Lee Su-Un, Kim Tae-Wan, Jeong Kwang-Eun, Lee Sungjune, Shin Min Cheol, Kim Chul-Ung
Chemical & Process Technology Division, Korea Research Institute of Chemical Technology 141, Gajeong-ro, Yuseong-gu Daejeon 34114 South Korea
RSC Adv. 2023 Jan 17;13(3):2168-2180. doi: 10.1039/d2ra06938e. eCollection 2023 Jan 6.
For producing a drop-in bio jet fuel, one-step hydrotreatment, which includes deoxygenation, isomerization and cracking in one step, is essential to overcome the typical biofuel drawbacks due to high oxygen content, out of jet fuel range hydrocarbons, and low isomerization degree. Herein, Co- or/and Mo-supported Beta(25) zeolites with various Co/Mo ratios were prepared as transition metal-supported zeolite catalysts without the need for sulfidation of conventional transition metal catalysts. Based on the catalyst characterization, the Co/Mo ratio alters the metal phase with the appearance of CoMoO and the altered Co metal phase strongly influences the acidic properties of Beta(25) by the formation of Lewis (L) acid sites with different strengths as CoO and CoMoO for strong and weak L acid sites, respectively. The catalytic activities were investigated for hydrotreatment of methyl palmitate as a biofuel model compound of fatty acid methyl esters. Primarily, Co is required for deoxygenation and Mo suppresses overcracking to enhance the yield of jet fuel range hydrocarbons. The Co/Mo ratio plays an important role to improve the C-C selectivity by modifying the acidic properties to inhibit excessive cracking. CoMo/Beta(25) achieved the best catalytic performance with the conversion of 94.2%, C-C selectivity of 89.7 wt%, and high isomer ratio of 83.8% in organic liquid product. This unique modification of acidic properties will find use in the design of optimal transition metal-supported zeolite catalysts for selective one-step hydrotreatment to produce bio jet fuel range hydrocarbons.
为了生产一种可直接替代的生物喷气燃料,一步加氢处理(包括一步脱氧、异构化和裂化)对于克服由于高氧含量、超出喷气燃料范围的碳氢化合物以及低异构化程度导致的典型生物燃料缺点至关重要。在此,制备了具有不同Co/Mo比的Co或/和Mo负载的Beta(25)沸石作为过渡金属负载的沸石催化剂,无需对传统过渡金属催化剂进行硫化。基于催化剂表征,Co/Mo比改变了金属相,出现了CoMoO,并且改变后的Co金属相通过分别形成具有不同强度的路易斯(L)酸位点(对于强L酸位点为CoO,对于弱L酸位点为CoMoO)强烈影响Beta(25)的酸性性质。研究了以棕榈酸甲酯作为脂肪酸甲酯的生物燃料模型化合物进行加氢处理的催化活性。首先,脱氧需要Co,而Mo抑制过度裂化以提高喷气燃料范围碳氢化合物的产率。Co/Mo比通过改变酸性性质来抑制过度裂化,从而在提高C-C选择性方面发挥重要作用。CoMo/Beta(25)在有机液体产物中实现了最佳催化性能,转化率为94.2%,C-C选择性为89.7 wt%,异构比高达83.8%。这种独特的酸性性质修饰将用于设计用于选择性一步加氢处理以生产生物喷气燃料范围碳氢化合物的最佳过渡金属负载沸石催化剂。