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Sustain. Chem. 2021, 2, FOR PEER REVIEW 2 Sustain. Chem. 2021, 2 287 specially where the renewable alternative does not seem to be extensively applied, for instance, in jet and maritime fuel. Biiodiiesellmanufactureiisaawwelell-le-setsatbalbislihsehdedprporcoecsesswsiwthitbhillbiiolnlisonofsgoafllgoanlslobnesinbgepinrgo- pdruocdeudceydeayrelayr;lyh;ohwoewvevr,eirt, isttsiltlilhl hasasroroomffoorriimprovementts to maximize ttheeeccoonnoomicic vaallueaandmininiimiizzeetthheeeennvviriroonnmeennttaallimimppaacctt,,eessppeecciaialllyininwhhaattccoonncceerrnnssddimimininisishhiningg waasstteeprrooduccttiion[[77,8,8]].. Avoiidiingtthegenerrattiionoffwastteiissssorreelleevaantttthaattiitthhaassbbeeenn hiighlilgighhteteddasasonoenoefothfethmeaimnaisinsuiesssusienscesitnhceefitrhstedfiisrcsutsdsiosncussasbionust eanbvoiurotnemnevnirtoalnpmresnetra-l vparteiosenr.vIantio19n8.0In,R1o9g8e0r,RShogeledroSnhpelrdoopnosperdopaomseedtraicmtoetmriceatsoumreetahseurperothdeucptriodnuecftfiiocnienefcfyi- tcaikeincgyitnatkoinagccionutontatchceouanmtotuhnetaomfowuanstteofgwenaesrtaetgeden,ethraetEed-f,atchteorE[-9fa].cTtohre[9fi]r.sTthperifnircsiptlperoinf- Green Chemistry, indeed, is waste preservation [3]. ciple of Green Chemistry, indeed, is waste preservation [3]. The main production process of biodiesel is the catalyzed transesterification of triglyc- The main production process of biodiesel is the catalyzed transesterification of tri- erides with an alcohol (mainly methanol and ethanol), generating an ester (biodiesel) and glycerides with an alcohol (mainly methanol and ethanol), generating an ester (biodiesel) glycerol (by-product) (Figure 1) [10]. and glycerol (by-product) (Figure 1) [10]. Fiigurree11..Biiodiiessellprroduccttiionwiitthggllyycceerroollaassbbyy--pprroodduucct.t. The main environmental disadvantage of the biodiesel industry is the massive amount The main environmental disadvantage of the biodiesel industry is the massive of glycerol generated as by-product, at a rate of 10–12% and a purity of about 50–55% [11]. amount of glycerol generated as by-product, at a rate of 10–12% and a purity of about 50– Since 68% of the glycerol supply comes from the biodiesel industry, the expected growth 55% [11]. Since 68% of the glycerol supply comes from the biodiesel industry, the expected in the supply of this commodity follows the tendency of the biofuel industry, with a growth in the supply of this commodity follows the tendency of the biofuel industry, with growth rate of 5.2% until 2027 [12,13]. In fact, the side production of glycerol, viewed a growth rate of 5.2% until 2027 [12,13]. In fact, the side production of glycerol, viewed as as a problem in the past, helped to alleviate the economic pressure over biodiesel plants a problem in the past, helped to alleviate the economic pressure over biodiesel plants as a as a consequence of the demand reduction by the COVID-19 pandemic, because as less consequence of the demand reduction by the COVID-19 pandemic, because as less bio- biodiesel was produced, the market felt glycerol supply pressure, and its prices rose to diesel was produced, the market felt glycerol supply pressure, and its prices rose to levels levels not seen in years. However, it is relevant to note that this effect was not due to a lack not seen in years. However, it is relevant to note that this effect was not due to a lack of of glycerol on the market, but due to logistics problems caused by the mobility restrictions. glycerol on the market, but due to logistics problems caused by the mobility restrictions. Glycerol is viewed as a safe chemical in terms of supply [12,14]. Glycerol is viewed as a safe chemical in terms of supply [12,14]. Despite that temporary shortcut, glycerol supply continues to expand at a much faster Despite that temporary shortcut, glycerol supply continues to expand at a much pace than the new applications to absorb it. Many alternatives have been studied to avoid faster pace than the new applications to absorb it. Many alternatives have been studied to treating this chemical as waste [15]. The alternatives are particularly interesting if the use avoid treating this chemical as waste [15]. The alternatives are particularly interesting if of crude glycerol is enabled, without the need of purifying it [16]. Refined glycerol has the use of crude glycerol is enabled, without the need of purifying it [16]. Refined glycerol found numerous applications in cosmetics, pharmaceuticals, and food industries for a has found numerous applications in cosmetics, pharmaceuticals, and food industries for long time and, by 2019, this segment accounted for 65.1% of the glycerol market [17,18]. a long time and, by 2019, this segment accounted for 65.1% of the glycerol market [17,18]. However, traditional markets are not able to absorb crude glycerol from biodiesel plants, However, traditional markets are not able to absorb crude glycerol from biodiesel plants, both because of its low purity and the amount generated [16]. both because of its low purity and the amount generated [16]. One of the most promising chemicals derived from glycerol is solketal (2,2–Dimethyl– One of the most promising chemicals derived from glycerol is solketal (2,2–Dime- 4–hydroxymethyl–1,3–dioxolane), an oxygenated cyclic ketal with two methyl groups. thyl–4–hydroxymethyl–1,3–dioxolane), an oxygenated cyclic ketal with two methyl It is produced by the ketalization of glycerol with acetone in the presence of an acidic groups. It is produced by the ketalization of glycerol with acetone in the presence of an catalyst, with water as the by-product (Figure 2). It is an emerging fuel additive by reason acidic catalyst, with water as the by-product (Figure 2). It is an emerging fuel additive by of improving the fuel octane number, enhancing liquid properties at low temperatures, reason of improving the fuel octane number, enhancing liquid properties at low temper- reducing gum formation, thus aiding maintenance and cleanliness of engines, and reducing atures, reducing gum formation, thus aiding maintenance and cleanliness of engines, and particle emission, which diminishes atmospheric pollution [10,19,20]. Its potential as a reducing particle emission, which diminishes atmospheric pollution [10,19,20]. Its poten- fuel additive for the aviation industry, responsible for 2% of the global CO2 emissions, is noteworthy because of its icing inhibition and de-icing properties, improving the storage stability of aviation fuels [21–23].PDF Image | Continuous Valorization of Glycerol into Solketal
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