Nanostructured Solid/Liquid Acid Catalysts for Glycerol Esterification: The Key to Convert Liability into Assets.

Owing to the growing concerns about the dwindling fossil fuel reserves, increasing energy demand, and climate emergency, it is imperative to develop and deploy sustainable energy technologies to ensure future energy supply and to transition to the net-zero world. In this context, there is great potential in the biorefinery concept for supplying drop in biofuels in the form of biodiesel. Biodiesel as a fuel can certainly bridge the gap where electrification or the use of hydrogen is not feasible, for instance, in heavy vehicles and in the farm and marine transportation sectors. However, the biodiesel industry also generates a large amount of crude glycerol as the by-product. Due to the presence of several impurities, crude glycerol may not be a suitable feedstock for all high-value products derived from glycerol, but it fits well with glycerol esterification for producing glycerol acetins, which have numerous applications. This review critically looks at the processes using nanostructured solid/liquid acid catalysts for glycerol esterification, including the economic viability of the scale-up. The homogeneous catalysts reviewed herein include mineral acids and Brønsted acidic ionic liquids, such as SO3H-functionalized and heteropoly acid based ionic liquids. The heterogeneous catalysts reviewed herein include solid acid catalysts such as metal oxides, ion-exchange resins, zeolites, and supported heteropoly acid-based catalysts. Furthermore, the techno-economic analysis studies have shown the process to be highly profitable, confirming the viability of glycerol esterification as a potential tool for economic value addition to the biorefinery industry.

Techno-Economic Assessment and Sensitivity Analysis of Glycerol Valorization to Biofuel Additives via Esterification.

Glycerol is a valuable feedstock, produced in biorefineries as a byproduct of biodiesel production. Esterification of glycerol with acetic acid yields a mixture of mono-, di-, and triacetins. The acetins are commercially important value-added products with a wide range of industrial applications as fuel additives and fine chemicals. Esterification of glycerol to acetins substantially increases the environmental sustainability and economic viability of the biorefinery concept. Among the acetins, diacetin (DA) and triacetin (TA) are considered high-energy-density fuel additives. Herein, we have studied the economic feasibility of a facility producing DA and TA by a two-stage process using 100,000 tons of glycerol per year using Aspen Plus. The capital costs were estimated by Aspen Process Economic Analyzer software. The analysis indicates that the capital costs are 71 M$, while the operating costs are 303 M$/year. The gross profit is 60.5 M$/year, while the NPV of the project is 235 M$ with a payback period of 1.7 years. Sensitivity analysis has indicated that the product price has the most impact on the NPV.

Hydrophobic functional liquids based on trioctylphosphine oxide (TOPO) and carboxylic acids.

Trioctylphosphine oxide (TOPO) is a hydrophobic extracting agent used in a number of commercially important separations of valuable solutes from aqueous streams (with examples ranging from lanthanides, through gallium, to carboxylic acids). TOPO is traditionally used as a solute in kerosene, its extraction efficiency limited by its solubility in the organic diluents. In this work, eighteen hydrogen bond donors (HBDs) were screened for their capacity to liquefy TOPO, employing strategies used to design deep eutectic solvents (DES). The selected HBDs were all useful in separations and were designed to formulate solvent-free, hydrophobic, bi-functional liquid extracting agents. Some TOPO:HBD mixtures yielded hydrophobic liquids that offer potential to be extremely efficient extractants, incorporating high intrinsic concentrations of TOPO. Following this initial screening, two systems: TOPO:malonic acid and TOPO:levulinic acid, were selected for detailed physico-chemical characterisation across their complete compositional ranges. Phase diagrams, thermal stabilities and the mechanism of thermal decomposition are reported, along with densities and insights from 31P NMR spectroscopic studies. The work was concluded with a proof-of-concept demonstration of the use of the TOPO:malonic acid (2 : 1 mol ratio) mixture for the extraction of gallium from acidic chloride feedstock (simulated pre-digestate of zinc leach residue). The loading capacity of the TOPO:malonic acid extractant was three orders of magnitude greater than that of the literature benchmark, encouraging further application-oriented studies.

Frustrated Lewis pairs in ionic liquids and molecular solvents - a neutron scattering and NMR study of encounter complexes.

The presence of the weakly-associated encounter complex in the model frustrated Lewis pair solution (FLP): tris(tert-butyl)phosphine (P(tBu)3) and tris(pentafluorophenyl)borane (BCF) in benzene, was confirmed via PB correlation analysis from neutron scattering data. On average, ca. 5% of dissolved FLP components were in the associated state. NMR spectra of the FLP in benzene gave no evidence of such association, in agreement with earlier reports and the transient nature of the encounter complex. In contrast, the corresponding FLP solution in the ionic liquid, 1-decyl-3-methylimidazolium bistriflamide, [C10mim][NTf2], generated NMR signals that can be attributed to formation of encounter complexes involving over 20% of the dissolved species. The low diffusivity characteristics of ionic liquids is suggested to enhance high populations of encounter complex. The FLP in the ionic liquid solution retained its ability to split hydrogen.