甲烷部分氧化制合成气催化剂的研究进展

综述了甲烷部分氧化制合成气的研究意义和现状，从金属活性组分，载体效应，载量选择，助剂添加和制备方法等因素对催化剂活性的影响及研究进行了系统。结合本课题组的研究结果及文献报道，分析了Ni基催化剂的失活特性，并提出使用等离子体技术对Ni基催化剂进行改笥处理，以提高其催化稳定性的技术展望。     

Oxidative coupling of methane over LaCoO3−δ-based mixed oxides

The catalytic activity of LaCoO_3–-based mixed oxides for the oxidative coupling of methane has been tested by TPR and cyclic reaction. Characterization has been done by XRD, TGA and Mössbauer spectrometry. It is likely that the perovskite-crystal structure containing hypervalent metal ions has an important role and that unique structural oxygen species in the perovskite contribute to the partial oxidation of methane.     

Kinetics of methane hydrate formation in aqueous electrolyte solutions

Experimental data on the kinetics of methane hydrate formation in aqueous electrolyte solutions are reported. The experiments were carried out in a semi-batch stirred tank reactor in three NaCl and two KCl solutions as well as in a solution containing a mixture of NaCl and KCl at three different nominal temperatures from 270 to 274 K and at pressures ranging from 3.78 to 7.08 MPa. The kinetic model developed by Englezos et al. (1987a) was adapted to predict the growth of hydrates. The model is based on the crystallisation theory coupled with the two-film theory for gas absorption in the liquid phase. The kinetic rate constant which appears in the model was that obtained earlier for methane hydrate formation in pure water. The effect of the electrolytes was taken into account through the computation of the three-phase equilibrium conditions and the corresponding fugacities. Overall, the model predictions match the experimental data very well with the largest prediction error being less than 10%.     

An apparent ensemble effect in the oxidative coupling of methane on hydroxyapatites with incorporated lead

The introduction of small quantities of lead into calcium hydroxyapatite catalysts produces marked increases in the selectivity to C₂₊ hydrocarbons, while the conversion of methane remains relatively constant. Small surface concentrations of lead are sufficient to achieve C₂₊ selectivities of 80 and 90%, with oxygen and nitrous oxide, respectively, in contrast with 18 and 46%, respectively, obtained in the absence of lead. Since surface concentration of lead species sufficient to stabilize pairs of methyl radicals in close proximity to each other would be expected to facilitate the formation of C₂ hydrocarbons, an ensemble effect appears to be extant.     

Impact of agriculture on soil consumption of atmospheric CH4 and a comparison of CH4 and N2O flux in subarctic, temperate and tropical grasslands

Increasing concentrations of methane (CH₄) in the atmosphere are projected to account for about 25% of the net radiative forcing. Biospheric emissions of CH₄ to the atmosphere total approximately 400 Tg C y^-1. An estimated 300 Tg of CH₄-C y^-1 is oxidized in the atmosphere by hydroxyl radicals while about 40 Tg y^-1 remains in the atmosphere. Approximately 40 Tg y^-1 of the atmospheric burden is oxidized in aerobic soils. Research efforts during the past several years have focused on quantifying CH₄ sources while relatively less effort has been directed toward quantifying and understanding the soil sink for atmospheric CH₄. Recent research has demonstrated that land use change, including agricultural use of native forest and grassland systems has decreased the soil sink for atmospheric methane. Some agricultural systems consume atmospheric CH₄ at rates less than 10% of those found in comparable undisturbed soils. While it has been necessary to change land use practices over the past centuries to meet the required production of food and fiber, we need to recognize and account for impacts of land use change on the biogeochemical nutrient cycles in the biosphere. Changes that have ensued in these cycles have and will impact the atmospheric concentrations of CH₄ and N₂O. Since CH₄ and N₂O production and consumption are accomplished by a variety of soil microorganisms, the influence of changing agricultural, forest, and, demographic patterns has been large. Existing management and technological practices may already exist to limit the effect of land use change and agriculture on trace gas fluxes. It is therefore important to understand how management and land use affect trace gas fluxes and to observe the effect of new technology on them. This paper describes the role of aerobic soils in the global CH₄ budget and the impact of agriculture on this soil CH₄ sink. Examples from field studies made across subarctic, temperate and tropical climate gradients in grasslands are used to demonstrate the influence of nutrient cycle perturbations on the soil consumption of atmospheric CH₄ and in increased N₂O emissions. This revised version was published online in August 2006 with corrections to the Cover Date.     

基于VB6.0的红外甲烷检测仪串行通信的实现

针对煤矿安全生产中存在的瓦斯爆炸问题,该文以MSP430系列单片机为核心,设计了红外甲烷检测仪.其中着重介绍了检测仪的串行通信,编写了串行通信程序,使检测仪能实现与PC机的数据通信功能,并使用VB6.0编写了人机交互界面,以方便用户及时观察和处理数据,实现对检测仪的校准、复位和阈值设置等操作功能.实验结果表明,编写的串行通信程序能实现检测仪与PC的数据通信功能,检测仪能快速、准确地检测出甲烷气体的浓度,具有较高的实用价值.     

Interaction of methane with surfaces of silica,aluminas and HZSM-5 zeolite. A comparative FT-IR study

Infrared investigations on the interaction of methane with silica, aluminas (, and ) and HZSM-5 zeolite have been carried out. At low temperature (173 K), methane adsorption was observed over these oxides and HZSM-5 zeolite. Our findings featured that the infrared inactive ₁ band (2917 cm^–1) of a gaseous methane molecule became active and shifted to lower frequencies (2900 and 2890 cm^–1) when it adsorbed on the surfaces of these adsorbents. Our results also demonstrate that hydroxyl groups played a very important role in methane adsorption over the acidic oxides and the HZSM-5 zeolite. When interaction between the hydroxyl groups and methane took place, the band shift of the hydroxyl groups varied with different oxides. The strength of the interaction decreased according to the following sequence, Si-OH-Al>Al-OH>Si-OH, which is in accordance with the order of their acidities. At higher temperatures, methane interacted quite differently with various oxides and HZSM-5 zeolite. It has been observed that the hydroxyl groups of silica, -alumina and HZSM-5 zeolite could exchange with CD₄ at temperatures higher than 773K, while those on -alumina could exchange at a temperature as low as 573 K. Another interesting observation was the formation of formate species over Al₂O₃ (both and ) at temperatures higher than 473 K. The formate species would decompose to CO₂, or produce carbonate at much higher temperatures. Formation of formate species was not observed over silica and HZSM-5 under similar conditions, -Al₂O₃ did not adsorb or react with methane in any case.     

V2O5催化甲烷液相部分氧化工艺过程研究

以V2O5为催化剂,在发烟硫酸中进行了甲烷液相选择性氧化的研究工作,考察了V2O5催化剂用量、反应温度、反应时间、发烟硫酸浓度等工艺条件对反应收率的影响,进行了甲烷液相选择性氧化的催化机理探讨和宏观动力学推导.甲烷在部分氧化反应中首先转化为硫酸甲酯,后者进一步水解得到甲醇.甲烷转化率可达54.5%,选择性45.5%,相应的工艺条件为催化剂用量0.0175 mol、反应温度180C、发烟硫酸中SO3含量50%(wt)、反应时间2 h.V2O5催化甲烷液相部分氧化反应遵循亲代取代机理,甲烷液相部分氧化反应为一级反应.     

Laboratory study of methane oxidation in paddy soils

Methane oxidation in paddy soils was investigated under laboratory conditions. Paddy soils collected before early rice transplanting could not oxidize atmospheric CH₄ but could oxidize CH₄ when the concentration exceeded 10 μl l^-1. Initial CH₄ oxidation rate increased with the increase of initial CH₄ concentration. Soil with the maximum potential to produce CH₄, also had the maximum CH₄ oxidation activity and the maximum emission flux from paddy soil. High CH₄ concentration stimulated the oxidation of CH₄. After 10 days' incubation under atmosphere containing 1000 μl^-1 or 10⁴ μl l^-1 CH₄, the soil which could not oxidize atmospheric CH₄ was able to oxidize it. This revised version was published online in August 2006 with corrections to the Cover Date.     

Dehydrogenation and aromatization of methane under non-oxidizing conditions

The dehydrogenation and aromatization of methane on modified ZSM-5 zeolite catalysts has been studied under non-oxidizing conditions with a fixed bed continuous-flow reactor and with a temperature programmed reactor. The results show that benzene is the only hydrocarbon product of the catalytic conversion of methane at high temperature (973 K). The catalytic activity of ZSM-5 is greatly improved by incorporating a metal cation (Mo or Zn). H₂ and ethene have been directly detected in the products with a mass spectrometer during TPAR. A carbenium ion mechanism for the activation of methane is suggested.