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Processes 2020, 8, 548 15 of 22 (1) amorphous sugar (e.g., molasse, starch), (2) lipids (e.g., vegetable oils), and (3) lignocellulosic biomass (the non-edible portion of biomass, e.g., bagasse, rice husk) and their current technologies, a green pathway for the generation of sustainable ethylene, propylene, and butylene have been proposed, as illustrated in Figure 9. Bio-based ethylene can be produced via the dehydration of ethanol [51] or via the cracking of renewable naphtha [52]. The bio-ethylene production from bioethanol, which is derived from fermentation of amorphous sugar, is an established method in polymer manufacturing and has been extensively used for polyethylene glycol production. Several industrial plants producing bio-ethylene through the dehydration of bioethanol have been established in China, India, and Brazil [53]. Ethanol or higher alcohols such as butanol can also be produced from lignocellulosic biomass via two main pathways. For the first pathway, pretreatment to breakdown the lignocellulosic structure and hydrolysis for converting to sugar are necessary before fermentation. Another pathway is gasification to produce syngas (as called ‘bio-based syngas’), and then further fermentation of the syngas to ethanol or a higher alcohol. Moreover, the bio-based syngas can be utilized to produce methanol which be converted to ethylene, propylene, and/or butylene via methanol-to-olefins (MTO) technology. Butylene can be produced from dehydration of butanol. Optionally, butylene can be subsequently reacted to with ethylene to produce propylene via meta-thesis. For the lipid platform, transesterification of vegetable oil or animal fat for biodiesel production produces glycerol as a by-product, which can be converted to propylene by hydrodeoxygenation [54]. Moreover, the bio-hydrotreated diesel production yields propane as a by-product, which can produce propylene via dehydrogenation of propane. The direct catalytic cracking of lipids (plant-based oil) may also produce propylene [55]. In addition, aside from ethylene oxide and propylene oxide, other types of epoxide can be produced from bio-waste, such as limonene oxide and limonene dioxide, which can be synthesized via the promising epoxidation of biomass waste limonene, such as citrus peels, oak, and pine tree, under solvent-free conditions with hydrogen peroxide and a tungsten-based catalyst [56]. Moreover, triglycerides and fatty acids from vegetable oils and their derivative esters contain a double bond (Figure 10) that can undergo epoxidation with H2O2. The epoxide product can be subsequently used as the precursor for cycloaddition reaction with CO2 [57,58]. Figure 10 shows an example of reactions between hydrogen peroxide and methyl oleate (Figure 10; R = CH3) or oleic acid (Figure 10; R = H) to produce epoxidized methyl oleate or epoxidized oleic acid. However, it is worth noting that epoxidation is a highly exothermic reaction (as ∆H = −55 kcal/mol for each double bond), thus H2O2 is slowly added or added by a stepwise manner in semi-batch operations, and requires a long reaction time. In order to avoid heat and mass transfer limitation, process intensification using a microreactor has been proposed by applying a novel TiO2 coated-wall microcapillary reactor [59]. The microreactor could decrease the reaction time from several hours to a few minutes with higher product selectivity.PDF Image | Green Pathway Utilizing CO2 Cycloaddition Reaction Epoxide
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