煤矿瓦斯水合分离与储运应用基础研究

Improving the extraction and utilization ratio of coal mine gas needs to be strengthened for the national energy conservation and emission reduction strategy. The advantages of gas separation based on hydrate technology, such as gas hydrate separation and storage and transportation integration, wide applicable scope (CH4 concentration > 7.8%) and other technical characteristics highlighted the urgency to carry out in-depth systematic research in improving the extraction and utilization of coal mine gas. In the experimental scope, gas hydrate phase equilibrium condition, separation kinetics and Raman spectra characteristics of hydration products, heat and mass transfer in the strengthening process, storage stability are investigated using self-developed equipments for phase equilibrium measurement, spray/bubbling strengthening, hydrate storage and transportation, combined with the in situ analysis technology such as laser Raman spectrometer. In the theory scope, multiple - multiphase gas hydrate phase equilibrium system model is established, based on the Chen-Guo theory, Van der Waals -Platteeuw model, Gas-liquid interface bidirectional diffusion, heat transfer theory, and CH4 hydrate decomposition model. Thus, the variation laws for gas hydrate induction time, separation rate, crystal structures of hydration products, gas ratio, gas purification concentration, gas recovery are clarified in the gas hydration process and the heat and mass transfer mechanism for the droplets/bubble - gas/water solution reaction system are revealed. Finally, the kinetics of gas hydrates decomposition is illustrated under the different temperature and pressure. The research work has important scientific significance and engineering value for establishing the theoretical system of the gas hydrate separation and gas hydrate storage and transportation and for promoting the industrial gas hydrate technology application.

提高煤矿抽采瓦斯利用率是国家节能减排战略需要。瓦斯水合分离与储运一体化、适用范围广（CH4浓度＞7.8%）等技术特点凸显了开展深入系统研究的迫切性。利用自主研制的相平衡测定、喷雾/鼓泡强化、水合物储运等实验装置，结合激光拉曼光谱仪等原位分析技术，开展瓦斯水合物相平衡条件测定、分离动力学、水合产物拉曼光谱特征、强化过程热质传递、储运稳定性等实验研究，结合Chen-Guo理论、van der Waals-Platteeuw模型、气液界面扩散-传热理论、CH4水合物分解模型，建立多元-多相体系瓦斯水合物相平衡模型，确定瓦斯水合过程诱导时间、分离速率、水合产物晶体结构、储气率、提纯浓度、回收率等变化规律，揭示液滴/气泡-瓦斯/水溶液反应体系热质传递机理，阐明不同温压控制条件下瓦斯水合物分解动力学规律。该研究工作对于构建瓦斯水合分离与储运理论体系、推动瓦斯水合技术工业应用具有重要科学意义和工程价值。

提高煤矿抽采瓦斯利用率是国家节能减排战略需要。瓦斯水合分离与储运一体化、适用范围广等技术特点凸显了开展深入系统研究的迫切性。围绕我国煤矿区典型抽采瓦斯混合气体，利用自主研制的相平衡测定、喷雾/鼓泡强化、水合物储运等实验装置，结合激光拉曼光谱仪等原位分析技术，开展了瓦斯水合物相平衡条件测定、分离动力学、水合产物拉曼光谱特征、强化过程热质传递、储运稳定性等实验研究，结合Chen-Guo理论、van der Waals-Platteeuw模型、气液界面扩散-传热理论、CH4水合物分解模型，获取了多元-多相体系瓦斯水合物相平衡参数及不同瓦斯水合分离产物的Raman光谱特征，确定了瓦斯水合过程诱导时间、分离速率、水合产物晶体结构、储气率、提纯浓度、回收率等变化规律，获得了不同体系中瓦斯水合分离目标参数的变化规律，确定了冰体系瓦斯水合分离动力学规律；建立液滴-瓦斯水合传热-传质数学模型，揭示了液滴/气泡-瓦斯/水溶液反应体系热质传递机理，阐明了不同温度压力控制条件下瓦斯水合物分解动力学规律。以理论规律指导实际应用，为实现瓦斯水合固化分离与储运技术的现场应用，本课题所进行的前期工作为后续实验开展、设备研制、技术开发提供了理论指导和基础数据支持，起到了积极的推动作用。基于本项目获得的实验规律对于构建瓦斯水合分离与储运理论体系、推动瓦斯水合技术工业应用具有重要科学意义和工程价值。