笼形水合物的科学与技术研究以及在能源和环境领域中的应用
Clathrate hydrate science and technology with energy and environmental applications
-
摘要: 能源与环境是人们越来越关注的问题,而笼形水合物同时在这两方面展示出了巨大的应用前景:(1) 在广阔的海底大陆架中蕴藏着大量的以甲烷为主体的笼型水合物——天然气可燃冰;(2) 将大气中日益增多的二氧化碳装入笼型水分子中并沉于海底以降减温室效应;(3) 氢气可燃冰作为一种清洁的能源载体具有很高的能量密度、可重复再生、可快速充氢;(4) 利用笼形水合物的形成过程,可以有效地分离气体、降低能耗、减轻污染.虽然笼形水合物在工程应用以及科学研究中有着重要的价值, 但其晶体结构, 成键机制, 温压相图, 热化学与力学稳定性, 合成与分解的反应动力学, 声学弹性, 与海底沉积的反应, 以及扩散和输运性质等都有待深入的研究.目前,科学家已经研发或者正在探讨将高压和低温装置与中子衍射技术以及激光光谱、热学测量、超声技术等有机的结合在一起, 从而能够进行一系列的实验研究来解决诸多的基本科学问题. 高压及低温环境下的中子衍射装置在氢气、甲烷以及二氧化碳气体水合物体系研究中显示了巨大的优势, 并且在确定水合物晶体结构, 气体分子在水合物笼格中的占据情况, 以及气体分子在笼格中的分布状态等方面取得了巨大的进展.Abstract: Energy and environment concerns are becoming more and more urgent for the existence and progress of human society. Clathrate hydrates hold great promise in a number of aspects: (1) vast methane hydrate deposits have been found in the continental shelf around the world; (2) oceanic sequestration of CO2 may be a feasible approach to reduce the greenhouse effect; (3) hydrogen clathrate hydrates of high energy density are readily rechargeable; (4) clathrate hydrate processing is a very effective way for gas separation and is great for energy saving and emission reduction. Despite the engineering and scientific importance of clathrate hydrates in energy resources and environmental aspects, much remains to be learned about their crystal structures, molecular bonding mechanisms, P-T phase diagrams, formation/decomposition kinetics, thermodynamic and mechanical stabilities, and acoustic (seismic) elasticity. Recent experimental studies of H2, CH4, and CO2 clathrate hydrates have been integrating neutron diffraction, laser spectroscopy, thermal analysis, and ultrasonic experiments at moderate (1 to 100 MPa) to high (0.1 to 1 GPa) pressures, and great progress has been made in the studies of their crystal comstructure, occupation of gas molecules in the hydrate cages, as well as their temperature-pressure phase diagrams.