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other half of glycerol, i.e., the stream leading to solketal production, was pressurized (12,000 kPa) before being fed into a conversion reactor with acetone and heterogeneous catalyst Amberlyst-15. The reaction was carried at 343 K for 1.5 h. The separation was promoted by a flash separator, where acetone with trace water was vaporized and recov- Sustain. Chem. 2021, 2 ered and the solketal stream was split into pure solketal and a recycle stream that was sent 314 back to the reactor to improve conversion, since glycerol conversion is only 35% but can be enhanced with product recycle, according to the authors [124]. Figure 13. FloFwigsuhree1t 3o.fFtlhoewinshdeuesttroifalthseoliknedtualstprrioaldsuocltkioetnalpplarnotdwucithiognlypclaenrotlwpiuthrifigclyactieornolppruopriofisceadtiboyn Cprho-l et al. [124]. posed by Chol et al. [124]. Another project proposed by Al-Saadi et al. is a plant where solketal would be The ecovnaolmoriczeadnainlysiitsuosfimimupltlaenmeoeunstilnygtothbisodiniedsuesltpriraoldfuloctwiosnh.eTethiesaaultshooprsrosmtuidsiendg,an industrial the cost of trfeaactiilnitgy onpertaotningofactraumdeolgalryrcaetriolowfo7u:1l:d10baecUetSo$n5e0:t4r5io,lweihn:imleettheanreovl,e3n2u3eKc,o1sth of reaction, and 0.5 mol of DBSA (p-Dodecylbenzenesulfonic acid) catalyst to oil. The objective was to would be US $8036, resulting in a profit of almost US $3000/ton of glycerol. The total in- attain triolein conversion of 98% and glycerol conversion of 82% [118,123]. vestment cost was expected to be recovered within three years of operation; considering The flowsheet (Figure 14) comprises one mixer where the catalyst (DBSA) and the oil that the first three years would be dedicated to building the facility, complete recovery is are fed, parallel to a mixer where fresh acetone, fresh methanol and the recycled streams made within six years. According to the authors, these margins are decent for a biodiesel are inserted. The reactants are preheated and delivered to the reactor (generic conversion plant and the increased profit indicate that it would be worth it investing in crude glycerol reaction vessel). The outlet of the reactor flows to a separator to be divided in a light purification and valorization plant [124]. organic fraction (the ‘biodiesel-rich phase’) and the heavy more polar fraction (glycerol, catalyst, solketal, unreacted methanol, and water). Then, the light fraction follows to a distillation column to separate acetone in the top and biodiesel in the bottom. The heavy fraction is separated in methanol in the top and low purity solketal in the bottom, and this is the most energetically demanding step. No information is given about the water produced as by-product or the recovery of the catalyst; however, it is stated that methanol and acetone are recycled [123]. Therefore, one can conclude that the flowsheet is not a complete industrial plant, as there are some missing purification steps necessary to attest the process is techno-economically feasible. Nonetheless, the economic analysis was performed considering an oil feed of 100,000 t/year and a plant lifetime of 20 years. Compared to an industrial process producing biodiesel alone, which would cost approximately US$927.9/ton of biodiesel, coupling the production with solketal makes the industry more profitable and the cost of producing biodiesel is reduced to US$824.8/ton [123].PDF Image | Continuous Valorization of Glycerol into Solketal
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