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

分离式膜反应器采用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，具有更好的反应性能。以氢奇异金属为分离膜材料，研制了一种高效的烃类与二氧化碳加氢反应器。进行了用于反应器的实际使用的实验工作，以实现膜特性的期望强度。在钯膜中，观察到了由催化剂表面上的非晶物质传播引起的膜剥离问题，这对使用是至关重要的打击。LaNi_5和CaNi_5在催化性能、透氢选择性和性价比方面具有上级特点，本研究采用连续管式分离膜反应器，考察了它们的分离性能和反应特性。在反应器中，饱和烃类，即甲烷，乙烷，丙烷，正丁烷的脱氢和二氧化碳的加氢发生在另一侧。通过改变金属组成、膜表面处理、气体压力、使用气体等操作条件，考察了LaNi_5和CaNi_5对氢渗透的选择性以及催化剂对上述反应的催化能力，表明该反应器具有实验室规模应用的可能性。此外，膜强度、重复使用的收缩效果、渗透选择性、催化剂性能等方面的改进，也是该反应器工业化设备的发展方向。

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.