This study explored the production of aromatic hydrocarbons from the longer-chain alkenes produced by the pyrolysis/cracking of crop oils. 1-Tetradecene, serving as a model compound for these alkenes, was reformed in a batch reactor with a HZSM-5 catalyst to produce a liquid hydrocarbon mixture with a high-aromatic content. These reactions resulted in a >99% conversion of the 1-tetradecene feedstock with a yield of up to 22 wt% of aromatic hydrocarbons. Surprisingly, isomers of C 3substituted benzenes along with xylenes and diaromatics (lower homologs of alkyl-substituted indanes and naphthalenes) were the main aromatic products rather than their lower-molecular-weight (MW) homologs, benzene, toluene, ethylbenzene and xylenes, which are commonly formed with high selectivity during zeolite-catalyzed reforming. The recovery of higher-MW aromatics, and particularly bicyclic naphthalenes and indanes, provides mechanistic insights for zeolite-catalyzed alkene reforming reactions suggesting that these higher-MW aromatics are likely formed near the catalyst surface at pore openings. Furthermore, the production of acyclic diene intermediates in the size range of C 7 -C 10 provides insight into the overall reaction pathway. The results suggest that this reaction pathway may be a commercially viable option for the production of renewable C 3 -substituted aromatic chemicals/ chemical intermediates as coproducts to complement the kerosene and diesel fuel blendstocks that are the primary products from crop oil cracking.

Background: The replacement of leaded high octane aviation gasoline with an unleaded renewable alternative would decrease the emissions of lead and fossil-derived carbon into the atmosphere. Replacement has been limited by the requirement of a very high octane number in many existing general aviation aircraft engines. Method: Two separate process pathways were developed that generate an unleaded octane fuel with a motor octane number >96 from triglyceride oils (TGs), such as crop oils and algae oil. A series of experiments coupled with process simulations was used to verify the feasibility of both pathways and to provide preliminary laboratory scale data that could form the basis for further development towards a commercial technology. In the first pathway, TG oil is catalytically cracked to produce a high concentration of simple aromatic hydrocarbons. These aromatic hydrocarbons are then alkylated using propylene to form a mixture, which after purification acquires fuel properties compliant with those in the ASTM specification for 100 octane low lead aviation gasoline (100LL AvGas). In the second process pathway, the aromatic hydrocarbons are isolated after cracking using a sulfolane solvent extraction process to increase alkylation efficiency and fuel quality. Result: The results demonstrate that it is technically feasible to produce a replacement for 100LL AvGas using either pathway, and thus these strategies may be attractive candidates for commercialization.