The solubility of methane in aqueous solutions of monoethanolamine,diethanolamine and triethanolamine

The solubility of methane in 3 kmol/m³ solutions of monoethanolamine, diethanolamine, and triethanolamine was measured from 25° to 125°C and pressures up to about 13 MPa. Measurements were also made for the solubility of methane in water at 25° to 125°C and pressures up to 18 MPa in order to confirm the accuracy of the experimental technique. It is demonstrated that methane is more soluble (in terms of mole fraction) in the amine solution than in pure water. Furthermore, the solubility is an increasing function of the size of the alkanolamine. The solubility data were modeled using a Henry's-law approach and the results summarized in terms of salting-in coefficients.     

沁水盆地郑庄煤层气储层裂隙的测井响应特征

煤层气储层的裂隙发育程度与储层的地球物理测井响应特征相关,通过对沁水盆地郑庄区块80余口井测井资料的分析,总结了地质构造作用及裂隙发育对测井特征的影响,认为研究区识别煤层气储层裂隙的敏感参数依次为体积密度（DEN）、深侧向电阻率（RD）、声波时差（AC）、井径（CAL）、自然伽马（GR）、中子孔隙度（CNL）等,通过判断深、中、浅三个电阻率值的差异识别裂隙发育程度,建立了夹矸层RD≥3000 Ω·m、3000Ω·m＞RD≥1000Ω·m、1000Ω·m＞RD≥500Ω·m、RD＜500Ω·m、及CNL＞ 45％等几种类型的测井响应参数,给出了相应的测井响应示例,为建立研究区的裂隙发育展布提供了参考.     

沁水盆地郑庄区块构造演化与煤层气成藏

基于沁水盆地郑庄区块的构造发育特征,研究了自二叠纪煤系形成以来该区域构造应力场演化,分析了其对煤层气藏的控制作用,包括构造-埋藏史、后期成藏演化及成藏控制因素.研究表明:郑庄地区主要经历了印支期、燕山期、喜马拉雅早期和喜马拉雅晚期—现代4个期次的构造应力场演化.在构造控制下,二叠纪煤层经历了印支期和燕山中—晚期两次成烃作用,特别是燕山中、晚期煤层生气量巨大,是煤层气的主要成藏期.此后,随着地壳持续抬升剥蚀,煤层埋藏不断变浅,并发育了多组封闭性较好的节理.受南东侧的寺头断层控制,煤层埋深处于600～1 200m,为煤层气成藏以来的最浅埋藏,虽然本区二叠系煤层气的成藏时间较早,但保留的煤层气含量大,煤储层厚度大,且煤层埋藏适中.     

煤层气中甲烷δ~3C值偏轻的机理探讨

文中列出了５１个典型煤层气样品的甲烷δ１３Ｃ值测试数据，系统地分析了煤层气甲烷稳定碳同位素组成特征，深入探讨了甲烷δ１３Ｃ值偏轻的原因。     

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.     

Effect of the method of preparation of a Nd2O3-MgO catalyst on its efficiency in the reaction of oxidative coupling of methane

It is shown that the decomposition of a mixture of nitrates or coprecipitated carbonates or hydroxides of Mg and Nd form catalysts manifesting similar catalytic properties, while the catalyst obtained by impregnation is more active but much less selective. The mechanism of formation of the catalytically active phase and the nature of the active sites are discussed.     

Complete Oxidation of Methane at Low Temperature over Pt Catalysts Supported on High Surface Area SnO2

The catalytic activity of Pt catalysts supported on high surface area tin(IV) oxide in the complete oxidation of CH₄ traces under lean conditions at low temperature was studied in the absence and in the presence of water (10 vol.%) or H₂S (100 vol.ppm). Their catalytic properties were compared to those of Pd/Al₂O₃ and Pt/Al₂O₃. In the absence of H₂S in the feed, Pt/SnO₂appears as a very promising catalyst for CH₄ oxidation, being even significantly more active under wet conditions than the best reference catalyst, Pd/Al₂O₃. Catalysts steamed-aged at 873 K were also studied in order to simulate long term ageing in real lean-burn NGV exhaust conditions. To this respect, Pt/SnO₂ is slightly less resistant than Pd/Al₂O₃. In the presence of H₂S, Pt/SnO₂catalysts are rapidly and almost completely poisoned, comparably to Pd/Al₂O₃and the catalytic activity is hardly restored upon oxidising treatment below 773 K. A synergetic effect between Pt and specific surface SnO₂sites active in CH₄oxidation is proposed to explain the superior catalytic behaviour of Pt/SnO₂.     

甲烷单加氧酶模型化合物的合成及性能测试

设计、合成了一个新的甲烷单加氧酶(MMO)模型化合物[Fe2(Ⅲ,Ⅲ)L(μ-OAc)2]·PF6,其中L为2,6-二{[(2-羟基-5-叔丁基-苄基)(吡啶-2-甲基)-氨基]-甲基}-4-甲基苯酚。与以往的模型体系[Fe2(Ⅱ,Ⅲ)(bpmp)(μ-OAc)2]·(BPh4)2相比,新模型增加了2个酚配体、2个叔丁基。这些基团的引入提高了中心金属Fe的价态,并增加了配体的电子云密度从而调节了Fe的氧化还原电位。该模型进一步缩小了人工模型体系与甲烷单加氧活性中心(MMOH)的差异。通过红外(IR)、电喷雾电离质谱(ESI-MS)、核磁共振NMR(gCOSY、gHMBC、gHSQC)及电化学对新配体及络合物进行了表征和测试。     

Reforming of methane and coalbed methane over nanocomposite Ni/ZrO2 catalyst

Nanocomposite Ni/ZrO₂-AN catalyst consisting of comparably sized Ni metal and ZrO₂ nanoparticles is studied in comparison with zirconia- and alumina-supported Ni catalysts (Ni/ZrO₂-CP and commercial Ni/Al₂O₃-C) for steam reforming of methane (SRM) and for combined steam and CO₂ reforming of methane (CSCRM). The reactions are performed under atmospheric pressure with stoichiometric amounts of H₂O and CH₄ or (H₂O + CO₂) and CH₄ at 1073 K. Under a wide range of methane space velocity (gas hourly space velocity of methane GHSV_CH4 = 12,000–96,000 ml/(h g_cat.), the nanocomposite Ni/ZrO₂-AN catalyst always shows higher activity and stability for both SRM and CSCRM reactions. The two supported Ni catalysts (Ni/ZrO₂-CP and Ni/Al₂O₃-C) exhibit fairly stable catalysis under low GHSV_CH4 but they are easily deactivated under high GHSV_CH4 and become completely inactive when they are reacted for ca.100 h at GHSV_CH4 = 48,000 ml/(h g_cat.). The CSCRM reaction is carried out with different H₂O/CO₂ ratios in the reaction feed while keeping the molar ratio (H₂O + CO₂)/CH₄ = 1.0, the results prove that the nanocomposite Ni/ZrO₂-AN catalyst can be highly promising in enabling a catalytic technology for the production of syngas with flexible H₂/CO ratios (ca. H₂/CO = 1.0–3.0) to meet the requirements of various downstream chemical syntheses.     

Combined Single-Pass Conversion of Methane Via Oxidative Coupling and Dehydroaromatization

A new reaction mode, i.e., the combined single-pass conversion of methane via oxidative coupling (OCM) over mixed metal oxide (SLC) catalysts and dehydroaromatization (MDA) over Mo/HZSM-5 catalysts, is reported. With the assistance of an OCM reaction over SLC catalysts in the top layer of the reactor, the deactivation resistance of Mo/HZSM-5 catalysts is remarkably enhanced. Under the selected reaction conditions, the CH₄ conversion decreased from 18 to 1% and the aromatics yield decreased from 12.8 to 0.1%, respectively, after running the reaction for 960min on both 6Mo/HZSM-5 and SLC-6Mo/HZSM-5 catalyst system without O₂ in the feed. On the other hand, for the SLC-6Mo/HZSM-5 catalyst system with O₂ in the feed, the deactivation was improved greatly, and after 960min onstream the CH₄ conversion and aromatics yield were still as high as 12.0 and 8.0%, respectively. The promotion effect mainly appears to be associated with in situ formation of CO₂ in the OCM layer, which reacts with coke via the reverse Boudouard reaction.