산처리한 Clinoptilolite Zeolite 의 흡착 및 촉매특성

Clinoptilolite zeolite samples were treated with hydrochloric acid, sulfuric acid and phosphoric acid of different strength and the adsorption characteristics and crystal structures of the original and acid-treated clinoptilolites were studied. By treating with hydrochloric acid, the adsorbed amount increased to 5-fold for nitrogen, to 3-fold for benzene, but for methanol no significant change was observed. As acid strength increased further, there were declines both in adsorption capacity and crystallinity. The results showed that the increase of adsorbed amount was caused by the rearrangement of the pore entrance and cation exchange. A method for determination of clinoptilolite content in natural mineral based on benzene adsorption on acid-treated sample is proposed. By this method, the original sample used in this study was found to contain approximately 40% of clinoptilolite. Using pulse technique in micro-catalytic reactor system, the catalytic activities of hydrochloric acid-treated clinoptilolites in cumene cracking and toluene disproportionation reactions were measured. For cumene cracking reaction, the maximum conversion was observed for the 0.5 N hydrochloric acid-treated sample. It is instructive to note that the maximum benzene adsorption was also observed for the sample treated with 0.5 N HCl. This suggest that the conversion rate was determined mainly by the rate of transport of reactants and the products through the pore structure. In the toluene disproportionation reaction, the same trend was observed. But the rate of deactivation was high for samples with strong acid sites. Since catalyst having higher activity was deactivated more easily, the conversion maximum was shifted to the sample treated with higher concentration of acid, -1N. The catalytic activity of $Ca^{2+} and La^{3+} ion exchanged samples for the toluene disproportion was much lower than that of acid-treated samples. Introduction of Ca^{2+} and La^{3+}$ into the pore structure apparently decreases the effective pore diameter of acid-treated clinoptilolite thus limiting the diffusion of reactants and products. 국내에서 산출되는 clinoptilolite 시료를 여러 농도의 염산, 황산 및 인산으로 처리하여 흡착특성 및 결정구조의 변화를 조사하였다. 염산으로 처리했을 때, 질소 흡착량은 5배까지, 벤젠 흡착량은 3배까지 증가되나 메탄올 흡착량은 별 변화가 없다. 처리하는 산의 농도가 높아져 알루미늄의 용출이 많아지면, 결정도가 감소되어 흡착량도 줄어든다. 이러한 결과는 세공 입구의 재배열과 양이온 교환에 기인하는 것으로 보인다. 산처리 시료의 벤젠 흡착량으로 부터 천연시료중의 clinoptilolite의 함량을 결정할 수 있으며, 이 방법으로 본 실험에 사용한 시료를 정량한 결과 약 40% clinoptilolite를 포함하고 있었다. 펄스방법과 microcataly