基于表面反应和扩散迁移控制的灰岩单裂隙渗流—溶解模型及其数值模拟

针对碳酸盐类可溶岩地区水电站坝址流场、化学场以及固相介质属性等随时间发生改变,从而对工程安全运行造成不利影响等问题,研究了灰岩地区地下水运移过程中各物理场间的相互作用,分析了影响灰岩溶解速率的两个因素,即表面反应控制和扩散迁移控制。在此基础上,建立了单裂隙中的渗流—溶解耦合模型,并进行数值求解。模拟结果表明,在垂直裂隙延伸方向,其溶蚀锋面为非齐整平面,而是呈似“虫洞”状非均一变化,而沿裂隙延伸方向即自上游侧向下游方向溶蚀程度逐渐减轻;而通过裂隙的流量呈现随时间逐渐增大的趋势,但变幅不大;根据流量求得的等效水力隙宽,其增幅和增长速率均小于实际平均隙宽;同时,化学场中Ca2+浓度的分布与裂隙开度变化具有相似性,不同时刻下上游侧反应速率R均大于下游侧。就反应机制而言,在初期均受表面反应控制,而随反应进行,位于上游补给区部位转为受扩散迁移控制,但在下游位置仍受表面反应控制。     

酸岩反应动力学实验影响因素研究

酸岩反应动力学实验影响因素主要包括酸液类型、酸液浓度、转子转速以及反应温度等条件,但针对不同的储层,酸岩反应影响因素的影响程度不同。通过改变上述条件,采用Crs-series Corrison Reactor System仪器进行酸岩反应动力学实验,对酸岩反应的影响因素得到了进一步的认识。     

Separation of propylene and propane with a microporous metal–organic framework via equilibrium-kinetic synergetic effect

Adsorption separation of olefin and paraffin can greatly lower the energy consumption associated with the currently utilized distillation technique but remains a great challenge. Herein, we report the efficient separation of propylene (C₃H₆) and propane (C₃H₈) in a phosphate anion-functionalized metal–organic framework (MOF) ZnAtzPO₄ by synergetic effect of equilibrium and kinetics. The material features periodically expanded and contracted apertures decorated with electronegative groups, offering eligible pore shape and pore chemistry to effectively trap C₃H₆ under moderate isosteric heat of adsorption (27.5 kJ mol⁻¹) while obstruct the diffusion of C₃H₈. It simultaneously combines excellent thermodynamic selectivity (uptake ratio of 1.71) and kinetic selectivity (~31) for C₃H₆/C₃H₈ separation, meanwhile can be easily regenerated. Breakthrough experiment for C₃H₆/C₃H₈ gas mixture was conducted and confirmed the outstanding separation capability of ZnAtzPO₄. The equilibrium and kinetics cooperative C₃H₆/C₃H₈ adsorption separation was for the first time found in anion-functionalized MOFs, and further confirmed by computational studies.     

A computational approach to characterize formation of a passivation layer in lithium metal anodes

Li metal anode is the “Holy Grail” material of advanced Lithium-ion-batteries (LIBs). However, it is plagued by uncontrollable dendrite growth resulting in poor cycling efficiency and short-circuiting of batteries. This has spurred a plethora of research to understand the underlying mechanism of dendrite formation. While experimental studies suggest that there are complex physical and chemical interactions between heterogeneous solid-electrolyte interphase (SEI) and dendrite growth, most of the studies do not reveal the mechanisms triggering these interactions. To deal with this knowledge gap, we propose a multiscale modeling framework which couples kinetic Monte Carlo and Molecular Dynamics simulations. Specifically, the model has been developed to account for (a) heterogeneous SEI, (b) dendrite-SEI interactions, and (c) effect of electrolyte on Li electrodeposition and potential dendrite formation. This allows the proposed computational model to be extended to various electrolytes and SEI species and generate results consistent with previous experimental studies.     

Thermal dehydrochlorination of pure PVC polymer: Part I—thermal degradation kinetics by thermogravimetric analysis

Thermal degradation of PVC occurs in two stages, with each stage subdivided into two substages. The first refers to the dehydrochlorination, where hydrochloric acid is formed, and giving polyene structures. Hitherto, the degradation mechanism and action of hydrochloric acid as a catalyst during the dehydrochlorination stage are poorly known. Recently, the importance of the tacticity has gained attention for its influence on the dehydrochlorination mechanism. The present work focused on the dehydrochlorination stage, studying the molecular structure by FTIR analysis and the kinetic parameters by TGA analysis in Nitrogen atmosphere, based on three mathematical methods: Friedman, Kissinger, and Flynn-Wall-Ozawa. The sample was a pure homopolymer obtained by suspension polymerization. The dehydrochlorination kinetics follows a first order reaction model and occurs by nucleation and growth. The dehydrochlorination begins with the loss of very labile chlorine atoms present in defective and isotactic molecular segments. The formed HCl acts as a catalyst in the degradation. Following 40% conversion, a drop in Ea is observed. After that, chlorine atoms present in syndiotactic and atactic sequences, are released and, added to the large number of polyene chain sequences, and an increase in Ea is observed up to 60% conversion, where the dehydrochlorination stage is concluded.     

云南电网低频问题下风机转子动能控制研究

风电机组提供频率响应后,转子转速恢复过程可能导致的频率二次跌落是制约风机提供向上调节能力的关键问题。文章对云南电网风机转子动能控制展开研究,提出风机转子动能控制参数整定方法,在扰动初期利用综合惯量控制快速抑制频率变化率,减小最大频率偏差;在扰动中后期与水火等常规同步机组和直流频率限制器(frequency limit controller,FLC)协调配合,避免频率二次跌落问题,实现频率整体动态过程的优化。仿真研究表明,增加虚拟惯性控制系数K_df,不利于改善频率最大偏差,会让频率在进入直流FLC死区后出现严重超调和反调现象;下垂控制系数K_pf是改善频率最大偏差和直流FLC动作量的关键,K_df和K_pf取值相同时,运行在最大功率追踪区的风电机组改善频率最大偏差的能力几乎相同。     

微波化学反应的无量纲准数动力学模型研究：以偶氮二异丁脒盐酸盐（AIBA）分解反应为例

微波辅助化学已成为备受关注的研究课题,但微波反应动力学模型缺乏系统的研究严重阻碍了微波在化学工业化上的应用,微波化学反应在化学工程化的放大设计及应用缺乏基础依据。以偶氮二异丁脒盐酸盐（AIBA）分解反应为例,通过选择合适的溶剂调整其复配比例,得到一系列具有不同沸点的混合溶剂作为反应介质,使反应在混合溶剂沸点下进行,以保证反应过程中微波的持续作用来研究微波反应动力学。从微波作用下动量传递、热量传递和质量传递的影响因素进行考虑,选择了对微波化学反应必须和充分的因素,包括微波功率密度 p、黏度 μ、密度ρ、反应物的浓度 C_A、温度 T、热导率 λ、损耗角正切δ 和微波辐射频率f。采用量纲分析方法,通过模型分析建立了微波分解反应动力学模型。通过大量的实验数据进行拟合,回归出特定反应的模型参数。该模型估算值与实验值的误差较小,相关性较高,具有一定的预测能力可解决微波反应过程放大的基础性问题,有望用于指导微波工业化生产。     

氧化石墨烯膜间距对电渗析空气除湿特性影响的分子动力学研究

电渗析空气除湿技术利用高压电场为气体分子荷电,通过多孔氧化石墨烯膜实现水分子和其他带电分子,如氧气分子的分离。双层膜间距将影响到气体分子的传输特性和热力学性质,本文采用分子动力学研究了带电后的水分子和氧气分子在不同膜间距下通过膜的扩散及吸附现象。结果表明：膜层间距主要影响层间氢键形成方式,继而影响多孔氧化石墨烯膜与气体分子间吸附能,存在最佳层间距离1.25 nm,水分子渗透效果最佳,气体选择性达到最高,为1.14,较无电场时扩大了3倍。     

利用转子动能的风机辅助频率控制最优策略

风机增加辅助频率控制模块是解决新能源取代同步机导致的电力系统频率安全问题的一种方案,其中利用转子动能的调频模式可以使风机运行在最大功率点,经济性比功率备用模式更好。已有研究主要让风机通过虚拟惯量和频率下垂控制模拟同步机,却未充分利用风机控制灵活、可塑性强的优点,且未考虑风机转子动能限制及系统频率二次跌落。论文跳出虚拟惯量加频率下垂控制的传统框架,提出利用转子动能的风机辅助频率控制最优策略。首先将风机输出功率曲线作为决策变量,通过优化得到最优功率曲线,然后设计对应的辅助频率控制策略,实现最优输出功率曲线。仿真结果验证所提策略的效果,并说明风机辅助频率控制不应局限于模拟同步机,而是有更优的策略。     

CVD法合成SiC晶须的实验研究

利用简单的实验设备，特殊的金属丝作触媒，以ＳｉＯ２和Ｃ为原料，利用碳热还原反应生成的ＳｉＯ和ＣＯ，通过ＣＶＤ的方法快速合成α－ＳｉＣ晶须，用光学显微镜研究了晶须的生长速度，通过ＴＥＭ研究α－ＳｉＣ晶须的结构和生长方式。讨论了这种方法中α－ＳｉＣ晶须生长的热力学条件，机理及生长动力学模型。