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Mesoporous alumina was prepared by varying the crystallization time and acid concentration and evaluated in the glycerol dehydration. The samples were characterized by X-ray diffractometry (XRD), specific surface area (SBET), NH3-Temperature-programmed desorption (NH3-TPD), and Temperature-programmed Oxidation (TPO). The gas phase dehydration of glycerol was performed in a fixed-bed quartz tubular reactor at 500 °C using a 10% glycerol aqueous solution. The specific surface area, the crystallinity and the acidic properties of the samples were dependent on both the crystallization time and the acid concentration. The catalytic properties are related to the specific surface area and acidic characteristics. Samples with higher crystallization time showed lower surface area and lower amount of acid sites. Samples with the highest acid concentration solution had the higher surface area. Conversions of glycerol above 92% were obtained for all samples. The selectivity for dehydration products was strongly related to the amount and strength of acid sites.

This study investigates the effects of reaction variables (including space velocity, temperature, and partial pressures of LA and H2O) and acidic and basic additives on the gas-phase dehydration of lactic acid (LA) for acrylic acid (AA) production, using an aluminum-rich K+-exchanged ZSM-5 zeolite (molar SiO2/Al2O3 = 27, K/Al = 1.0, K/Na = 8) identified among many high-silica zeolites as the most efficient catalyst in our prior work (Yan et al. ACS Catal. 2017, 7, 538−550). Under widely varied reaction conditions (340–380 °C, feed GHSV: 9,500–38,000 h–1, 1.8–11.7 kPa LA, 52.0–73.0 kPa H2O), the catalyst offers not only high selectivity for AA (>75 mol %) but also long-term catalytic stability. Rate equations and their associated kinetic parameters for LA consumption and AA production are obtained by measuring the kinetically relevant catalytic rates under high feed space velocity (GHSV ≥ 57,000 h–1). Acidic (CO2, acetic acid, and trifluoroacetic acid) and basic (NH3) additives are added, respectively, to the reaction feed to investigate their effects on performance of the working catalyst. While addition of either CO2 or acetic acid shows no effect on the catalyst performance, the addition of either NH3 or trifluoroacetic acid causes significant decline in both the catalyst activity and selectivity for AA production, due to poisoning of the surface acidic sites by NH3 or basic sites by trifluoroacetic acid. These data well highlight the excellent catalytic performance of the investigated catalyst and offer a new piece of evidence in support of the cooperative acid–base bifunctional catalysis for the LTA reaction.

The activity of catalytic systems based on polyoxometalates in the gas-phase dehydration of glycerol into acrolein has been investigated. The catalysts synthesized have been characterized using FTIR spectroscopy, X-ray phase analysis, scanning electron microscopy, and low-temperature nitrogen adsorption/desorption (BET method). It has been shown that the nature of the surface acid sites of catalysts has a significant effect on the direction of glycerol transformation. An increase in the fraction of Bronsted acid sites in the catalyst leads to an increase in the yield of acrolein. At the same time, an increase in the fraction of Lewis acid sites in the catalyst leads to an increase to the yield of acetol, which is formed through a competing route. Among the catalytic systems considered, the best results have been obtained with the silicomolybdic acid anion supported onto alumina (SiMo/A). The main patterns of the gas-phase glycerol dehydration have been studied using SiMo/A as a catalyst, and the conditions responsible for the highest yield of acrolein have been determined.