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Energies 2019, 12, 809 16 of 41 chemical polymers [128]. Hydrogenolysis takes place under alkaline conditions over supported metal catalysts such as Ru, Pd, Pt, Ni and Cu [128–131]. The effluent of the APR reactor contains oxygenated molecules such as alcohols, ketones, aldehydes and organic acids with less than six carbon atoms that can be converted into the desired liquid fuel in subsequent chemical processes. Green gasoline is produced through direct catalytic condensation using acid catalysts such as solid acids and zeolites like the ZSM-5 zeolite catalyst employed by Virent. On the other hand, green jet fuel is produced through a base catalyzed route. Finally, green diesel may be produced through dehydration, alkene oligomerization and alkene saturation. Alkenes or olefins are unsaturated hydrocarbons with one double bond (C=C) and general chemical formula CnH2n. Traditionally they are produced by the steam or catalytic cracking of fossil hydrocarbons but as oil resources are decreasing production routes are becoming increasingly expensive. Catalytic dehydration is an alternative pathway for the production of alkenes from oxygenated feedstocks and a first step for the production of higher hydrocarbons. The dehydration of an alcohol takes place through acidic catalysis and provides the corresponding alkene with the same number of carbon atoms. SAPO-34 has shown excellent performance on the dehydration of methanol [132–136] and high activity on the dehydration of ethanol and butanol [126,127]. Zeolites such as HZSM-5 [137–142] and mesoporous Si-based materials such as Ni-MCM-41 and Zr-KIT-6 [143–147] have also shown good dehydration activity. According to various studies [145,148,149] materials with fewer Brønsted and more Lewis acid sites provide higher selectivity to the desired alkenes and show better stability since they are less conducive to carbon formation and deposition. In the case of the APR effluent the dehydration of alcohols is straightforward but the ketones, aldehydes and organic acids which are present can also be dehydrated after catalytic hydrogenation which will cause their reduction to the respective primary or secondary alcohols. Oligomerization describes a reaction which produces molecules with only a few monomer units in contrast to polymerization which produces large molecules of high molecular weight. Alkene oligomerization describes the conversion of lower alkenes such as propylene, butylene and pentene to heavier alkenes in the boiling range of gasoline and petroleum diesel. The reaction may proceed over acid catalysts such as zeolites or over supported Ni catalysts [150–154]. Two commercial processes of alkene oligomerization are the Mobil Olefins to Gasoline and Distillates (MOGD) [154,155] and Conversion of Olefins to Diesel (COD) ones [156–158]. The MOGD process appeared in 1982 at the former Mobil refinery in Paulsboro in New Jersey, USA, in combination with Mobil’s successful fluidized bed Methanol to Olefin (MTO) technology. The success of these technologies lies on the unique properties of Mobil’s shape selective zeolite catalysts like H-ZSM-5 which inhibit carbon formation reactions and promote the selective production of high quality diesel range (C10 to C20) iso-alkenes. After hydrogenation these provide a mixture of saturated hydrocarbons on the diesel boiling point with a cetane number slightly above 50. On the other hand, the COD process was developed by Air Liquide (formerly Lurgi) during the 1990s. A COD reactor normally operates at about 120 ◦C with a zeolite catalyst like H-ZSM-5. The reactor operates discontinuously due to the deposition of heavy hydrocarbons on the catalyst which reduce its activity. As a result, at the end of each catalyst cycle the operation is discontinued and the catalyst is regenerated. Due to this three or more COD reactors are operated in a staggered sequence. The effluent stream of the COD reactors contains alkenes with a wide range of carbon atoms, starting from a small amount of propylene (C3H6) and up to heavy C23H46. The distribution curve shows a dominant maximum on the gasoline range, for C12H24. After hydrogenation the effluent produces a diesel fuel with a cetane number close to 56. 5. Thermal Conversion of Lignocellulosic Biomass 5.1. Biomass Pyrolysis and Production of Bio-Oil Pyrolysis is the endothermic reaction that takes place by heating lignocellulosic biomass at 300–900 ◦C in absence of air. Most of the pyrolysis research has been conducted using different typesPDF Image | Green Diesel: Biomass Feedstocks, Production Technologies
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