ZSM-5分子筛酸位分布及其甲醇制烯烃催化性能的定向管理与调控

ZSM-5分子筛在甲醇制烯烃(MTO)过程中的催化性能和反应机理与其孔道中酸位点分布位置紧密相关. 本文证明在水热合成过程中加入适量的钠离子(Na⁺)可以增加ZSM-5分子筛交叉腔酸位点比例; 从而促进高级甲基苯的生成并加速芳烃循环, 有利于乙烯生成. 相反, 在合成过程中不添加钠离子, 所制备的ZSM-5分子筛直孔道和正弦孔道酸位点比例明显提高, 有利于促进烯烃循环并提高丙烯和C₃₊烯烃选择性.     

Interpretation of wake instability at slip line in rotating detonation

ABSTRACT

In studies on instabilities of flowfield in rotating detonation, one of the most common concerns is the instability at the slip line originating from the conjunction of the detonation wave and oblique shock. Using Euler equations associated with the 7-species-and-8-reaction finite-rate chemical reaction model of hydrogen/air mixtures, further studies are performed to simulate the 2-D rotating detonation, and the flow mechanism of instability at the slip line is investigated in depth. The results show that the distinct wake profile exists at the slip line, which is different from the typical mixing layer. Analysis indicates that the generation of wake is caused by the transition shock between the detonation wave and oblique shock. Because of the wake profile, the vorticity distribution therein appears in a double-layer layout, and different evolutions exist in different vorticity layers. Based on the velocity profile across the slip line, the analysis by the linear stability theory is made, and two main unstable modes which have different shape profiles and phase velocities are found. Discrete Fourier transformation is utilised to analyse the numerical results, and similar shape profiles are obtained. A general coincidence in velocity of vortex movement is also attained between the theoretical predictions and simulations. Investigations show that the wake instability is responsible for the unstable mechanism, and corresponding unstable structures differ from the canonical ones in typical mixing layers.     

H-ZSM-5分子筛不同孔道处的酸位在甲醇制烯烃反应中的催化作用

甲醇制烯烃(MTO)作为一条由煤、天然气和生物质等含碳资源制备重要有机化学品的非石油路线,近年来备受关注.作为MTO催化剂,分子筛的骨架拓扑结构和酸性质对于其催化活性、反应路径和产物分布等具有重要的影响.H-ZSM-5分子筛是一种典型的MTO反应催化剂,酸位可以分布在MFI拓扑结构的直孔道、正弦孔道和交叉位点处.虽然目...     

Surfactant Assembly within Pickering Emulsion Droplets for Fabrication of Interior‐Structured Mesoporous Carbon Microspheres

Large‐sized carbon spheres with controllable interior architecture are highly desired, but there is no method to synthesize these materials. Here, we develop a novel method to synthesize interior‐structured mesoporous carbon microspheres (MCMs), based on the surfactant assembly within water droplet‐confined spaces. Our approach is shown to access a library of unprecedented MCMs such as hollow MCMs, multi‐chambered MCMs, bijel‐structured MCMs, multi‐cored MCMs, “solid” MCMs, and honeycombed MCMs. These novel structures, unattainable for the conventional bulk synthesis even at the same conditions, suggest an intriguing effect arising from the droplet‐confined spaces. This synthesis method and the hitherto unfound impact of the droplet‐confined spaces on the microstructural evolution open up new horizons in exploring novel materials for innovative applications.     

氮气热处理对硫代硫酸铵预硫化的Mo／Al2O3催化剂的影响

考察了氮气预处理温度对硫代硫酸铵预硫化的Mo/Al2O3催化剂噻吩加氢脱硫(HDS)活性的影响. 采用X射线衍射、高分辨电镜、光电子能谱、热重质谱和硫分析等方法对催化剂进行了表征. 结果表明,预硫化催化剂经80 ℃低温处理并于200 ℃氢气原位活化后噻吩转化率达到最高. 对于氮气低温预处理或常温干燥的预硫化催化剂,载体氧化铝被硫酸根修饰,减少了Mo与载体的相互作用,使得催化剂活化后硫化程度高, MoS2活性相呈多层的Ⅱ型结构,因而HDS活性高. 高于200 ℃的氮气热处理造成硫代硫酸铵的分解,并有少量的多层MoS2活性相生成,但高温热处理造成硫的流失使得活性金属活化后硫化程度偏低,而且MoS2活性相呈现单层的Ⅰ型结构,因而HDS活性较低.     

A comparative investigation of Co2+ and Mn2+ incorporation into aluminophosphates by in situ XAS and DFT computation

The incorporation processes of Mn2+ and Co2+ into the framework of aluminophosphate molecular sieve AlPO4-5, at the onset of crystallization, were investigated by in situ synchrotron X-ray absorption spectroscopy (XAS) and density functional theory (DFT) computation. The results indicated that the syntheses of MnAPO-5 and CoAPO-5 were different in the incorporation mechanism of metal ions. For the synthesis of CoAPO-5, Co2+ transferred from an octahedral into tetrahedral structure with crystal formation, while, for MnAPO-5, the Mn2+ transition to the tetrahedral structure was much more difficult and it occurred after the appearance of long-range ordered microporous structure. The DFT computations of model intermediates involved in the synthesis process suggested that much higher transformation energy of [Mn(OP(OH)3)4]2+ than that of [Co(OP(OH)3)4]2+ was responsible for the diversity of the incorporation behaviors.     

Structure and stability of β-Mo2C bulk and surfaces: A density functional theory study

Density functional theory calculations have been performed on the structure and stability of β-Mo₂C bulk and the corresponding low-index surfaces. The eclipse configuration with a Mo-C-Mo-C stacking is the most stable, followed by the structure with a Mo-C-Mo-Mo-C stacking where there is an empty carbon layer every fourth layer. For (0 0 1) and (1 0 0) surfaces, the pure C terminations are more stable than the pure Mo terminations. For (0 1 0) and (1 1 1) surfaces, the Mo terminations are more stable than the C terminations. For the (0 1 1) surface, the mixed Mo/C termination is a little more stable than the Mo termination. Relaxation of these surfaces is moderate with no relaxation degree exceeding 12.8%. Among these surfaces, the mixed Mo/C termination of the (0 1 1) surface is the most stable with the lowest surface free energy, followed by the (1 0 1) surface and the T_Mo-2 termination of the (0 1 0) surface.     

CeO2-TiO2混合氧化物及Pd/CeO2-TiO2催化剂的氧化还原性能

 以溶胶-凝胶-超临界流体干燥法制备了CeO2-TiO2混合氧化物(n(Ce)/n(Ti)=0.05～0.40),以其为载体,通过等体积浸渍法制备了Pd/CeO2-TiO2催化剂. XRD分析结果表明,在低Ce/Ti比的CeO2-TiO2混合氧化物中,CeO2高度分散于TiO2上; Ce/Ti比高于0.10时,大晶粒锐钛矿相TiO2和TiO2-CeO2固溶体或其前驱体无定形相共存. 采用H2-TPR对所合成材料的氧化还原性能进行了研究. H2-TPR谱中500 ℃附近的耗氢峰对应于CeO2-TiO2中CeO2的还原,还原过程中不存在表面晶格氧与体相晶格氧的差别. 由于TiO2与CeO2的协同作用,混合氧化物中形成了丰富的结构缺陷,提高了CeO2的氧化还原性能,其中Ce/Ti比为0.20时TiO2与CeO2的协同作用最显著. 负载上Pd后,载体中CeO2的还原温度(＜150 ℃)大大降低,同时随着Ce/Ti比的增大,PdO与载体间的相互作用增强,导致PdO难于还原,相应的H2-TPR还原峰向高温方向移动.     

Beta分子筛催化剂上甲苯和三甲苯烷基转移反应条件优化及其反应机理研究

以Beta分子筛为催化剂, 系统考察了反应条件和催化剂酸性变化对甲苯和三甲苯烷基转移反应催化性能的影响. 实验结果表明, 反应条件、分子筛晶粒尺寸及其酸性对烷基转移催化活性和稳定性都具有显著影响. 研究发现: 当反应温度为450 ℃、压力为3 MPa以及反应物甲苯和三甲苯物质的量比为1时, 二甲苯收率达到最高; 分子筛催化活性随硅铝比升高而降低; 催化剂晶粒尺寸减小能够显著提高反应稳定性. 同时, 还对甲苯和三甲苯烷基转移反应机理进行了深入研究, 推导出了可能的反应机理路线图.     

Conservation relation of generalized growth rate in boundary layers

The elementary task is to calculate the growth rates of disturbances when the e^N method in transition prediction is performed. However, there is no unified knowledge to determine the growth rates of disturbances in three-dimensional (3D) flows. In this paper, we study the relation among the wave parameters of the disturbance in boundary layers in which the imaginary parts of wave parameters are far smaller than the real parts. The generalized growth rate (GGR) in the direction of group velocity is introduced, and the conservation relation of GGR is strictly deduced in theory. This conservation relation manifests that the GGR only depends on the real parts of wave parameters instead of the imaginary parts. Numerical validations for GGR conservation are also provided in the cases of first/second modes and crossflow modes. The application of GGR to the e^N method in 3D flows is discussed, and the puzzle of determining growth rates in 3D flows is clarified. A convenient method is also proposed to calculate growth rates of disturbances in 3D flows. Good agreement between this convenient method and existing methods is found except the condition that the angle between the group velocity direction and the x-direction is close to 90° which can be easily avoided in practical application.