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Direct Production of Aviation Fuel Range Hydrocarbons and Aromatics from Oleic Acid without an Added Hydrogen Donor Qiurong Tian, Kai Qiao, Feng Zhou, Kequan Chen, Tianfu Wang, Jie Fu, Xiuyang Lu, and Pingkai Ouyang Energy Fuels, Just Accepted Manuscript • DOI: 10.1021/acs.energyfuels.6b00978 • Publication Date (Web): 12 Aug 2016 Downloaded from http://pubs.acs.org on August 14, 2016
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Energy & Fuels
Direct Production of Aviation Fuel Range Hydrocarbons and Aromatics from Oleic Acid without an Added Hydrogen Donor
Qiurong Tiana, Kai Qiaob, Feng Zhoub, Kequan Chenc, Tianfu Wangd, Jie Fua*, Xiuyang Lua, Pingkai Ouyanga,c a
Key Laboratory of Biomass Chemical Engineering of Ministry of Education, College of
Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, China b
Fushun Research Institute of Petroleum and Petrochemicals, SINOPEC, Fushun 113001,
China c
State Key Laboratory of Materials-Oriented Chemical Engineering, College of
Biotechnology and Pharmaceutical, Nanjing Tech University, Nanjing 211816, China d
Xinjiang Technical Institute of Physics and Chemistry, Chinese Academy of Sciences,
Urumqi 830011, China Abstract: We herein report an atom-economic approach to produce aviation fuel range hydrocarbons and aromatics from oleic acid without an added hydrogen donor.
The
effects of catalyst loading, reactant loading, and reaction temperature on the conversion of oleic acid and the yields of hydrocarbons and aromatics were investigated. 1 ACS Paragon Plus Environment
The
Energy & Fuels
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conversion of oleic acid was 100%, and the yield of heptadecane (the main product) can reach 71% after 80 min at 350 °C.
Moreover, an aromatics yield of 19% was determined,
which is the critical composition of the aviation fuels due to their ability to maintain the swelling of fuel system elastomers, indicating that it is a complicated reaction system including in-situ hydrogen transfer, aromatization, decarboxylation and cracking.
To
probe the mechanism of the conversion of oleic acid without an added hydrogen donor, variations of the reactant and products as time elapsed at different temperatures, and the reaction behavior of 1-heptadecene and stearic acid at 350 °C in the catalysis system were investigated.
The main mechanism proposed was that oleic acid was decarboxylated to
8-heptadecene, followed by the dehydrogenation of 8-heptadecene to polyenes.
Then,
polyenes were cyclized to aromatics by an intramolecular Diels-Alder reaction, which provided hydrogen to hydrogenate the unreacted oleic acid to stearic acid.
Finally, stearic
acid was decarboxylated to heptadecane. Keywords: In-situ hydrogen transfer; Decarboxylation; Oleic acid; Aromatics; Hydrocarbons.
2 ACS Paragon Plus Environment
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Energy & Fuels
1. Introduction Aviation fuel represents one of the largest operating costs for air transport, corresponds to approximately 30% of the total 1.
With the rapid development of the aviation industry,
the global consumption of aviation fuel is increasing to 1500-1700 million barrels/year, and CO2 emissions will double in 25 years compared to their level in 2012 2. To solve the energy crisis and protect the global environment, research is being conducted regarding substitutions for fossil fuels, and aviation biofuel is a promising selection. The blend of synthetic paraffinic kerosenes (SPKs) produced from vegetable oils with conventional jet fuels can reach 50:50 in the new adopted specification (ASTM D7566-14a) 3. Aviation biofuels are a complex mixture of C8–C17 hydrocarbons, which include paraffins, aromatics and naphthenes 4.
Paraffins have better burning properties 5, and aromatics cannot exceed 25
vol.% in aviation fuel 6, while a content of aromatics in aviation fuels
