基于Raman光谱的煤体瓦斯水合过程动力学研究

The effective acquisition of kinetic parameters of mine gas hydration process inthe outburst coal mass is the key to promoting engineering applications of minegas hydration curing and outburst prevention technology in industrial field.Accordingly, Raman data will be acquired from mine gas hydration process inbriquette body with different particle sizes and the information of special peak,acreage and strength process will be precisely monitored by via the laser Ramanspectroscopy online test system for the gas hydrate curing reaction, analyzinginformation of Raman spectroscopy and in-situ characterization mass transfer.Then, the crystal structures are determined based on the vibration modes of guestmolecules and the loose-cage-tight-cage model. In addition, the cage occupancyratio and hydration number are analytically determined from the van derWaals-Platteeuw model, the gas hydrate reaction micro mass transfer process willbe analyzed. At last, the kinetic model of hydrate formed in the coal wasestablished based on the connection of the Chen-Guo hydrate theory with discussingthe interaction rules among the types of coal samples, driving forces andhydration numbers etc. from the view of driving force being changed by the porestructure of coal influencing the phase equilibrium, we will try researchingmicrokinetics process of coal gas hydrate formation from molecular level.Engineering applications of mine gas hydration curing and outburst preventiontechnology will be improved by the research results, as well as theoreticallyimproving the gas hydrate curing technology and developing the technology ofcoal and gas outburst prevention in depth and breadth has important scientificsignificance.

突出煤体瓦斯水合过程动力学参数的有效获取是促进瓦斯水合固化防突技术工业应用的关键。据此，首先利用瓦斯水合固化反应激光Raman光谱在线测试实验平台，开展不同粒径下型煤瓦斯水合过程Raman光谱测试，获取不同反应时刻水合产物Raman光谱，分析Raman特征峰位移、面积、强度等信息；而后，基于客体分子振动模式、van der Waals-Platteeuw模型，确定瓦斯水合物晶体结构，计算孔穴占有率、水合指数等结构参数，分析煤体瓦斯水合反应物质传递微观过程；最后，从煤样孔隙结构相平衡影响及其驱动力改变角度，探索煤样类型、驱动力、水合指数等相互作用规律，结合Chen-Guo水合物理论，建立煤体瓦斯水合过程动力学模型，尝试从分子水平揭示煤体瓦斯水合物生长微观动力学过程。研究成果对于完善瓦斯水合固化防突技术、推动煤与瓦斯突出防治技术向纵深发展具有重要科学意义。

煤与瓦斯突出是最严重的的煤矿事故之一，极大程度上威胁着煤矿的安全高效开采和矿井工作人员的生命安全。煤矿瓦斯是引发煤与瓦斯突出的动力条件，瓦斯水合固化防突技术能有效降低瓦斯压力和煤与瓦斯突出发生的危险性，煤体中瓦斯水合物合成热力学与生长动力学则是瓦斯水合固化防突技术的关键所在。因此，本项目以CH4/CO2和4种粒径煤粒为研究对象，先利用瓦斯水合物相平衡测定装置对不同煤粒中瓦斯水合物相平衡条件进行测定，而后在测定的相平衡条件基础上依次开展瓦斯气样、驱动力、粒径煤粒影响下的瓦斯水合物生长动力学实验，获取各实验体系瓦斯水合物生长过程的目标参数，掌握煤粒中瓦斯水合物生长动力学及煤样类型、驱动力等相互作用规律。利用瓦斯水合反应Raman光谱在线测试平台对温度275.15K、压力2.5MPa、3.0MPa、3.5MPa条件下瓦斯气体水合反应进行原位测试，获取了三种驱动力下瓦斯水合产物的Raman谱图，基于客体分子振动模式、“松笼-紧笼”模型及Raman谱带面积比，结合Van der Waals-Platteeuw模型，确定出水合物晶体结构，计算出晶体孔穴占有率、水合指数等结构参数。.在本项目资助下，目前共发表学术论文5篇，其中SCI检索1篇、EI检索2篇；出版专著1部；申请授权国家专利2项；培养青年学术骨干2名，培养博士1名、硕士2名，已有1位硕士顺利毕业。