College of Biotechnology and Pharmaceutical Engineering, Nanjing University of Technology, Nanjing, China.
Biotechnol J. 2010 Nov;5(11):1186-91. doi: 10.1002/biot.201000139.
Bio-ethanol dehydration to ethylene is an attractive alternative to oil-based ethylene. The influence of fusel, main byproducts in the fermentation process of bio-ethanol production, on the bio-ethanol dehydration should not be ignored. We studied the catalytic dehydration of bio-ethanol to ethylene over parent and modified HZSM-5 at 250°C, with weight hourly space velocity (WHSV) equal to 2.0/h. The influences of a series of fusel, such as isopropanol, isobutanol and isopentanol, on the ethanol dehydration over the catalysts were investigated. The 0.5%La-2%PHZSM-5 catalyst exhibited higher ethanol conversion (100%), ethylene selectivity (99%), and especially enhanced stability (more than 70 h) than the parent and other modified HZSM-5. We demonstrated that the introduction of lanthanum and phosphorous to HZSM-5 could weaken the negative influence of fusel on the formation of ethylene. The physicochemical properties of the catalysts were characterized by ammonia temperature-programmed desorption (NH(3)-TPD), nitrogen adsorption and thermogravimetry (TG)/differential thermogravimetry (DTG)/differential thermal analysis (DTA) (TG/DTG/DTA) techniques. The results indicated that the introduction of lanthanum and phosphorous to HZSM-5 could inhibit the formation of coking during the ethanol dehydration to ethylene in the presence of fusel. The development of an efficient catalyst is one of the key technologies for the industrialization of bio-ethylene.
生物乙醇脱水制乙烯是一种有吸引力的石油基乙烯替代品。在生物乙醇生产的发酵过程中,杂醇(主要副产物)对生物乙醇脱水的影响不容忽视。我们研究了在 250°C 下,通过重量时空速度(WHSV)等于 2.0/h,用原始和改性 HZSM-5 对生物乙醇催化脱水制乙烯的情况。考察了一系列杂醇,如异丙醇、异丁醇和异戊醇,对催化剂上乙醇脱水的影响。与原始和其他改性 HZSM-5 相比,0.5%La-2%PHZSM-5 催化剂表现出更高的乙醇转化率(100%)、乙烯选择性(99%),特别是增强的稳定性(超过 70 h)。我们证明,将镧和磷引入 HZSM-5 可以削弱杂醇对乙烯形成的负面影响。通过氨程序升温脱附(NH(3)-TPD)、氮气吸附和热重(TG)/差热重(DTG)/差示热分析(DTA)(TG/DTG/DTA)技术对催化剂的物理化学性质进行了表征。结果表明,在存在杂醇的情况下,将镧和磷引入 HZSM-5 可以抑制乙醇脱水制乙烯过程中积碳的形成。开发高效催化剂是生物乙烯工业化的关键技术之一。