Techno-Economic Analysis of Glycerol Valorization via Catalytic Applications of Sulphonic Acid-Functionalized Copolymer Beads.

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-SOH) 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 were $707 M for the two-stage, $384 M for the one-stage at 6:1 acetone to glycerol molar ratio, and $703 M for the one-stage at 12:1 acetone to glycerol molar ratio. The break-even prices for these solketal processes were $2,058/ ton for the one-stage at 12:1 of acetone and two-stage and $2,088/ton for the one-stage at 6:1 of acetone, which is lower than the current price of solketal at $3,000/ton. The two-stage process was found to be the most effective method of glycerol valorization production to solketal.