HZSM5分子筛膜复合二氧化锡对甲烷的气敏性能研究

采用液相氧化法制备二氧化锡纳米颗粒,并利用浸渍法制备Pd负载二氧化锡纳米材料,通过丝网印刷得到气敏传感膜并在其表面印刷分子筛层。基于动态气敏测试系统探究传感器对甲烷气体的灵敏度及其在CO和乙醇干扰气体下的选择性。研究结果表明,在Pd-SnO₂敏感层表面印刷Pd-HZSM5层后,传感器对甲烷的响应能力显著提高,并且在体积分数为5×10^-4的CO存在时,对甲烷的选择性也得到明显的提升。同样,在质量分数为2×10^-5乙醇的存在下,传感器对甲烷的响应也没有受到干扰。通过对分子筛进行表征和催化分析,发现Pd-HZSM5对CO的催化效率可达100%,使得CO在扩散过程中被催化氧化,这可能是印刷Pd-HZSM5分子筛膜从而提高传感器选择性的主要原因。同时研究还表明,在敏感层表面印刷分子筛层并不会影响传感器的响应和恢复速率。     

Electrochemical behaviour of Mn3+/Mn2+, Co3+/Co2+ and Ce4+/Ce4+ redox mediators in methanesulfonic acid

The redox behaviour of Mn³⁺/Mn²⁺, Co³⁺/Co²⁺ and Ce⁴⁺/Ce³⁺ mediators commonly used in indirect oxidation of organic compounds were evaluated in methane sulfonic acid on a glassy carbon working electrode employing cyclic voltammetry. Manganic methanesulfonate exhibits higher instability in dilute methanesulfonic acid. The solid MnO₂ formed during disproportionation on the glassy carbon electrode further affects the reproducibility. Cobaltic methanesulfonate formation occurs only at oxygen evolution region rendering the overall oxidation process less efficient. Ceric methane sulfonate formation is highly efficient over a wide acid concentration range. Ceric methanesulfonate can also be employed over a wide temperature range to oxidize different aromatic compounds.     

不同方法制备K2MnAl11O19六铝酸盐催化剂及其甲烷的燃烧活性

介绍了共沉淀法和异丙醇盐水解法制备了六铝酸盐催化剂K2MnAl11O19,用XRD、BET、SEM和TG-DTA技术及甲烷燃烧活性对催化剂进行了表征和活性验证。结果表明,两种方法所制备的催化剂经1200℃焙烧4h后均可以形成完整的六铝酸盐晶型,同时都具有高的催化性能和高温稳定性,其中异丙醇盐水解法制备的K2MnAl11O19催化剂具有较高的比表面积和甲烷催化燃烧活性。     

Partial Oxidation of Methane to Syngas over Calcined Ni–Mg/Al Layered Double Hydroxides

The catalytic partial oxidation of CH₄ to syngas was carried out over an Ni–Mg/Al mixed-oxide catalyst prepared from layered double hydroxide-type precursors. The catalysts were characterized by XRD, TPR, UV-DRS, XRF, BET and CHNS analysis. The effects of the catalyst composition and the calcination temperature on the catalytic performance and the extent of catalyst deactivation were investigated. Ni–Mg/Al oxide catalysts converted CH₄ into syngas efficiently with high selectivity. The catalyst performance was strongly related to the Ni particle size and the calcination temperature. The catalysts that were calcined at higher temperature exhibited a better catalytic performance. In conclusion, the NiAl₂O₄ spinel phase had a positive effect on the stability of the catalyst.     

晋城矿区煤层气发电现状及规划

晋城矿区赋有丰富的煤层气资源 ,为充分利用这部分煤层气资源 ,晋城无烟煤矿业集团利用美国的打钻、压裂、排采技术实施煤层气开发示范工程 ,经潘庄、寺河两矿煤层初步发电试验 ,取得成功 ,2 0 0 2年初运转的 1 1× 1 0 4kW发电示范工程 ,取得良好的经济效益 ,为后续煤层气资源利用积累了宝贵的经验。     

氯化石蜡-52光引发氯化工艺条件的研究

建立了1套光引发氯化制备氯化石蜡-52的小试实验装置及对反应过程进行分析测试的方法，运用正交设计实验方法，系统地考察了各工艺条件如光强度，光引发时间，氯气流量，反应温度对氯化反应的影响。确定了较佳的工艺参数，为开发万吨级连续化生产装置提供了依据。     

煤层气水合物定容生成实验研究

为了有效利用与回收直接排放的大量抽放瓦斯,提出了利用水合物技术处理与储运的新方法,根据气体成分确立了水合物生成的温度与压力条件,通过对气体进行初始压力为9.5 MPa的定容法实验,研究了含表面活性剂下水合物生成过程中温度-压力与CH4转化率的变化规律。实验结果表明,水合反应的进行应保持一定的反应驱动力,根据不同温度下反应驱动力进而确定最佳反应条件,同时反应过程中CH4能被有效提取,但要进行高效生产,应进行多级水合分离技术以提高产率。     

Methane Transport Capacity of Rice Plants. II. Variations Among Different Rice Cultivars and Relationship with Morphological Characteristics

Of the total methane (CH4) emitted from a rice field during the growing season 60–90% is emitted through the rice plants. We determined the methane transport capacity (MTC) of rice plants at different physiological growth stages using an automatic measuring system under greenhouse conditions. A total of 12 cultivars (10 inbred varieties and 2 hybrids) were studied in sets of two experiments and was distinguished into three groups according to the patterns of MTC development. MTC is generally increasing from seedling stage to panicle initiation (PI), but differs in the development from PI to maturity. While the hybrid showed a gradual increase in MTC, the inbred cultivars showed either minor changes in MTC or a drastic decrease from flowering to maturity. Among tall cultivars, Dular showed the highest MTC, followed by B40; the lowest MTC was found in Intan. High-yielding dwarf cultivars showed MTC in the descending order of IR72 > IR52 > IR64 > PSBRc 20. New plant type cultivars showed very low MTC with IR65600 exhibiting the smallest MTC at PI, flowering, and maturity. Hybrids (Magat and APHR 2) showed the largest MTC that continued to increased with plant growth. The MTC patterns were attributed to growth parameters and the development of morphological characteristics of the aerenchyma. These results suggest that in tall, dwarf, and NPT cultivars, increase in root or aboveground biomass during initial growth determines a corresponding increase in MTC. Once aerenchyma has fully developed, further increase in plant biomass would not influence MTC. However, in the case of hybrids, a positive relationship of MTC with root + shoot biomass (r = 0.672, p 0.05) and a total plant biomass including grain (r = 0.849, p 0.01) indicate continuous development of aerenchyma with plant growth, resulting in enhanced MTC. In all cultivars, tiller number, but not height, was linearly related to MTC, indicating that the number of outlets/channels rather than plant size/biomass determines the transport of CH₄. These results clearly demonstrate that rice cultivars differ significantly in MTC. Therefore, the use of high-yielding cultivars with low MTC (for example, PSBRc 20, IR65598, and IR65600) could be an economically feasible, environmentally sound, and promising approach to mitigate CH₄ emissions from rice fields.     

氧泵型催化膜反应器中甲烷氧化偶联反应(Ⅰ)——氧泵型催化膜的制备及其反应性能

本文采用1％Sr/La_2O_3-Ag-YSZ氧泵型催化膜反应器进行了甲烷氧化偶联反应研究。比较了不同制备方法的催化膜的反应性能,结果发现浸涂法(Ag-YSZ管随旋转轴转动涂制)制备的膜性能最佳。研究了操作条件对甲烷氧化偶联反应的影响。研究证明,传递氧与气相氧同时进料是一种较好的反应方式。结果表明,利用该反应器不仅可以简化分离过程,而且还可得到更高的C_2烃选择性。     

Catalytic Combustion of Methane over Rare Earth Stannate Pyrochlore

Well-defined Ln₂Sn₂O₇ powders (Ln = La, Sm and Gd) with a phase-pure pyrochlore structure were synthesized by hydrothermal reaction. The catalytic activities of Ln₂Sn₂O₇ powders for methane combustion were measured. Methane oxidation started at 500 °C and increased with oxidation temperature. Catalytic methane combustion is strongly influenced by the presence of oxygen vacancies that form by breaking Sn–O lattice bonds as the temperature increases. Addition of manganese to the rare earth pyrochlores improved methane oxidation activity. Manganese-doped samarium stannate pyrochlore (Sm₂Sn_1.8Mn_0.2O₇) shows highest the catalytic activity. Light-off and complete oxidation temperatures were measured at about 400 and 650 °C, respectively.