TiO_2;the formed La_2Ti_2O_7 and La_4Ti_9O_(24) aredistributed in the inner surface layer and Mn exists in outer surface layer in lowvalence states.The high activity and C_2 selectivity of catalyst Li-La-Mn/TiO_2are intimately related to the valence states of Mn,Li,La and theirdistribution on the catulyst surface layer.     

STUDIES OF MULTICOMPONENT COMPLEX OXIDE CATALYSTS FOR OXIDATIVE COUPLING OF METHANE VI.SURFACE BASICITY AND SURFACE ACTIVE OXYGEN SPECIES OF LiTi_xLa_(1-x)O_2 λ MULTICOMPONENT OXIDE CATALYSTS

The surface basicity of Ti-La-Li multicoinponent oxides has been investigated by means of CO2-TPD. The experiment results show that C2 (C2H6 C2H4) selectivity is related to surface basic strength. The surface active oxygen species have also been characterized by means of XPS, O2-TPD and so on. It has been indicated that C2 selectivity and CH4 conversion are correlated with lattice oxygen and the adsorbed oxygen on the surface of the catalyst respectively In the O2-TPD experiments, it has also been found that there are three kinds of oxygen species on the surface of the series catalvsts, which are a (100℃ 750℃) Among them α-oxvgen causes deep oxidation whileβand γ oxygen species are related to oxidalive coupling of methane (OCM).     

Plasma-chemical decomposition of methane during diamond synthesis

Using a mass spectrometric sampling method, we have observed the decomposition of CH₄ in an rf plasma usedfor diamond deposition. The gas samples were extracted through an orifice located downstream of the plasma zone and analyzed online. For the experiments a dilute mixture of H₂ and CH₄ containing 0.1–3% CH₄ has been used. CH₄ is converted to C₂H₂ and C₂H₄ quantitatively. Small amounts of heavier hydrocarbons are formed. A comparison of the experimental results with a recent kinetic model treating a purely thermal environment is made and the differences between our experiment and the model are explained. The role of acetylene as a species formed in an atmosphere rich in atomic hydrogen is proposed. The electron impact dissociation process is suggested as the rare-determining step in the plasma-chemical decomposition of methane.     

Methane production from synthesis gas using a mixed culture ofR. rubrum M. barkeri,and M. formicicum

The components of synthesis gas, CO, H₂, and CO₂, may be converted into CH₄ biologically through either acetate or H₂/CO₂ as intermediates. Of these two routes, conversion through H₂/CO₂ is preferred. This paper presents results of mixed-culture studies employing the photosynthetic bacteriumR. rubrum for converting CO to CO₂ and H₂ by the water gas shift reaction and two methanogens,M. formicicum andM. barkeri, for converting CO₂ and H₂ into CH₄. Results are presented for triculture operation in two types of reactors, the packed bubble column and the trickle-bed reactor.     

Methane conversion to C2 hydrocarbons in solid electrolyte membrane reactors

Solid electrolyte membrane reactors (SEMRs) have been used to both study and influence catalytic reaction rates. Methane coupling is the reaction most thoroughly and intensively studied in these membrane reactors. In the last 20 years, oxygen ion (O²⁻), proton (H⁺) and mixed (O²⁻-e⁻, H⁺-e⁻) conducting membranes have been tested in order to maximize the conversion of methane to C₂ compounds. The present review contains the fundamental operating principles of the various SEMR types and their applications in this reaction. The difficulties that should be overcome in order to promote this SEMR process to an industrial scale are discussed.     

瓦斯煤尘爆炸火焰光谱的实验研究

本文概述了瓦斯煤尘爆炸火焰光谱实验研究的重要性,我们在弱爆炸和探测器小视场角的条件下,利用自己研制的多波道仪,在一端开口的Φ200cm×2900cm大型管道里,得到了CH4、空气和煤尘的混合物在不同状态下,特征波长λ等于0.8875、1.000、1.505、2.801和4.346微米(μ)的绝对辐射强度及其有关的变化规律,对结果进行了分析讨论,并与国外实验结果进行了对比,根据测量λ=4.346μ绝对辐射强度和我们选择的黑体辐射模型,获得了爆炸火焰的温度,该项研究不仅在工业中具有重要意义,而且对燃烧和化学动力学的研究也具有参考价值。     

Analysis of the CH3D Nonad from 2000 to 3300 cm

As part of the simultaneous analysis of line positions and intensities of the first two polyads of monodeuterated methane, the results achieved for the region 3-5 μm are reported. It involves the three highest fundamentals, (ν₁, ν₂, ν₄), overlapped by overtone (2ν₃, 2ν₅, 2ν₆) and combination (ν₃+ν₆, ν₃+ν₅, ν₅+ν₆) bands. The theoretical model was based on the global tensorial model implemented in the MIRS package. Some 10 000 line positions and 2400 line intensities have been modeled to ±0.000 88 cm⁻¹ and ±3.6% respectively, using measurements obtained at 0.0056 and 0.011 cm⁻¹ resolution with the Fourier transform spectrometer at National Solar Observatory located at Kitt Peak. The strongest band in this polyad is ν₄(E) at 3016.7 cm⁻¹ with a strength of 6.3×10⁻¹⁸ cm⁻¹/(molecule cm⁻²) at 296 K; the weakest band is 2ν₃(E) at 2597.7 cm⁻¹ with a strength of 1.9×10⁻²⁰ cm⁻¹/(molecule cm⁻²) at 296 K. The total calculated absorption arising from the CH₃D nonad is 8.95×10⁻¹⁸ cm⁻¹/(molecule cm⁻²) at 296 K.     

Determination of 13C/12C-Ratios in Rumen Produced Methane and CO2 of Cows,Sheep and Camels

Abstract

Naturally produced methane shows different δ¹³C-values with respect to its origin, e.g., geological or biological. Methane-production of ruminants is considered to be the dominant source from the animal kingdom. Isotopic values of rumen methane—given in literature—range between ?80‰ and -50‰ and are related to feed composition and also sampling techniques. Keeping cows, camels and sheep under identical feed conditions and sampling rumen gases via implanted fistulae we compared δ_PDB ¹³C-values of methane and CO₂ between the species. Referring to mean values obtained from 4 or 5 samples at different times of 11 animals (n = 47) we calculated δ_PDB ¹³C-medians resulting in small but not significant differences within and significant differences between the species for CO₂ and methane. The δ_PDB ¹³C-differences between methane and CO₂ were statistically equal within and also between the species. Therefore a linear regression of methane values on CO₂ is appropriate and leads to: δ_PDB ¹³C(methane)‰ = 1,57 * δ_PDB ¹³C(CO₂)‰-47‰ with a correlation coefficient of r = 0,87.     

Numerical study of the effect of turbulence on rate of reactions in the MILD combustion regime

In this paper, the importance of fluctuations in flow field parameters is studied under MILD combustion conditions. In this way, a turbulent non-premixed CH₄+H₂ jet flame issuing into a hot and deficient co-flow air is modeled using the RANS Axisymmetric equations. The modeling is carried out using the EDC model to describe the turbulence-chemistry interaction. The DRM-22 reduced mechanism and the GRI2.11 full mechanism are used to represent the chemical reactions of H₂/methane jet flame. Results illustrate that although the fluctuations in temperature field are small and the reaction zone volume are large in the MILD regime, the fluctuations in temperature and species concentrations are still effective on the flow field. Also, inappropriate dealing with the turbulence effect on chemistry leads to errors in prediction of temperature up to 15% in the present flame. By decreasing of O₂ concentration of hot co-flow air, the effect of fluctuations in flow field parameters on flame characteristics are still significant and its effect on species reaction rates does not decrease. On the other hand, although decreasing of jet inlet Reynolds number at constant inlet turbulence intensity addresses to smaller fluctuations in flow filed, it does not lead to lower the effect of turbulence on species distribution and temperature field under MILD combustion conditions.     

Methane dissolution inside bulk or porous-medium-confined water at near-hydrate equilibrium conditions

In this study, we perform a series of mass-balance-type calculations, in order to estimate the minimum volume of liquid water required to dissolve completely a single methane gas bubble, located inside different types of domains that are near or under hydrate equilibrium pressure/temperature conditions. We examine the case of methane bubble dissolution in the bulk, along with the cases of methane bubble dissolution within simple/regular networks of pores, where all pores have the same size. In our calculations, we consider experimental values for the equilibrium solubilities of methane in water, along the hydrate-forming line, as well as, values obtained from predictive tools that are based on different thermodynamic models. The effect of aqueous NaCl solutions on the results is also investigated. As a result of the relatively low solubility of methane in water, large volumes of water are required for complete dissolution of a methane bubble.