Department of Chemical and Biological Engineering, Colorado School of Mines , Golden, Colorado 80401, United States.
ACS Appl Mater Interfaces. 2017 Sep 20;9(37):31993-32000. doi: 10.1021/acsami.7b11638. Epub 2017 Sep 11.
The deoxygenation of palmitic and lauric acids over 0.5 wt % Pt/ZIF-67 membrane/zeolite 5A bead catalysts is demonstrated. Almost complete conversion (% deoxygenation of ≥95%) of these two fatty acids was observed over both fresh and recycled catalyst after a 2 h reaction time. The catalysts displayed high selectivity to pentadecane and undecane via decarboxylation reaction pathway even at low 0.5 wt % Pt loading. Selectivity to pentadecane and undecane as high as ∼92% and ∼94% was observed under CO atmosphere when palmitic and lauric acids were used respectively as reactants. Depending on the reaction gas atmosphere, two distinctive reaction pathways were observed: decarboxylation and hydrodeoxygenation. Specifically, it was found that decarboxylation reaction pathway was more favorable in the presence of helium and CO, while hydrodeoxygenation pathway strongly competed against the decarboxylation pathway when hydrogen was employed during the deoxygenation reactions. Esters were identified as the key reaction intermediates leading to decarboxylation and hydrodeoxygenation pathways.
在 0.5wt%Pt/ZIF-67 膜/沸石 5A 珠催化剂上,对棕榈酸和月桂酸进行脱氧。在 2 小时的反应时间后,无论是新鲜催化剂还是回收催化剂,这两种脂肪酸的转化率(脱氧率≥95%)都几乎达到完全。即使在低负载量 0.5wt%Pt 的情况下,催化剂通过脱羧反应途径表现出对十五烷和十一烷的高选择性。当分别使用棕榈酸和月桂酸作为反应物时,在 CO 气氛下,观察到十五烷和十一烷的选择性高达约 92%和 94%。根据反应气体气氛,观察到两种不同的反应途径:脱羧和加氢脱氧。具体而言,发现当存在氦气和 CO 时,脱羧反应途径更有利,而当在脱氧反应中使用氢气时,加氢脱氧途径强烈竞争脱羧途径。酯被确定为导致脱羧和加氢脱氧途径的关键反应中间体。