The oxidative coupling of methane on alkali- and alkaline earth-phosphate catalysts

The oxidative coupling of methane has been tested over alkali- and alkaline earth-phosphate catalysts at 700 and 775 °C with and without the introduction of a small quantity of tetrachloromethane (TCM) to the feedstream. In general, the conversion of methane was enhanced by the addition of TCM but the effect on selectivity was dependent on the catalyst being examined. The selectivity to C₂ and higher hydrocarbons and that to oxidation products have been shown to have a dependence on the cation radius/charge ratio.     

二安替比林甲烷分光光度法测定电镀废水中钛的含量

在酸性介质中,以抗坏血酸和焦磷酸钠共同作掩蔽剂,用二安替比林甲烷分光光度法测定电镀废水中钛的含量,方法简便,准确度高.     

热水解厌氧消化工艺的分析和应用探讨

热水解厌氧消化工艺可提高污泥的水解效果和有机物降解率,增加沼气产量;杀灭污泥中病菌;缩短厌氧消化的停留时间、提高消化池内的污泥浓度,节省占地面积和土建工程投资;同时使消化后的污泥易于脱水,污泥体积减少。与传统的厌氧消化工艺比较,热水解厌氧消化工艺强化了污泥的减量化、稳定化、无害化和资源化的处理目标,当与后续热干化工艺结合时,可降低运行成本。从热水解技术的原理和形式出发,结合实际工程方案,对热水解厌氧消化工艺的可行性和应用中的问题进行了初步探讨。     

Methane coupling at low temperatures on Ru(0001) and Ru(11¯20) catalysts

The conversion of methane to higher hydrocarbons on single crystal Ru catalysts has been investigated using combined elevated-pressure kinetic measurements/surface science studies. The reaction consists of activation of methane on Ru(0001) and Ru(11¯20) surfaces to produce carbonaceous intermediates at temperatures between 350 and 700 K and rehydrogenation of these species to ethane and propane at 370 K. It is found that under the reaction conditions employed, the maximum yield in ethane/propane production occurs at 500 K on both surfaces. Influence of the hydrogenation temperature on the production of ethane and propane is also examined. On Ru(0001), the yields of ethane and propane maximize at = 400 K, whereas no maximum yield was observed on Ru(11 0) in the 300–500 K temperature range. Under optimum reaction conditions, hydrocarbon products consist of 16% ethane and 2% propane. High-resolution electron energy-loss spectroscopy (HREELS) has been used to identify various forms of hydrocarbonaceous intermediates following methane decomposition. An effort is made to relate the hydrocarbon intermediates identified by HREELS to the gas phase products observed in the elevated pressure experiments.     

Application of the independent molecule model to elucidate the dynamics of structure I methane hydrate: a second report

Two model systems of methane hydrate are constructed. One has a small cage surrounded by 12 large cages. The other has a large cage surrounded by four small cages and ten large cages. Three different H-bonding network patterns between waters are formed, and three random configurations of methane in each cage are chosen. A new method called the surface water fixed model is presented in which the energy minimum conformations for both model systems are preserved close to the X-ray crystallized structure. With normal mode analysis, we calculated frequencies of 2916.6 cm⁻¹ for a small cage at a centre, 2915.9 cm⁻¹ not at a centre, and 2911.7 cm⁻¹ for a large cage at a centre, and 2911.3 cm⁻¹ not at a centre. These frequencies are in moderate agreement with the corresponding Raman spectra, though not adequate. With our new method, however, it should be possible to improve agreement with the Raman spectra, if a model system vastly larger than the present model systems were constructed.     

Simulation of the interaction of methane,carbon dioxide and coal

Gas adsorption has an important influence on gas flow in a coal body. Research on the characteristics of coal and gas adsorption is the theoretical basis for studying gas flow in coal. In this paper, the interaction between methane, carbon dioxide and surface molecules of anthracite was simulated using the quantum chemistry method. Adsorption energy and adsorption configurations of different quantities of gas molecules absorbed on the coal surface were calculated. The results show that adsorption between coal and the two kinds of gas molecules is a physical adsorption process and there is an optimal configuration. Gas molecules are more easily adsorbed in the hydroxyl-containing side chain, while it is difficult for them to be adsorbed at the position of the benzene ring. Besides, carbon dioxide molecules are more readily adsorbed on the coal surface than methane molecules. The findings have an important significance in revealing the nature of gas adsorption in coal.     

Low-temperature catalytic combustion of methane over Pd/CeO2 prepared by deposition–precipitation method

Ceria supported 2 wt% Pd catalysts for low-temperature methane combustion were prepared by the impregnation (IM) and deposition–precipitation (DP) methods, which are denoted as Pd–IM and Pd–DP, respectively. DP was found to be an available method for achieving high activity and stability of the Pd/CeO₂ catalyst. The temperatures for methane ignition (T_10%) and total conversion (T_100%) over Pd–DP are 224 and 300 °C at GHSV of 50,000 h⁻¹, which are 83 and 110 °C lower than the corresponding temperatures of Pd/Al₂O₃. X-ray diffraction (XRD), Raman and X-ray photoelectron spectroscopy (XPS) analyses show that palladium species in Pd–DP is highly dispersed, positively charged and difficultly reduced. Raman spectra disclosed that the largest concentration of defects and/or oxygen vacancies was formed in Pd–DP catalyst. A kind of cationic PdO^δ+ sites with higher binding energies than PdO are in close vicinity to the oxygen vacancies in the CeO₂ support and might act as the active centers for methane oxidation. Furthermore, the deactivation and steam aging tests for Pd–DP showed that the performance of this type of palladium was very stable and could be repeatedly recovered after several long time aging tests.     

Oxygen permeation properties and surface modification of acceptor-doped CeO2/MnFe2O4 composites

The preparation and oxygen permeation properties of the (Ce_0.8Pr_0.2)O_2−δ − x vol% MnFe₂O₄ composites, where x = 0 to 35, have been investigated. The samples were prepared by the Pechini method. In the case of Ce_0.8Pr_0.2O_2−δ, an oxygen flux density of 6 μmol⋅cm⁻²⋅s⁻¹ (L = 0.0247 cm) and the maximum methane conversion of 50% were attained at 1000^∘C. Unlike composites consisting of Gd-doped CeO₂ and MnFe₂O₄, the oxygen permeability of the (Ce_0.8Pr_0.2)O_2−δ – x vol% MnFe₂O₄ composites was almost constant regardless of the volume fraction of MnFe₂O₄; however, the optimum volume fraction of MnFe₂O₄ was determined to be 5 to 25 in the context of the chemical and mechanical stabilities under methane conversion atmosphere. In addition, the surface modification of the (Ce_0.8Gd_0.2)O_2−δ – 15 vol% MnFe₂O₄ composite was performed by using the FePt nanoparticles. The catalyst loading of 2.8 mg/cm² on the both side of the 0.3 mm-thick (Ce_0.8Gd_0.2)O_2−δ – 15vol% MnFe₂O₄ composite increased the oxygen flux density from 0.30 to 0.76 μmol⋅cm⁻²⋅s⁻¹ in the case of He/air gradients; however, the effect seems to be reduced in the case of high oxygen flux density caused by a large pO₂ gradient. Moreover, the Langmuir-Blodgett film of the FePt nanoparticles were successfully prepared on the tape-cast (Ce_0.8Gd_0.2)O_2−δ – 15vol% MnFe₂O₄ composite. Hydrophobic treatments for the surface of the composite were crucial to achieve high transfer ratio for the deposition of the LB film.     

掺杂六铝酸盐LaMnMxAl11-xO19-δ的制备及高温催化性能

以Triton X-100/正已醇/环己烷组成的反相微乳液为媒介,采用反相微乳-共沉淀法制备系列金属掺杂的六铝酸盐LaMnMxAL11-xO19-δ(M为Ni,Co)催化剂,用BET,XRD进行物性表征,确定最佳焙烧温度,以甲烷燃烧为探针反应考察催化剂的催化活性,以Ni掺杂的六铝酸盐催化剂为对象,研究了反相微乳体系中前驱溶液浓度对催化剂性能的影响.结果表明,1 200℃左右可以形成完整的六铝酸盐晶型,并具有较高的催化性能;金属Co的存在可以促进六铝酸盐晶相的形成,而降低成晶温度;金属Ni可以明显提高催化剂的高温活性.反相微乳液中前驱液离子浓度对催化剂的比表面积、粒径及催化活性有一定影响.     

CH4传感系统微弱光电信号处理电路的研究

为改善以CH4为目标气体的检测系统的信噪比,提高系统的检测灵敏度.基于微弱信号的锁定检测原理,以方波调制系统LED为光源,设计以锁相放大器为核心的微弱信号处理电路和计算机控制电路,将携带浓度信息的光强信号转换为直流电压输出.实验结果表明,电路输出电压与检测甲烷气体浓度呈线性关系.分析表明,理论上电路对甲烷浓度检测极限值为1.5×10-4.系统灵敏度可通过设计光源功率稳定电路和温度控制电路得到进一步提高.