煤层气在多孔介质填充管线反应器中的水合实验研究

针对目前传统方式（低温液化、变压吸附、膜分离等）对低浓度煤层气增浓工业化应用的不适用性问题，提出通过合成水合物的方式实现低浓度煤层气中CH4的富集。但该技术的实现需要解决煤层气水合物合成过程中合成速率慢，储气密度低两个问题。借鉴日本对管线式反应器的试验结果与目前理论与实验研究所得出的THF与SDS分别对水合物合成相平衡条件、储气密度、合成速率的最佳促进浓度配比和多孔介质的加入对水合物合成促进作用的研究成果，以5×10-10 m沸石分子筛填充管线反应器作为水合界面，研究了17 mol%THF+300PPmSDS理论最佳促进体系下的水合物合成速率变化与工业化实现指标。实验结果表明：随着压力的升高，整体管线反应速率加快，合成速率峰值沿反应管线前移；水合驱动力的升高可有效提高水合物储气效率，且过压驱动力对水合储气的影响强于过冷驱动力；284 K/1.5 MPa条件下利用一次反应后多孔介质进行二次合成，达到相同储气量时，反应时间仅为一次合成的10%；随着水合时间的加长284 K/1.8 MPa条件下水合单位耗气达到了67.25 mL/mL，配合二次合成对水合时间的缩短效应，可大大提高水合物合成的储气速率与储气密度。

Experiment study on CBM hydrates formation in tubular reactor stuff with porous medium

As a traditional purification technology (low temperature liquefaction,pressure swing absorption,membrane separation,etc.) is not applicable to low concentration coal bed methane (CBM),a new technology is put forward,which achieves the enrichment of CH4 with low concentration CBM in a hydrates formation way.However,to implement such technology,there are two problems in the process of CBM hydrates formation,such as low hydrates formation rate and low gas storage density,which are required to be solved.The tubular reactor test results in Japan and the research achievements obtained from the current theoretical research and experimental study including the optimum concentration ratio promoted by THF and SDS based on the hydrates formation phase equilibrium condition,gas density and hydrates formation rate and the promotion of porous medium to hydrates formation are used for reference in this study.The change of hydrates formation rate and industrial implementation under the optimum promotion system of 17mol%THF+300PPmSDS theory are investigated by taking the tubular reactor filled with 5×10-10 m zeolite as the CBM hydrates formation interface.The results show that with the increase of the formation pressure,the rate of the whole pipeline reaction rate increases and the peak moves forward along the pipeline； with the increase of the hydrate driving force,the gas storage efficiency of hydrate is improved,and the effect of over-voltage driving force on hydrate gas storage is stronger than that of under-cooling driving force； in the condition of 284 K/1.5 MPa,after primary formation,the second formation is generated by porous medium,when the same gas storage capacity is achieved,ge,the secondary formation time is only 10% of the first formation time； in the condition of 284 K/1.8 MPa,with the increase of the formation time,the gas consumption per formation unit reaches 67.25 mL/mL,and the formation rate and gas density of the hydrates can be improved greatly by using the shortening effect of secondary formationtime.