The objective of the present work is to achieve high yield to 1-propanol (1-POH) by crude glycerol hydrogenolysis in liquid phase and find an alternative to the use of noble metals by employing Ni catalysts. Two Ni catalysts with different supports, alumina (γ-Al₂O₃), and a phosphorous-impregnated carbon composite (CS-P) were studied and characterized in order to determine their acid properties and metallic phases. With the Ni/γ-Al₂O₃ catalyst, which presented small particles of metallic Ni interacting with the acid sites of the support, it was possible to obtain a complete conversion of crude glycerol with high selectivity towards 1,2-propylene glycol (1,2 PG) (87%) at 220 °C whereas with the Ni/CS-P catalyst, the presence of AlPOx species and the Ni₂P metallic phase supplied acidity to the catalyst, which promoted the C-O bond cleavage reaction of the secondary carbon of 1,2 PG to obtain 1-POH with very high selectivity (71%) at 260 °C. It was found that the employment of two consecutive reaction stages (first with Ni/ γ-Al₂O₃ at 220 °C and then with Ni/CS-P at 260 °C) allows reaching levels of selectivity and a yield to 1-POH (79%) comparable to noble metal-based catalysts.

Research on the use of biomass resources for the generation of energy and chemical compounds is of great interest worldwide. The development and growth of the biodiesel industry has led to a parallel market for the supply of glycerol, its main by-product. Its wide availability and relatively low cost as a raw material make glycerol a basic component for obtaining various chemical products and allows for the development of a biorefinery around biodiesel plants, through the technological integration of different production processes. This work proposes a review of one of the reactions of interest in the biorefinery environment: the hydrogenolysis of glycerol to 1,2-propylene glycol. The article reviews more than 300 references, covering literature from about 20 years, focusing on the heterogeneous catalysts used for the production of glycol. In this sense, from about 175 catalysts, between bulk and supported ones, were revised and discussed critically, based on noble metals, such as Ru, Pt, Pd, and non-noble metals as Cu, Ni, Co, both in liquid (2–10 MPa, 120–260 °C) and vapor phase (0.1 MPa, 200–300 °C). Then, the effect of the main operational and decision variables, such as temperature, pressure, catalyst/glycerol mass ratio, space velocity, and H₂ flow, are discussed, depending on the reactors employed. Finally, the formulation of several kinetic models and stability studies are presented, discussing the main deactivation mechanisms of the catalytic systems such as coking, leaching, and sintering, and the presence of impurities in the glycerol feed. It is expected that this work will serve as a tool for the development of more efficient catalytic materials and processes towards the future projection of glycerol biorefineries.

Humanity’s growing dependence on non-renewable resources and the ensuing environmental impact thus generated have spurred the search for alternatives to replace chemicals and energy obtained from petroleum derivatives. Within the group of biofuels, biodiesel has managed to expand worldwide at considerable levels, going from 20 million tn/year in 2010 to 47 million tn/year in 2022, boosting the supply of glycerol, a by-product of its synthesis that can be easily used as a renewable, clean, low-cost raw material for the manufacture of products for the chemical industry. The hydrogenolysis of glycerol leads to the production of glycols, 1,2-propylene glycol (1,2-PG) and 1,3-propylene glycol (1,3-PG). In particular, 1,3-PG has the highest added value and has multiple uses including its application as an additive in the polymer industry, the manufacture of cosmetics, cleaning products, cooling liquids, etc. This review focuses on the study of the hydrogenolysis of glycerol for the production of 1,3-PG, presenting the main reaction mechanisms and the catalysts employed, both in liquid and vapor phase. Engineering aspects and the effect of the operating variables to achieve maximum yields are discussed. Finally, studies related to the stability and the main deactivation mechanisms of catalytic systems are presented.

Bentonites are natural clays found in abundance in deposits all over the planet and possess certain properties that make them interesting for various industrial applications. Through their activation or acid treatment, they can be used as catalysts in several reactions of interest. However, these materials form colloidal suspensions in water or in aqueous solutions, which makes their separation and recovery difficult and prevents their implementation on an industrial scale. To overcome these limitations, in the present work, a silica-resin-bentonite composite material was synthesized and activated with HNO₃. The activated solids were characterized and evaluated in the catalytic reaction of solketal synthesis from glycerol and acetone. The best results were obtained for a composite containing 47 wt.% acidified bentonite at 90 °C, with a HNO₃ concentration of 0.5 mol L⁻¹, which was attributed to both its acid site density—3.9 mmol per gram of bentonite—and the acidic strength of these sites.