A density functional theory study of methane activation on MgO supported Ni9M1 cluster: role of M on C–H activation

Methane activation is a pivotal step in the application of natural gas converting into high-value added chemicals via methane steam/dry reforming reactions. Ni element was found to be the most widely used catalyst. In present work, methane activation on MgO supported Ni–M (M = Fe, Co, Cu, Pd, Pt) cluster was explored through detailed density functional theory calculations, compared to pure Ni cluster. CH₄ adsorption on Cu promoted Ni cluster requires overcoming an energy of 0.07 eV, indicating that it is slightly endothermic and unfavored to occur, while the adsorption energies of other promoters M (M = Fe, Co, Pd and Pt) are all higher than that of pure Ni cluster. The role of M on the first C–H bond cleavage of CH₄ was investigated. Doping elements of the same period in Ni cluster, such as Fe, Co and Cu, for C–H bond activation follows the trend of the decrease of metal atom radius. As a result, Ni–Fe shows the best ability for C–H bond cleavage. In addition, doping the elements of the same family, like Pd and Pt, for CH₄ activation is according to the increase of metal atom radius. Consequently, C–H bond activation demands a lower energy barrier on Ni–Pt cluster. To illustrate the adsorptive dissociation behaviors of CH₄ at different Ni–M clusters, the Mulliken atomic charge was analyzed. In general, the electron gain of CH₄ binding at different Ni–M clusters follows the sequence of Ni–Cu (–0.02 e) < Ni (–0.04 e) < Ni–Pd (–0.08 e) < Ni–Pt (–0.09 e) < Ni–Co (–0.10 e) < Ni–Fe (–0.12 e), and the binding strength between catalysts and CH ₄ raises with the CH₄ electron gain increasing. This work provides insights into understanding the role of promoter metal M on thermal-catalytic activation of CH₄ over Ni/MgO catalysts, and is useful to interpret the reaction at an atomic scale.     

膨胀管技术在西北油田TH10233CH井的应用

侧钻是降低油气开采成本的有效途径之一。西北油田受井眼尺寸、避水要求、不稳定泥岩、复杂压力体系等原因的影响,侧钻难度极大。为解决这一难题,在TH10233CH井采用膨胀管技术进行了实际应用。采用φ139.7mm膨胀管封固上部不稳定地层,膨胀管膨胀前内径124.2mm,膨胀后内径可达134.5mm,采用φ130mm钻头钻进,顺利完钻。膨胀管钻井技术在TH10233CH井的成功应用对西北油田侧钻井钻进具有重大指导意义。     

基于STM32微控制器和CH438Q数据采集器的设计与实现

为有效解决深海资源探测传感器搭载数量以及控制系统小型化问题,结合STM32F103RCT6和CH438Q设计了一种能够在深海区域控制多种传感器并将实时探测到的数据进行分类存储的小型化数据采集控制系统.海上试验结果表明,数据采集系统工作稳定、数据完整,可广泛应用于各种海洋环境监测和深海资源探测系统的建设中.     

改性纳米多孔钴低温催化二氧化碳加氢制甲醇

低温条件下二氧化碳（CO2）加氢制甲醇（CH3OH）被认为是一项重要且仍具挑战性的工作,本文制备了纳米多孔钴（NP-Co）及改性纳米多孔钴NP-CoxM（M=Cr,V,Mo,Mn,Ce,W,x=nCo∶nM）催化剂,评价其在60-140 ℃的温和条件下催化CO2加氢制CH3OH,铬作为改性元素显著提高了催化剂性能。采用N2-物理吸脱附、SEM、TEM、XRD、XPS和CO2-TPD对NP-Co、NP-Co3Cr进行表征,结果显示CrxO作为改性组分显著增强了CO2与活性位点之间的强相互作用、表面羟基的大量增加促进了CO2低温活化,具体表现为采用NP-Co3Cr的表观活化能（59.08 kJ/mol）相比NP-Co（89.12 kJ/mol）显著降低。CH3OH作为主要产物,其60 ℃下的时间收率为106.4 μmol/（gCat.·h）且选择性达92.8%,相同反应条件下的NP-Co则未观察到CH3OH生成。     

煤与天然气气流床共气化制合成气试验研究

为提高煤、天然气资源综合利用效率,优化合成气成分,进行了煤与天然气气流床共气化技术研究。介绍了煤与天然气气流床共气化的试验装置及工艺流程,考察了气化温度、压力、水煤浆浓度、CH4与煤比对共气化反应的影响。结果表明,气化温度和CH4与煤比是共气化反应的主要影响因素,较高的气化温度对共气化反应有利,气化温度为1 350℃时,共气化指标较好,有效气体积分数大于90%;随着CH4与煤比的增大,合成气n(H2)/n(CO)增高。CH4与煤比为0.9 m3/kg时,合成气中n(H2)/n(CO)约1.2。根据后续合成工艺要求,通过调节气化温度和CH4与煤比,可获得n(H2)/n(CO)在0.8~2.0的合成气。     

[Bmim][PF6]高效吸收二氯甲烷及流程模拟

采用智能重量吸附仪测量了不同温度、压力下二氯甲烷(CH2Cl2)在离子液体1-丁基-3-甲基咪唑六氟磷酸盐([Bmim][PF6])中的溶解度,用NRTL方程建立了离子液体?二氯甲烷体系的气液平衡模型,拟合得到二元交互作用参数,计算所得的二氯甲烷溶解度与实验数据吻合良好,平均相对误差为3.16%. 构建了离子液体处理含二氯甲烷尾气及资源回收利用的常压吸收?减压闪蒸解吸工艺和模型,模型适用范围为温度278.15~308.15 K,压力0~0.1 MPa. 对吸收塔进行了模拟和灵敏度分析,获得了常温常压吸收条件下的最佳操作工艺参数.     

NO removal by CH4 on Co-NaX-CO and Ag-NaX catalysts in a dual-bed system

NO removal using CH₄ as a reductant in a dual-bed system has been investigated with Co-NaX and Ag-NaX catalysts, which were prepared by Co²⁺-, Ag⁺-ion exchange into zeolite NaX, respectively, and activation for 5 h at 500 °C. The experimental result has been compared with that of a Co-NaX-CO catalyst, additionally pre-treated under CO flow for the Co-NaX catalyst. The cobalt crystal structure of a Co-NaX-CO catalyst is Co₃O₄, which promotes NO oxidation to NO₂ by excess O₂ at a low temperature (523 K). The mechanical mixture of Co-NaX-CO and Ag-NaX catalysts shows a synergy effect on NO reduction to N₂ by CH₄ in the presence of excess O₂ and H₂O, but the NO reduction decreases quickly as time passes. However, the NO reduction to N₂ in a deNO bed at 523 K and a deNO₂ bed at 423 K, which are relatively lower than the reaction temperatures for common SCR systems, still remained at 67% even in a H₂O 10% gas mixture after 160 min.     

铁离子改性碳分子筛对氮气/甲烷分离性能的研究

针对碳分子筛对氮气/甲烷分离体系分离比低的问题,采用浸渍法以市售空分碳分子筛（CMS）为基体,制备了分离氮气/甲烷的铁离子改性碳分子筛。通过静态吸附量、分离比、吸附动力学及热力学性质考察了铁离子负载量对碳分子筛吸附分离氮气/甲烷性能的影响。结果表明：铁（Ⅲ）的负载减小了CMS的比表面积、微孔体积和孔径,使CMS超微孔的孔径分布呈现更集中的趋势。这种集中性以动力学性能下降为代价,明显提高了碳分子筛对氮气/甲烷的吸附分离比。在303 K、0.7 MPa条件下,综合性能优异的0.3%铁改性CMS具有6.03的氮气/甲烷吸附分离比。     

基于二阶矩封闭湍流模型的非预混湍流火焰的数值模拟

Turbulent nonpremixed CH4/H2 flame has been simulated using several typical differential secondmoment turbulence closure (SMTC) models. To clarify the applicability of the various models, the LRR-IP model,JM model, SSG model as well as two modified LRR-IP models were tested. Some of above-mentioned SMTC models cannot provide the overall satisfactory predictions of this challenging case. It is confirmed again that the standard LRR-IP model considerably overpredict the centerline velocity decay rate, and therefore performs not well. Also it is interesting to observe that the JM model does not perform well in this challenging test case, although it has already been proved successful in other cases. The SSG model produces quite satisfactory prediction and performs equally well or better than the two modified LRR-IP models in the reacting case. It can be concluded that the modified LRR-IP models as well as the SSG model are superior to the other SMTC models in the turbulent nonpremixed CH4/H2 flame.