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Review Continuous Valorization of Glycerol into Solketal: Recent Advances on Catalysts, Processes, and Industrial Perspectives Isabella Corrêa , Rui P. V. Faria * and Alírio E. Rodrigues Laboratory of Separation and Reaction Engineering–Laboratory of Catalysis and Materials (LSRE-LCM), Department of Chemical Engineering, Faculty of Engineering, University of Porto, 4200-465 Porto, Portugal; up201902799@fe.up.pt (I.C.); arodrig@fe.up.pt (A.E.R.) * Correspondence: ruifaria@fe.up.pt Abstract: With the global biodiesel production growing as never seen before, encouraged by gov- ernment policies, fiscal incentives, and emissions laws to control air pollution, there has been the collateral effect of generating massive amounts of crude glycerol, a by-product from the biodiesel industry. The positive effect of minimizing CO2 emissions using biofuels is jeopardized by the fact that the waste generated by this industry represents an enormous environmental disadvantage. The strategy of viewing “waste as a resource” led the scientific community to propose numerous processes that use glycerol as raw material. Solketal, the product of the reaction of glycerol and acetone, stands out as a promising fuel additive capable of enhancing fuel octane number and oxidation stability, diminishing particle emissions and gum formation, and enhancing properties at low temperatures. The production of this chemical can rely on several of the Green Chemistry principles, besides fitting the Circular Economy Model, once it can be reinserted in the biofuel production chain. This paper reviews the recent advances in solketal production, focusing on continuous production processes and on Process Intensification strategies. The performance of different catalysts under various operational conditions is summarized and the proposed industrial solketal production processes are compared. Keywords: glycerol valorization; solketal; continuous process; heterogeneous catalyst; Green Chem- istry; process intensification strategies 1. Introduction The growing interest in processes that can combine economical savings and envi- ronmental preservation has driven not only research groups but also industry to find alternative technologies and methods that conform to Green Chemistry principles [1]. It was not a tough challenge to combine the interests of society, industry, and scientific groups when it has become clear that applying these principles is economically profitable [2]. The first concepts regarding Green Chemistry arose in 1990 and, since its creation, it has been based on improving design to reduce consumption of raw materials rather than treating waste [2,3]. Anastas and Warner introduced, in 1998, the guidelines necessary to redesign processes and products systematically, more known as The Twelve Principles of Green Chemistry [3]. Even before the introduction of the concepts of Green Chemistry, stimulated by the international petroleum crisis from the 1970s, the search for renewable energy sources led to the discovery of biofuel as the most promising alternative to the use of fossil fuels, since it is appropriate for the transportation sector, responsible for 57% of the global oil demand and for 24% of direct CO2 emissions [4–6]. Considering the significant share of the transportation sector on the Greenhouse Gases emissions and on the air quality of cities, replacing fossil fuel with biofuel arises as a promising alternative to diminish emissions, specially where the renewable alternative does not seem to be extensively applied, for instance, in jet and maritime fuel. Citation: Corrêa,I.;Faria,R.P.V.; Rodrigues, A.E. Continuous Valorization of Glycerol into Solketal: Recent Advances on Catalysts, Processes, and Industrial Perspectives. Sustain. Chem. 2021, 2, 286–324. https://doi.org/10.3390/ suschem2020017 Academic Editor: Matthew Jones Received: 12 March 2021 Accepted: 12 April 2021 Published: 21 April 2021 Publisher’s Note: MDPI stays neutral with regard to jurisdictional claims in published maps and institutional affil- iations. Copyright: © 2021 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https:// creativecommons.org/licenses/by/ 4.0/). Sustain. Chem. 2021, 2, 286–324. https://doi.org/10.3390/suschem2020017 https://www.mdpi.com/journal/suschemPDF Image | Continuous Valorization of Glycerol into Solketal
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