The process and energy intensifications for the synthesis of glycerol carbonate (GC) from glycerol and dimethyl carbonate (DMC) using an eggshell-derived CaO heterogeneous catalyst were investigated. The transesterification reaction between glycerol and DMC was typically limited by mass transfer because of the immiscible nature of the reactants. By varying the stirring speed, it was observed that the mass transfer limitation could be neglected at 800 rpm. The presence of the CaO solid catalyst made the mass transport-limited reaction process more prominent. Mass transfer intensification using a simple kitchen countertop blender as an alternative to overcome the external mass transfer limitation of a typical magnetic stirrer was demonstrated. A lower amount of the catalyst and a shorter reaction time were required to achieve 93% glycerol conversion or 91% GC yield, and the turnover frequency (TOF) increased almost 5 times from 1.5 to 7.2 min−1 when using a conventional magnetic stirrer and countertop blender, respectively. In addition, using a simple kitchen countertop blender with 7200 rpm, the reaction temperature of 60 °C could be reached within approximately 3 min without the need of a heating unit. This was the result of the self-frictional heat generated by the high-shear blender. This was considered to be heat transfer intensification, as heat was generated locally (in situ), offering a higher homogeneity distribution. Meanwhile, the trend toward energy intensification was promising as the yield efficiency increased from 0.064 to 2.391 g/kJ. A comparison among other process intensification techniques, e.g., microwave reactor, ultrasonic reactor, and reactive distillation was also rationalized.

Waste eggshell is proposed as a highly active catalyst for glycerol carbonate production from dimethyl carbonate (DMC) and glycerol. The effect of reaction temperature, reaction time and catalyst loading on the reaction performance were investigated in order to find a suitable operating condition. CaO derived from waste eggshell exhibits catalytic activity comparable to commercial CaO. By using CaO eggshell, glycerol conversion of 96% can be achieved within 90 min of reaction time under 2.5:1 feed molar ratio of DMC to glycerol, 0.08 mole ratio of CaO to glycerol and reaction temperature of 60°C. The catalyst was examined by XRD, TGA/DSC, SEM, N2 adsorption-desorption and Hammett indicators method. Utilization of eggshell as a catalyst for glycerol carbonate production not only provides a cost-effective and value-added of waste eggshell as a green catalyst, but also decrease amount of waste and its treatment cost which is ecologically friendly.

Biopharmaceuticals are commonly present in relatively low concentrations in aqueous solutions, making their detection and purification detrimental. In this work, we used novel aqueous biphasic systems based on glycerol formal to extract an important antibiotictetracycline. We report cloud points (solubility curve) and tie-lines for three ternary systems, containing glycerol formal (GF), water and inorganic salt (either K3PO4, K2HPO4 or K2CO3) at constant temperature of 298 K and at 0.1 MPa. The tie-line data of these ternary systems were correlated using the non-random two-liquid (NRTL) model and binary interaction parameters of activity coefficients were estimated. The experimental and correlated tie-line data were compared in terms of average root mean square deviation and showed satisfactory agreements. The partition coefficients of tetracycline between two phases were measured and corresponding extraction efficiencies were calculated. The maximum value of partition coefficient was 1551 for the system containing K3PO4, followed by values of 1145 and 927 for systems containing K2CO3, and K2HPO4, respectively. The calculated extraction efficiencies were very highgreater than 98.8%, demonstrating high potential for using aqueous biphasic systems, which are based on glycerol formal, for separation and purification process.

The novel bifunctional NiÀ Re supported on bimodal SAPO-11 catalyst was designed for an economically combined process of direct triglycerides hydro-deoxygenation and isomerization into low-cold flow diesel. The catalyst with a Ni to Re molar ratio of 1 : 0.12 exhibited superior performance for diesel production containing large fraction of iso-alkanes in comparison to Ni and Re benchmarks. Comprehensive characterizations revealed that the detection of Ni and Re co-existed with NiO and ReO x on SAPO-11 after the reduction confirmed by XRD, XANES, and XPS analysis gave a large distribution of Lewis acid sites (> 80 %) noticed by Pyridine-DRIFTS measurement. Under investigations of WHSV, reaction temperature, and H 2 pressure, the NiRe 0.12 catalyst contributed a nearly theoretical 77.1 % liquid yield, accompanied by a 18.2 % jet-range and 52.1 % diesel-range yields with a classification for 46.8 % iso-alkanes and 23.5 % normal alkanes yields; whereas, the cold-flow properties of liquid product were in the ranges of winter diesel standard. It was remarkably noticed that the combination effects of Ni and nanosized Re species substantially improved the diesel production comprising iso-alkanes components with proper catalyst lifetime and low carbon deposition attributing to the fabricated active metal species on bimodal SAPO-11 features with large distribution of Lewis acidic sites.

Summary Glycerol carbonate (GC) was synthesized by transesterification of glycerol with dimethyl carbonate (DMC) using calcium oxide (CaO) derived from eggshell as a catalyst. The best results of 96% glycerol conversion and 94% GC yield were achieved under the following reaction conditions: 0.08 mole ratio of CaO to glycerol, 1:2.5 mole ratio of glycerol to DMC, 60°C reaction temperature, and 3 hours reaction time. As expected, CaO showed deteriorated catalytic performance when recycling as observed by a rapid decrease in GC yield. This research showed that the active CaO phase first was converted to calcium methoxide (Ca[OCH3]2) and calcium diglyceroxide (Ca[C3H7O3]2) and finally to carbonate phase (CaCO3) which can be confirmed by XRD patterns. According to the phase transformation, the basicity decreased from 0.482 mmol/g to 0.023 mmol/g, and basic strength altered from strong basic strength (15.0 < H_ < 18.4) to weak basic strength (7.2 < H_ < 9.8), resulting in the lower catalytic activity of the consecutive runs. Despite the fact that the GC selectivity was almost 100%, the reaction products (methanol and GC) were not obtained in their stoichiometric ratio and their extents corresponded with that of the catalyst phase transformation to CaCO3. The mechanism of CaO catalyzed transesterification based on the condensation reaction of glycerol and catalyst was proposed, and in situ formation of water‐derivative species was hypothesized as a cause of CaO transformation. CaO could react with DMC and water, generating methanol and CaCO3. This enabled unconventional monitoring of catalyst deactivation by checking if the mole ratio of methanol to GC was higher than 2:1 of its reaction stoichiometric ratio. It was also demonstrated that calcination of post‐run catalyst at 900°C to CaO exhibited almost constant catalytic activity, and the mole ratio of methanol to GC was constant at its reaction stoichiometry (2:1) for at least 4 times use.