Development of Asymmetric Permeative Membrane with high hydrogen selectivity and Its Application for Separation Membrane Reactor

分离式膜反应器性能优异，通过化学反应与分离过程的良好结合，使化学反应平衡向产物侧移动。以异氢金属为分离膜材料，研制了一种高性能烃类与二氧化碳加氢反应反应器。为使反应器在实际应用中达到所要求的强度，进行了实验研究。在钯膜中发现了炭化物质在催化剂表面传播导致膜剥离的问题，这对钯膜的使用具有重要的影响。LaNi5和CaNi_5在催化性能、透氢选择性和性价比等方面均具有优异的性能。采用连续管式分离膜反应器对分离性能和反应特性进行了研究。反应器的另一侧发生了甲烷、乙烷、丙烷、正丁烷等饱和烃的脱氢反应和二氧化碳的加氢反应。通过改变操作条件，如金属成分、膜表面处理、气体压力、所用气体等，讨论了这些性能。最后，发现了LaNi_5和CaNi_5对氢的选择性，以及对上述反应的催化能力，因此，实验室规模反应器应用的可能性是明显的。此外，该反应器在膜强度、重复使用收缩效果、渗透选择性、催化能力等方面的改善，也有望成为工业设备的发展方向。

A Separate type membrane reactor was developed for much effective reactor performance, in which the chemical reaction equilibrium could be moved toward the products side by adopting good combination of chemical reaction and separation process. Hydrogen strange metals were used as separation membrane material for developing a high performance reactor carrying out the hydrogenation between hydrocarbon and carbon dioxide. Experimental work for the practical use of the reactor was carried out to achieve the desired strength in membrane characteristics. In the palladium membrane, peel problems of membrane by carbonized matter propagation on the catalyst surface were observed, which are vital blows for use. Superior characteristics of LaNi5 and CaNi_5 were found on catalytic ability, selectivity in hydrogen permeation and cost performance.In this study, Separation ability and reaction characteristics were investigated by adopting a continuous tubular type separation membrane reactor. In the reactor, dehydrogenation of saturated hydrocarbons, that is, methane, ethane, propane, n-butane and hydrogenation of carbon dioxide occurred at the other side. These performances were discussed by changing the operating conditions such as metal composition, membrane surface treatment, gas pressure, used gases and so on. Finally selectivity in hydrogen permeation was found for LaNi_5 and CaNi_5 as well as catalyst ability on the above reactions, so the possibility of the labo-scale reactor toward the application is apparent. Furthermore, the development for industrial equipment of the reactor would be expected by the improvements of membrane strength, contractior effects by repetition uses, permeation selectivity, catalyst ability and so on.