Concentration fluctuation caused by reaction-diffusion coupling near catalytic active sites

The coupling of reaction and diffusion between neighboring active sites in the catalyst pore leads to the spatiotemporal fluctuation in component concentration, which is very important to catalyst performance and hence its optimal design. Molecular dynamics simulation with hard-sphere and pseudo-particle modeling has previously revealed the non-stochastic concentration fluctuation of the reactant/product near isolated active site due to such coupling, using a simple model reaction of A → B in 2D pores. The topic is further developed in this work by studying the concentration fluctuation due to such coupling between neighboring active sites in 3D pores. Two 3D pore models containing an isolated active site and two adjacent active sites were constructed, respectively. For the isolated site, the concentration fluctuation intensifies for larger pores, but the product yield decreases, and for a given pore size, the product yield reaches a peak at a certain reactant concentration. For two neighboring sites, their distance (d) is found to have little effect on the reaction, but significant to the diffusion. For the same reaction competing at both sites, larger d leads to more efficient diffusion and better overall performance. However, for sequential reactions at the two sites, higher overall performance presents at a smaller d. The results should be helpful to the catalyst design and reaction control in the relevant processes.     

On‐surface polymerization – a versatile synthetic route to two‐dimensional polymers

Two‐dimensional (2D) polymers are novel covalent sheet materials with promising properties, but also great synthetic challenges. The inadequacy of traditional wet chemical synthesis calls for new synthetic paradigms. In this respect, employing surfaces as inherently 2D reaction venues appears an adequate choice and has recently already yielded encouraging results. Polymerization at air ? liquid and liquid ? liquid interfaces has been reported from time to time over the last decades, whereas recent efforts on solid surfaces are less traditional. In either case, both movement and coupling of monomers are already confined in two dimensions at interfaces or on surfaces. Accordingly, this approach naturally affords low‐dimensional reaction products. To achieve 2D reticulation, monomers are functionalized with multiple reactive groups of the same or a different kind, whereby their number and stereochemical arrangement predefines the ideal structure of the resulting 2D polymer. This perspective article exemplifies different approaches, i.e. types of surfaces, coupling chemistry and activation schemes, to employ surfaces for novel synthetic routes for the bottom‐up synthesis of 2D polymers. © 2015 Society of Chemical Industry     

千米深井大断面硐室双强壳体支护成套技术的应用

从分析深井高应力大断面巷道和硐室破碎围岩的变形破坏特点入手,指出巷道稳定性的控制机理在于及时强化失稳区围岩的残余强度,阻止初次失稳的发展,并施加高强的主动支护结构,从而使巷道进入二次稳定状态,同时采取高强的被动封闭支护技术。提出了全断面双强壳体支护设计、3S耦合协调支护设计和抗张拉强基础梁支护设计等设计方案来控制巷道变形。并对绞车房进行现场施工,支护效果良好,达到预期目标。     

激励方式对锆钛酸铅钡锶压电陶瓷介电性能的影响

采用扎膜工艺和固相反应法制备了(Pb0.70Ba0.26Sr0.04)(Zr0.52Ti0.48)O3(PBSZT)压电陶瓷。通过扫描电子显微镜和X射线衍射表征PBSZT陶瓷的结构和物相组成,用电容介损测试仪表征压电陶瓷的介电性能与激励场强,通过自建电路集成直流电源、标准电容,在低频频率特性测试仪上得到偏场强度对压电陶瓷介电性能的影响关系。结果表明:压电陶瓷材料的介电性能随着加载的电场强度的增大先逐渐升高,而后出现拐点开始降低;在偏压电场中,自由电容CT随正向偏场强度的增加逐渐减小,但随着反向偏场强度的增加逐渐增大。tanδ则随着正、反偏场强度的增加均呈现上升;压电陶瓷的机电耦合系数kp与偏场强度的关系是以0点为界,随着负偏场增强,kp略显下降,反之,随正偏场增强,kp缓慢增大。因此,压电陶瓷应用时应避开强场损耗高点;并在环境中施加正向偏场,有助于抑制压电陶瓷性能衰减。     

玄武岩短纤维增强硅橡胶复合材料的制备及性能

采用玄武岩短纤维(BF)增强硅橡胶,制备了BF/硅橡胶复合材料,考察了硅烷偶联剂的种类、BF用量以及硫化条件对复合材料力学性能的影响,并用扫描电子显微镜观察了复合材料的微观形貌。结果表明,用KH 550对BF进行表面处理,所得复合材料的力学性能优于以Si 69处理的材料;当BF用量为20份时,BF/硅橡胶复合材料的力学性能最好;制备复合材料的最佳硫化条件为10 MPa×175℃×25 min;用KH 550处理BF,BF与硅橡胶的相容性比用Si 69处理的好。     

钯催化Suzuki偶联反应的研究进展

金属Pd催化的Suzuki偶联反应是碳-碳偶联反应中重要的反应之一。综述了近年来Pd催化Suzuki偶联反应的研究进展,其中包括Suzuki反应机理、配体种类及其在有机合成中的应用。介绍了含N、P配体的钯催化剂和碳纳米管、磁性材料、多孔材料、水滑石、金属氧化物、高分子材料等负载的无配体钯催化剂的研究进展。     

Higher Hydrocarbon Production through Oxidative Coupling of Methane Combined with Hydrogenation of Carbon Oxides

In the production of higher hydrocarbons, combining oxidative coupling of methane (OCM) with hydrogenation of the formed carbon oxides in a separate reactor provides an alternative to the currently applied methane conversion to syngas followed by Fischer‐Tropsch synthesis. The effects of CH₄:O₂ feed ratio in the OCM reactor and partial pressures of H₂ or/and H₂O in the hydrogenation reactor were analyzed to maximize production of C₂₊ hydrocarbons and reduce CO_x formation. The highest C₂₊ yield was achieved with low CH₄:O₂ feed ratio for OCM and removal of the formed water before entering the hydrogenation reactor.     

Inorganic microencapsulated core/shell structure of Al–Si alloy micro-particles with silane coupling agent

Al–Si eutectic alloy is a kind of ideal high temperature phase change materials (PCMs) because of its high latent heat and good heat transfer performance. However, it is difficult for Al–Si alloy to be safely applied because of its causticity and incompatibility. In this paper, an inorganic Al–Si/Al₂O₃ micro-particles core/shell structure was prepared by the sol–gel process with the modification of silane coupling agent. The direct evidence for the forming of the dense and stable α-Al₂O₃ shell layer, whose thickness is about 3–5 μm, is presented by means of scanning electron microscopy (SEM) and X-ray diffraction (XRD). In terms of the analyses of Fourier transform infrared (FT-IR) and thermogravimetry (TG), it is apparent that the silane coupling agent is successfully grafted on the surface of Al–Si alloy micro-particles, which promotes the condensation between boehmite sols and silanol groups. The latent heat of the encapsulated Al–Si alloy was 307.21 kJ/kg and decreased during the process of microencapsulation. The reasons for the reduction of the latent heat are the excess alumina sols and the depletion of Al–Si alloy.     

无卤阻燃剂二乙基次膦酸铝的表面改性

硅烷偶联剂KH550,KH560和KH570被用于对二乙基次膦酸铝粉体阻燃剂的表面改性。经该法改性的二乙基次膦酸铝粉体的吸水率被明显降低,在PBT中的相容性被提高,并且在PBT中的分散度也得到提高。该改性方法有效地解决了利用化学沉淀法制备该阻燃剂时粉体易团聚的问题。     

10-K-302C往复压缩机润滑油管路振动数值模拟分析和优化设计

新疆某石化公司的10-K-302C离心式甲烷制冷压缩机自开机以来,其润滑油管线振动位移一直较大,运用Workbench有限元软件对空管系统进行模态分析,获得管道的固有频率和振型;采用双向流-固耦合的数值模拟方法,分析对比了润滑油在耦合时的压力、速度变化及管道耦合前后的振动频率、位移变化规律;通过将数值模拟振动分析结果与实际管路实测振动结果对比,肯定了数值模拟分析的准确性,得出了共振和管内流体速度在管道弯头处突变而造成瞬间激振力过大是管道振动主要原因的基本结论;依据上述结论,对管路系统进行了减振控制,设计后的数值模拟分析表明,管系振动大幅减少,满足工业化生产要求。