物理化学教学中安全工程教育的融合与内化实例*

如何强化安全工程教育是化学化工类专业高等教育的一个重要课题。通过对蒸汽锅炉爆炸、火灾爆燃事故以及锈蚀危害等3个实例的详细讲述,指出在物理化学的教学中,若适时融入相关的安全工程教育,可以使学生深刻理解安全事故发生及防范所依赖的物理化学原理,从而起到安全意识的内化作用。教学中现代教育技术的引入可以增强这一效果。     

真空中铝单丝电爆炸的实验研究

开展了铝单丝在负极性电流脉冲作用下电爆炸特性的研究.利用皮秒激光探针,搭建了阴影、纹影和干涉的光学诊断平台,得到了不镀膜铝丝典型的能量沉积过程,在电压崩溃时刻其沉积能量为2.4 eV/atom.为了增加金属丝内的沉积能量,开展了相同电参数及金属丝尺寸下的镀膜铝丝电爆炸实验,其沉积能量可达到5 eV/atom,实现了在电压崩溃之前铝丝完全气化(完全气化所需能量为4 eV/atom).阴影图像展示了高密度丝核区域的膨胀过程,不镀膜铝丝平均膨胀速度为2.2 km/s,而镀膜铝丝因为沉积能量大,其膨胀速度约为不镀膜铝丝的2.3倍,高密度区域膨胀速度为5 km/s.由于阴影不能反映低密度等离子体的膨胀,开展了平行双丝实验,通过测量自发光辐射,估算了低密度等离子体的膨胀速度.利用条纹相机拍摄了不镀膜铝丝电爆炸过程中自发光区域的图像.纹影图像清晰地展示了不镀膜铝丝在电爆炸过程中形成的核冕结构,而镀膜铝丝电爆炸过程中核冕结构得到了一定程度的抑制.从干涉图像计算了相移,在轴对称假设下对相移进行阿贝尔逆变换,重构了三维的铝原子数密度分布.     

开放式天然气泄漏甲烷气体检测技术研究

天然气集输站场是天然气输送和储存过程中的枢纽,也是天然气泄漏检测的重点对象。传统的天然气泄漏检测技术响应慢、效率低,难以满足实际所需。可调谐半导体激光吸收光谱技术(TDLAS)以其响应速度快、灵敏度高、无需维护等优点得到广泛应用。使用可调谐半导体激光吸收光谱技术实现了同时对天然气的主要成分甲烷、乙烯、乙炔三种气体实时测量的开放式检测和报警系统。实验结果表明,该系统响应时间小于2s,其甲烷、乙烯、乙炔的测量精度分别小于100ppm-m,40ppm-m,50ppm-m,为石油化工行业中天然气泄漏检测技术提供了新的技术方法。     

基于Aspen Plus的小型含氧煤层气液化工艺分析

针对某一典型含氧煤层气气源,构建了适用于小型液化装置的丙烷预冷氮-甲烷膨胀液化精馏工艺,并采用Aspen Plus对该流程进行建模及分析。以流程比功耗、甲烷回收率为评价指标,分别研究了制冷剂高压压力PN2和低压压力PN7对流程比功耗的影响。结果表明,在PN2为3.8MPa,P_(N7)为0.3MPa时,比功耗为0.513k Wh·Nm~3,甲烷回收率为93.42%,LNG产品纯度接近100%。结合爆炸极限计算表明,含氧煤层气在压缩、冷却、液化及节流过程中,甲烷浓度均高于爆炸上限,操作安全性较高,而精馏塔顶部甲烷浓度变化会穿越爆炸上下限区间,基于此,采用原料气低压初脱氧的方式来控制精馏塔顶部氧气含量。分析结果表明,对当粗脱氧后进入压缩机的煤层气含氧量低于2.4mol%时,流程操作安全可靠。     

LNG尾气中提取氦气的流程分析

LNG产业的蓬勃发展为资源利用开发了新的途径。基于液化天然气尾气的特点,文中提出了一种与液化天然气产业联产氦气的新方法,设计了相应的工艺流程。通过对尾气进行增压脱酸、冷凝分离、加氧脱氢、内纯化除杂等多种处理,可对天然气尾气中的氦进行有效提取分离,最终达到纯氦的技术指标。该方法有望使国内不具备工业提取价值的氦资源重新得到利用,在国内建立一种新型的氦供应途径。     

微型平面复合薄膜电爆炸开关的设计和研究（英文）

开关技术是影响爆炸箔起爆系统可靠作用、微型化、低能化、集成化的关键技术。电爆炸平面开关是利用强脉冲电流使触发极金属桥箔发生电爆炸,产生高温高压等离子体,使爆炸桥区两侧的电极导通。基于微加工技术,采用Al/CuO复合薄膜材料作为触发电极,设计制造了微型平面复合薄膜电爆炸开关。采用扫描电子显微镜、差示扫描量热法和光谱谱线测温研究了触发极Al/CuO复合薄膜的形貌、反应性和电爆炸等离子体温度,通过放电电流测试研究了开关性能。结果表明,在主回路电压2000V时,开关输出电流峰值约为1938A,上升时间390ns,性能优于仅以铜薄膜为触发电极的电爆炸平面开关。     

ZnO添加量对Pd/Zr0.5Al0.5O1.75催化剂净化稀燃天然气汽车尾气性能的影响

以掺杂不同含量ZnO的Zr_0.5Al_0.5O_1.75为载体,制备了系列1.5%Pd催化剂.在模拟稀燃天然气汽车尾气条件下,测试了催化剂的活性和抗水性,并用N₂吸附-脱附、X射线衍射、H₂程序升温还原和X射线光电子能谱等手段对催化剂进行了系统表征.研究结果表明,ZnO的添加及添加量对催化剂的活性和抗H₂O性有明显影响,其中以ZnO添加量为15%时制备的复合氧化物为载体的催化剂活性最佳.当模拟尾气中不含H₂O时,该催化剂对甲烷的起燃温度（T₅₀）和完全转化温度（T₉₀）分别为278和314℃;在含H₂O时,该催化剂的T₅₀和T₉₀分别为342和371℃.     

常见客体分子对笼型水合物晶格常数的影响

Natural gas hydrates are considered as ideal alternative energy resources for the future, and the relevant basic and applied research has become more attractive in recent years. The influence of guest molecules on the hydrate crystal lattice parameters is of great significances to the understanding of hydrate structural characteristics, hydrate formation/decomposition mechanisms, and phase stability behaviors. In this study, we test a series of artificial hydrate samples containing different guest molecules (e.g. methane, ethane, propane, iso-butane, carbon dioxide, tetrahydrofuran, methane + 2, 2-dimethylbutane, and methane + methyl cyclohexane) by a low-temperature powder X-ray diffraction (PXRD). Results show that PXRD effectively elucidates structural characteristics of the natural gas hydrate samples, including crystal lattice parameters and structure types. The relationships between guest molecule sizes and crystal lattice parameters reveal that different guest molecules have different controlling behaviors on the hydrate types and crystal lattice constants. First, a positive correlation between the lattice constants and the van der Waals diameters of homologous hydrocarbon gases was observed in the single-guest-component hydrates. Small hydrocarbon homologous gases, such as methane and ethane, tended to form sI hydrates, whereas relatively larger molecules, such as propane and iso-butane, generated sⅡ hydrates. The hydrate crystal lattice constants increased with increasing guest molecule size. The types of hydrates composed of oxygen-containing guest molecules (such as CO₂ and THF) were also controlled by the van der Waals diameters. However, no positive correlation between the lattice constants and the van der Waals diameters of guest molecules in hydrocarbon hydrates was observed for CO₂ hydrate and THF hydrate, probably due to the special interactions between the guest oxygen atoms and hydrate "cages". Furthermore, the influences of the macromolecules and auxiliary small molecules on the lengths of the different crystal axes of the sH hydrates showed inverse trends. Compared to the methane + 2, 2-dimethylbutane hydrate sample, the length of the a-axis direction of the methane + methyl cyclohexane hydrate sample was slightly smaller, whereas the length of the c-axis direction was slightly longer. The crystal a-axis length of the sH hydrate sample formed with nitrogen molecules was slightly longer, whereas the c-axis was shorter than that of the methane + 2, 2-dimethylbutane hydrate sample at the same temperature.     

三维无溶剂含能Ag-MOF的制备、热分解动力学及爆炸性能

Solvent molecules can significantly reduce the heat of detonation and stability of energetic metal-organic framework (EMOF) materials, and the development of solvent-free EMOFs has become an effective strategy to prepare high-energy density materials. In this study, a solvent-free EMOF, [Ag₂(DTPZ)]_n (1) (N% = 32.58%), was synthesized by reacting a high-energy ligand, 2, 3-di(1H-tetrazol-5-yl)pyrazine (H₂DTPZ), with silver ions under hydrothermal conditions, and it was structurally characterized by elemental analysis, infrared spectroscopy, X-ray diffraction, and thermal analysis. In 1, the DTPZ²⁻ ligands that adopted a highly torsional configuration bridged the Ag⁺ ions in an octadentate coordination mode to form a three-dimensional framework (ρ = 2.812 g∙cm⁻³). The large steric effect and strong coordination ability of DTPZ²⁻ effectively prevented the solvent molecules from binding with the metal centers or occupying the voids of 1. Moreover, the strong π-π stacking interactions [centroid-centroid distance = 0.34461(1) nm] between the tetrazole rings in different DTPZ²⁻ ligands provided a high thermal stability to the framework (T_e = 619.1 K, T_p = 658.7 K). Thermal analysis showed that a one-step rapid weight loss with intense heat release primarily occurred during the decomposition of 1, suggesting potential energetic characteristics. Non-isothermal thermokinetic analyses (based on the Kissinger and Ozawa-Doyle methods) were performed using differential scanning calorimetry to obtain the thermoanalysis kinetic parameters of the thermodecomposition of 1 (E_a = 272.1 kJ·mol⁻¹, E_o = 268.9 kJ·mol⁻¹; lgA =19.67 s⁻¹). The related thermodynamic parameters [enthalpy of activation (ΔH^≠ = 266.9 kJ·mol⁻¹), entropy of activation (ΔS^≠ = 125.4 J·mol⁻¹·K⁻¹), free energy of activation (ΔG^≠ = 188.3 kJ·mol⁻¹)], critical temperature of thermal explosion (T_b = 607.1 K), and self-accelerating decomposition temperature (T_SADT = 595.8 K) of the decomposition reaction were also calculated based on the decomposition peak temperature and extrapolated onset temperature when the heating rate approached zero. The results revealed that 1 featured good thermal safety, and its decomposition was a non-spontaneous entropy-driven process. The standard molar enthalpy for the formation of 1 was calculated to be (2165.99 ± 0.81) kJ·mol⁻¹ based on its constant volume combustion energy determined using a precise rotating oxygen bomb calorimeter. Detonation and safety performance tests revealed that 1 was insensitive to impact and friction, and its heat of detonation (10.15 kJ·g⁻¹) was higher than that of common ammonium nitrate explosives, such as octogen (HMX), hexogene (RDX), and 2, 4, 6-trinitrotoluene (TNT), indicating that 1 is a promising high-energy and insensitive material.     

LNG耐超低温柔性管道研究进展综述

LNG (液化天然气)耐超低温柔性管道是开采、运输、存储LNG过程中的关键装备之一, 被誉为是LNG外输系统的“血管”. 近年来, 随着LNG的开发逐渐由近海走向深远海, 耐超低温柔性管道作为LNG外输系统中的核心输运装备迎来了更加广阔的发展前景, 同时也面临着由更加严苛的海洋环境带来的结构失效的挑战. 本文针对LNG耐超低温柔性管道的工程应用背景、结构设计、内流分析等方面进行了调研与综述, 总结了LNG耐超低温柔性管道上述各项技术的研究进展. 分析了LNG耐超低温柔性管道的波纹管状结构、螺旋缠绕结构和高分子材料的柔顺性结构特征的力学机理, 总结了实现柔顺性结构的方法, 梳理了LNG耐超低温柔性管道管内流体计算分析的规律, 并对LNG耐超低温柔性管道相关技术的未来研究热点提出了展望. 我国在LNG耐超低温柔性管道相关技术的研究工作中起步相对较晚, 突破LNG耐超低温柔性管道的结构设计分析与工业应用中的关键力学问题, 实现LNG耐超低温柔性管道的国产化研制, 对于实现我国深远海天然气资源开发的“卡脖子”技术的自主可控, 助力“碳达峰”国家战略目标的实现具有重要意义.