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forward reaction. As for đžđ¤đđĄđđ, it is notable that Amberlystâ35 has much more affinity to this compound [10,104]. Esteban et al. compared the PH, LHHW, and ER models and concluded that the latter provided the best fit, considering that the rate law is zero order for the reactants. However, the activation energy was high (over 120 kJ¡molâ1) compared to the remainder estimations Sustain. Chem. 2021, 2 304 in Table 2 [70]. Conversely, using the same model but with a rate law of the first order for the reactants, Sulistyo et al. found a slightly lower value with Indion 225 Na [78]. As pre- viously stated, this is probably due to the different characteristics of the catalysts. TThheegenerallly accepted mechaniismfoforrththeesosloklekteatlaslysnytnhtehseisiussuinsginBgrøBnrsøtnesdteadcidacciadt- catalysts is shown in Figure 8. alysts is shown in Figure 8. FFigiguurere88..MeecchhaannisismooffrereaacctitoionnooffBBrørønnstseteddaacicdidcacatatalylystsst.s. The difference between the ketalization catalyzed by Brønsted and Lewis acids is that for the first, a short-lived hemiketal is formed and suffers a nucleophilic attack from one of the hydroxyl groups of glycerol to its central carbon, leading to the formation of solketal or the six-membered ring ketal (2,2âdimethylâ1,3âdioxanâ5âol). For Lewis catalysts, the metal site coordinates and activates the carbonyl group of acetone, followed by an attack from the glycerol alcoholic group to this carbonyl and a consequent bond forming between the carbonyl oxygen atom and the secondary carbon atom of glycerol. Finally, dehydration occurs to form the five-membered ring [48,91]. The products of the reaction are a five-membered ring (solketal) and a six-membered ring (5âhydroxyâ2,2âdimethylâ1,3âdioxane), with much higher selectivity for the first compound [10,48]. This is probably due to the more likely acetone attack on the end-chain hydroxyl group than on the middle-chain hydroxyl group [10]. Additionally, the most energetically favorable product is the five-membered ring, because one of the methyl groups of the six-membered ring is in the axial position of the chair conformation, an unstable position due to the steric repulsion between the methyl group and the hydrogens bonded to the carbons of the ring [55]. 4.3. Recent Advances on the Continuous Process Among the continuous process strategies studied, the fixed-bed reactor stands-out owing to its relatively simple operation with mild conditions, the use of heterogeneous catalysts, and the possibility of coupling other processes (as downstream distillation separation), or unit operations (as adsorption or membrane permeation). Most of the recent studies still relied on ion exchange resins and hierarchical zeolites. The latest developments and tests on conventional continuous processes are summarized in Table 3.PDF Image | Continuous Valorization of Glycerol into Solketal
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