热等离子体裂解天然气制备C2烃

采用氮气热等离子体来裂解天然气制备乙炔乙烯,着重研究了天然气转化率和乙炔、乙烯收率随氮气流量和天然气流量的变化.结果表明,天然气流量与氮气流量之比为11时,可得到较好的结果.当等离子体功率为15kW、天然气流量为3Nm3*h-1、氮气流量为3Nm3*h-1时得到最好的结果.这时天然气转化率为57%,乙炔、乙烯的收率分别为34%和9%;乙炔在反应气中的体积浓度为7.5%,与部分氧化法相似;扣除不参加反应的氮气,乙炔在气相产品中的体积浓度为13.2%,与热力学平衡计算结果基本符合.     

Radical Couplings as Key Steps for the Preparation of Derivatives of Nonactic Acid

Summary. Free radical couplings from furan, as cheap starting material, were studied in view of developing a rapid strategy en route to the synthesis of derivatives of nonactin. The chain containing the alcohol function was introduced in one or two steps in 86% yield. For the introduction of the second chain with the ester function two different coupling methods were tested. Starting from the advanced intermediates obtained nonactin derivatives can be prepared by catalytic hydrogenation of the furan ring.     

Non-linear approximations for natural convection in a horizontal annulus

Two different problems are proposed as approximations of the usual system modelling natural convection under the Oberbeck-Boussinesq assumptions. The error is evaluated by means of the norm of its gradient in the Hilbert space. The average Nusselt number is also estimated.     

Electronic structure and vibrational spectra of cis-diammine(orotato)platinum(II), a potential cisplatin analogue: DFT and experimental study

Orotic acid (vitamin B₁₃) is a key intermediate in biosynthesis of the pyrimidine nucleotides in living organisms, moreover, it may serve as the biological carrier for some metal ions. cis-Diammine(orotato)platinum(II), cis-[Pt(C₅H₂N₂O₄)(NH₃)₂] can be considered as a new potential cisplatin analogue. The FT-Raman and FT-IR spectra of the title complex are reported, for the first time. The molecular structure, vibrational frequencies, and the theoretical infrared and Raman intensities have been calculated by the density functional mPW1PW91 method. The detailed vibrational assignment has been made on the basis of the calculated potential energy distribution. The theoretically predicted IR and Raman spectra show very good agreement with experiment. Natural bond orbital (NBO) analyses were performed for cisplatin, carboplatin and the title complex. The results provided new data on the nature of platinum–ligand bonding in these compounds. Strong intramolecular hydrogen bond between the orotate ligand and the coordinated ammonia group stabilizes the structure of the platinum(II) complex. Thus, it is suggested that the orotate ligand in the title complex is more inert to the substitution reactions than the chloride ligands in cisplatin.     

Generalized Physical and SRB Measures for Hyperbolic Diffeomorphisms

In this paper we introduce the notion of generalized physical and SRB measures. These measures naturally generalize classical physical and SRB measures to measures which are supported on invariant sets that are not necessarily attractors. We then perform a detailed case study of these measures for hyperbolic Hènon maps. For this class of systems we are able to develop a complete theory about the existence, uniqueness, finiteness, and properties of these natural measures. Moreover, we derive a classification for the existence of a measure of full dimension. We also consider general hyperbolic surface diffeomorphisms and discuss possible extensions of, as well as the differences to, the results for Hènon maps. Finally, we study the regular dependence of the dimension of the generalized physical/SRB measure on the diffeomorphism. For the proofs we apply various techniques from smooth ergodic theory including the thermodynamic formalism. 2000 Mathematics Subject Classification. Primary: 37C45, 37D20, 37D35, Secondary: 37A35, 37E30     

Upward and downward heat and mass transfer with miniature periodically operating loop thermosyphons

Upward and downward two-phase heat and mass transfer has been considered in the present paper. The heat and mass transfer with the condenser located below the evaporator has been obtained by inserting an accumulator tank in the liquid line of a loop thermosyphon and enforcing a pressure pulsation. In previous papers these heat transfer devices have been called pulsated two phase thermosyphons (PTPT). A mini PTPT has been experimentally investigated. It has shown a stable periodic heat transfer regime weakly influenced by the position of the condenser with respect to the evaporator. In contrast a classical loop mini thermosyphon (diameter of connecting pipes 4 mm) did not achieve a stable functioning for the investigated level differences between evaporator and condenser lower than 0.37 m. The present study shows that the functioning of a PTPT device does not directly depend on the level difference or the presence of noncondensable gas. In order to obtain a natural circulation in mini or micro loops, a periodically operating heat transfer regime should therefore be considered.     

Effect of biotransformation on multispecies plume evolution and natural attenuation

Biological transformation of volatile organic compounds is one of the key factors that influence contaminant-plume evolution and thus natural attenuation. In this study we investigate the effect of biological transformation on the transport of contaminants in the aqueous and gaseous phases. The analysis includes the study of the effect of density-driven advection of contaminants in the gaseous phase on multiphase and multispecies flow, fate and transport modeling in the subsurface. Trichloroethylene (TCE) and its two byproducts, dichloroethylene and vinyl chloride, are analyzed as the target contaminants. Our results indicate that density-driven advection of the gaseous phase, which is initiated by evaporation of TCE as a nonaqueous phase liquid, increases the downward and also the lateral migration of TCE within the unsaturated zone. This process also influences the location of high-concentration zones of the byproducts of TCE in the unsaturated and the saturated zones. Biotransformation of TCE contributes to the reduction of dissolved TCE plume development as expected. The daughter byproducts, which are introduced into the subsurface system, show distinct transport patterns as they are affected by their independent degradation kinetics and density-driven advection. These observations, which are based on our simulation results for biotransformation and transport of TCE and its byproducts, are useful in evaluating the natural attenuation processes, its potential health hazards and also the evaluation of potential plume development at contaminated sites.     

甲醛与乙腈相互作用的理论研究

在HF/ 6 311G(d ,p)、MP2 / 6 311G(d ,p)和B3LYP/ 6 311G(d ,p)水平上 ,对H2 CO和CH3 CN以及设计的 4种结构H2 CO…CH3 CN复合物等进行几何全优化和振动频率计算 ,排除振动频率为负值的非局域极小点结构 ,并对稳定的环状构型复合物结合能进行基组重叠误差校正和零点振动能校正 .分子间相互作用的能量分解分析显示 ,静电能在H2 CO…CH3 CN相互作用能量中占主导地位 ,电荷转移能居第二位 .     

回填材料膨润土对放射性气体滞留能力模拟研究

利用各种分析手段对膨润土的物理特性进行了表征 .X射线衍射分析表明钠基膨润土呈典型的六方晶胞 ,晶胞参数是 :a轴 4 .913,c轴 5 .4 0 5 ;差热分析曲线在低温区和高温区有明显的吸热峰出现 ;元素分析钠、钾离子的含量大于钙、镁离子的含量 ,在性能上表现为钠质膨润土具有较强的离子交换能力 ;显微分析表明其表面呈皱隙状 ,测定比表面积高达 2 4 .5 2m2 /g;吸水率测定表明膨胀率大 ,说明它具有密封功能 ,可有效阻滞地下水的渗入 .利用SF6示踪技术 ,通过采集不同时间段取样池样品 ,分析样品中示踪气体浓度 ,绘制取样池示踪气体浓度随时间的变化关系曲线 ,根据费克扩散定律计算扩散系数 .实验结果表明 ,随着压实膨润土密度的增大 ,示踪气体扩散系数迅速减小 ,当密度大于 1.8g/cm3 时 ,扩散系数降至 10 -9m2 /s.研究结果表明 ,膨润土性能优化是通过在膨润土中添加适量的活性炭 ,可明显改善其对气体的阻滞能力 ;增加其对放射性气体滞留能力 ;添加少量的石英砂增加其机械性能、导热性和减少蠕变性 ,将引起对气体阻滞能力的下降 .综合考虑 ,在膨润土中各添加 5 %活性炭和石英砂 ,既对气体具有较好的滞留能力 ,又具有较好的工程特性 .     

The samarium(II)-mediated intermolecular couplings of ketones and β-alkoxyacrylates: a short asymmetric synthesis of an antifungal γ-butyrolactone

The samarium(II) iodide-mediated coupling of ketones with β-alkoxyacrylates gives β-hydroxy-γ-butyrolactones in moderate yield. The process has been applied to the asymmetric synthesis of an antifungal, γ-butyrolactone natural product.