Melo Josué Alves, de Sá Mirele Santana, Moral Ainara, Bimbela Fernando, Gandía Luis M, Wisniewski Alberto
Petroleum and Energy from Biomass Research Group (PEB), Federal University of Sergipe, UFS, São Cristóvão 49100 000, SE, Brazil.
Grupo de Reactores Químicos y Procesos para la Valorización de Recursos Renovables, Institute for Advanced Materials and Mathematics (INAMAT2), Universidad Pública de Navarra (UPNA), 31006 Pamplona, Spain.
Nanomaterials (Basel). 2021 Jun 24;11(7):1659. doi: 10.3390/nano11071659.
In this work, the production of renewable hydrocarbons was explored by the means of waste cottonseed oil (WCSO) micropyrolysis at 500 °C. Catalytic upgrading of the pyrolysis vapors was studied using α-AlO, γ-AlO Mo-Co/γ-AlO, and Mo-Ni/γ-AlO catalysts. The oxygen removal efficiency was much lower in non-catalytic pyrolysis (18.0%), whilst γ-AlO yielded a very high oxygen removal efficiency (91.8%), similar to that obtained with Mo-Co/γ-AlO (92.8%) and higher than that attained with Mo-Ni/γ-AlO (82.0%). Higher conversion yields into total renewable hydrocarbons were obtained with Mo-Co/γ-AlO (61.9 wt.%) in comparison to Mo-Ni/γ-AlO (46.6%). GC/MS analyses showed a relative chemical composition of 31.3, 86.4, and 92.6% of total renewable hydrocarbons and 58.7, 7.2, and 4.2% of oxygenated compounds for non-catalytic bio-oil (BOWCSO), BOMoNi and BOMoCo, respectively. The renewable hydrocarbons that were derived from BOMoNi and BOMoCo were mainly composed by olefins (35.3 and 33.4%), aromatics (31.4 and 28.9%), and paraffins (13.8 and 25.7%). The results revealed the catalysts' effectiveness in FFA decarbonylation and decarboxylation, as evidenced by significant changes in the van Krevelen space, with the lowest O/C ratio values for BOMoCo and BOMoNi (O/C = 0-0.10) in relation to the BOWCSO (O/C = 0.10-0.20), and by a decrease in the presence of oxygenated compounds in the catalytic bio-oils.
在本研究中，通过在500℃下对废棉籽油（WCSO）进行微热解来探索可再生碳氢化合物的生产。使用α-Al₂O₃、γ-Al₂O₃、Mo-Co/γ-Al₂O₃和Mo-Ni/γ-Al₂O₃催化剂研究了热解蒸汽的催化升级。非催化热解中的氧去除效率低得多（18.0%），而γ-Al₂O₃产生了非常高的氧去除效率（91.8%），与Mo-Co/γ-Al₂O₃（92.8%）获得的效率相似，且高于Mo-Ni/γ-Al₂O₃（82.0%）。与Mo-Ni/γ-Al₂O₃（46.6%）相比，Mo-Co/γ-Al₂O₃（61.9 wt.%）获得了更高的总可再生碳氢化合物转化率。气相色谱/质谱分析表明，非催化生物油（BOWCSO）、BOMoNi和BOMoCo的总可再生碳氢化合物相对化学组成分别为31.3%、86.4%和92.6%，含氧化合物分别为58.7%、7.2%和4.2%。源自BOMoNi和BOMoCo的可再生碳氢化合物主要由烯烃（35.3%和33.4%）、芳烃（31.4%和28.9%）和石蜡（13.8%和25.7%）组成。结果表明，催化剂在游离脂肪酸脱羰和脱羧方面有效，这在范克雷维伦空间的显著变化中得到证明，BOMoCo和BOMoNi的O/C比值最低（O/C = 0-0.10），相对于BOWCSO（O/C = 0.10-0.20），并且催化生物油中含氧化合物的含量有所降低。
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