摘要
以H-ZSM-5系列分子筛、HY、Hβ、Al2O3等固体酸作为催化剂,在固定床反应器中考察了其对四氢呋喃催化氨化合成吡咯烷反应的催化性能。结果表明,n(Si)/n(Al)=80的H-ZSM-5催化剂的活性最佳,其催化四氢呋喃氨化合成吡咯烷的最佳工艺条件为:常压,反应温度350℃,氨气与四氢呋喃摩尔比6,停留时间6.9s,此时四氢呋喃的转化率为82.9%,吡咯烷的收率为62.3%。在优化条件下催化剂连续工作600h,四氢呋喃的转化率保持在75%以上,吡咯烷的选择性有所降低,但吡咯烷的收率仍然保持在55%以上。利用XRD、N2吸附-脱附和NH3-TPD等手段对使用前后的催化剂进行表征,得出催化剂活性下降是由于较长时间的连续反应使得催化剂表面产生了积炭,堵塞了催化剂内部较小孔径的孔道,覆盖了催化剂表面的酸性位点。利用空气氧化法对催化剂进行在线再生后,催化剂的催化性能基本恢复到初始水平。
The catalytic performance of a series of solid acid catalysts like H-ZSM-5,HY,Hβ and Al2O3 for the amination of tetrahydrofuran to pyrrolidine were investigated in a fixed-bed reactor.H-ZSM-5(80) exhibited excellent catalytic activity on tetrahydrofuran amination.The reaction conditions over H-ZSM-5(n(Si)/n(Al)=80) were optimized as: atmospheric pressure,350℃,molar ratio of ammonia to tetrahydrofuran 6,and contact time 6.9 s.Under these conditions,the conversion of tetrahydrofuran reached 82.9% with pyrrolidine yield of 62.3%.H-ZSM-5(n(Si)/n(Al)=80) was effective for at least 600 h,during this period the conversion of tetrahydrofuran exceeded 75% with the yield of pyrrolidine above 55%.The catalyst characterization results suggested that the deterioration of catalyst activity was attributed to the surface carbonaceous deposition,which might block the smaller holes and cover the acid centers in the catalyst matrix.The catalyst activity could be recovered by oxidation of the carbonaceous deposition on line.
出处
《石油学报（石油加工）》
EI
CAS
CSCD
北大核心
2012年第S1期127-132,共6页
Acta Petrolei Sinica(Petroleum Processing Section)
基金
国家自然科学基金(20976034)
河北省教育厅百名优秀创新人才支持计划(CPRC012)
河北省青年科学基金(B2009000009)资助
