The design of experiments response surface analysis was employed for the first time to study the effect of divinylbenzene (DVB) (20-80 wt. %), diluent (0-100 wt.%), and mixing (200-900 rpm) on the beads' physical properties and on swelling ability. The beads with the highest performances, in terms of mechanical stability, surface area, and swelling ability, were sulphated, and tested in converting glycerol to a valuable product "solketal." Process options for glycerol valorization to solketal using synthesized sulphonic acid-functionalized styrene-divinylbenzene (ST-DVB-SO 3 H) copolymer beads and techno-economic analysis of the processes have been investigated. Three processes were evaluated: two one-stage processes at 8.5 wt.% catalyst and 50 • C, based on either 6:1 acetone to glycerol molar ratio (87% conversion) or 12:1 (98% glycerol to solketal conversion), and a two-stage route (two acetone additions), where ≥98% conversion can be achieved with lower overall acetone use (10:1 acetone to glycerol molar ratio and 50 • C). Techno-economic analyses of the three solketal options were performed using Aspen (HYSYS), based on a fixed capacity of 100,000 te/y and 20-years lifetime. The techno-economic analyses showed that the net present values for the solketal process options

This study investigated a reactive coupling to determine the optimal conditions for transesterification of rapeseed oil (RSO) to fatty acid methyl ester (FAME) and glycerol carbonate (GLC) in a one-step process, and at operating conditions which are compatible with current biodiesel industry. The reactive coupling process was studied by transesterification of RSO with various molar ratios of both methanol and dimethyl carbonate (DMC), using triazabicyclodecene (TBD) guanidine catalyst and reaction temperatures of 50–80°C. The optimal reaction conditions obtained, using a Design of Experiments approach, were a 2:1 methanol-to-RSO molar ratio and 3:1 DMC-to-RSO molar ratio at 60°C. The FAME and GLC conversions at the optimal conditions were 98.0 ± 1.5 and 90.1 ± 2.2%, respectively, after 1 h reaction time using the TBD guanidine catalyst. Increase in the DMC-to-RSO molar ratio from 3:1 to 6:1 slightly improved the GLC conversion to 94.1 ± 2.8% after 2 h, but this did not enhance the FAME conversion. Methanol substantially improved both FAME and GLC conversions at 1:1–2:1 methanol-to-RSO molar ratios and enhanced the GLC separation from the reaction mixture. It was observed that higher methanol molar ratios (>3:1) enhanced only FAME yields and resulted in lower GLC conversions due to reaction equilibrium limitations. At a 6:1 methanol-to-RSO molar ratio, 98.4% FAME and 73.3% GLC yields were obtained at 3:1 DMC-to-RSO molar ratio and 60°C. This study demonstrates that formation of low value crude glycerol can be reduced by over 90% compared to conventional biodiesel production, with significant conversion to GLC, a far more valuable product.

A mesoscale oscillatory baffled reactor (meso-OBR) served as a continuous screening platform to rapidly investigate the operating conditions for acid-catalyzed production of fatty acid methyl ester (FAME) from triglyceride feedstock. The acid catalyst was 4-dodecylbenzenesulfonic acid (DBSA) and the triglyceride feedstock was rapeseed oil (RSO). The parameter space was explored by means of a design of experiments (DoE) methodology. The variables screened were methanol-to-RSO molar ratio, catalyst-to-oil molar ratio, and residence time. Over 98 % conversion of RSO to FAME could be achieved under optimized conditions.

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