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Sustain. Chem. 2021, 2 310 5. Solketal Production The number of studies on solketal synthesis available in the open literature is sub- stantial, with many new catalysts being explored. However, the number of studies on solketal production at an industrial scale grows at a much slower pace and the literature on large-scale methods for the production of solketal is rather scarce. Solketal production plants are normally divided into Reaction Section and Separation Section. On a usual flowsheet, there is necessarily a reactor, the type depending on the catalyst and on the process, and a separation unit, usually a sequence of distillation columns. There can also be one or more mixers to homogenize the reactants and a heat exchanger to heat the compounds to the reaction temperature. Usually, a vessel is used to collect the products before they enter the separation section. The distillation columns are responsible for solketal purification and for the recovery of the eluent and unreacted reactants that can be recycled back to the column. The proposed flowsheets found after an extensive bibliographic search are described with more details in Section 5.1. Then, the patented processes that could be industrially implemented are described in Section 5.2. 5.1. Processes Zaharia et al. proposed an industrial flowsheet divided into two sections: in the reaction section, solketal production would be carried in a Continuously Stirred Tank Reactor (CSTR) and in the separation section, three distillation columns would purify the products and recycle the unconverted reactants. The proposed flowsheet is exhibited in Figure 10. The authors used the kinetic and thermodynamic data from Nanda et al. to estimate the mass and energy balances necessary to process a glycerol stream resultant from a biodiesel plant, aiming to reach a glycerol conversion of 76.5% with Amberlyst–35 as a catalyst [53]. The stream is considered pure glycerol and there is no information about its pre-treatment. The flowsheet was designed in Aspen Plus software. The reaction section comprises two mixers, one for each reactant, followed by a heat exchanger to assure the reactor’s inlet stream is at 308 K and then the CSTR. The authors proposed that the catalyst could be retained inside the reactor by placing it in a basket or it could be later separated in a cyclone or in a decanting unit. The separation section consists of three distillation columns; in the first, acetone would be separated and recycled, in the second, water would be removed as distillate with 99.9% of purity, and in the third, solketal would be recovered as distillate also with high purity (99.8%) and the unreacted glycerol would be recycled [120]. In this study, an economic evaluation of the industrial plant is presented; however, the authors have not accounted for the reactants and catalyst costs. Moreover, they have not provided information about glycerol purification costs, which is a necessary step once Amberlyst–35 is deactivated when salts are present in crude glycerol. Thus, considering a payback period of five years, the cost to produce 3720 t of solketal/year was estimated at US$128.50/ton, a much lower value than what was estimated in other studies and which can be considered unrealistic [10,25,120].PDF Image | Continuous Valorization of Glycerol into Solketal
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