Catalytic Deactivation of HY Zeolites in the Dehydration of Glycerol to Acrolein

The study of the deactivation of HY zeolites in the dehydration reaction of glycerol to acrolein has represented a challenge for the design of new catalysts. HY zeolites with SiO2/Al2O3 molar ratios between 3.5 and 80 were studied. The solids were characterized by XRD, N2 physisorption, SEM-EDXS, Raman and UV-vis spectroscopies, infrared spectroscopy of pyridine (FTIR-Py) and catalytic activity tests from 250 °C to 325 °C. It was found that the total amount of acid sites per unit area of catalyst decreased as the SiO2/Al2O3 molar ratio increased from 3.5 to 80, resulting in the decrease in the initial glycerol conversion. The initial acrolein selectivity was promoted with the increase of the Brønsted/Lewis acid sites ratio at any reaction temperature. The deactivation tests showed that the catalyst lifetime depended on the pore structure, improving with the presence of large surface areas as evidenced by the deactivation rate constants. The characterization of the deactivated catalysts by XRD, N2 physisorption and thermogravimetric analysis indicated that the deposition of coke resulted in the total obstruction of micropores and the partial blockage of mesopores. Moreover, the presence of large mesopores and surface areas allowed the amount of coke deposited at the catalyst surface to be reduced.

Immobilization of Ir(OH)3 Nanoparticles in Mesospaces of Al-SiO2 Nanoparticles Assembly to Enhance Stability for Photocatalytic Water Oxidation

Iridium hydroxide (Ir(OH)3) nanoparticles exhibiting high catalytic activity for water oxidation were immobilized inside mesospaces of a silica-nanoparticles assembly (SiO2NPA) to suppress catalytic deactivation due to agglomeration. The Ir(OH)3 nanoparticles immobilized in SiO2NPA (Ir(OH)3/SiO2NPA) catalyzed water oxidation by visible light irradiation of a solution containing persulfate ion (S2O82−) and tris(2,2′-bipyridine)ruthenium(II) ion ([RuII(bpy)3]2+) as a sacrificial electron acceptor and a photosensitizer, respectively. The yield of oxygen (O2) based on the used amount of S2O82− was maintained over 80% for four repetitive runs using Ir(OH)3/SiO2NPA prepared by the co-accumulation method, although the yield decreased for the reaction system using Ir(OH)3/SiO2NPA prepared by the equilibrium adsorption method or Ir(OH)3 nanoparticles without SiO2NPA support under the same reaction conditions. Immobilization of Ir(OH)3 nanoparticles in Al3+-doped SiO2NPA (Al-SiO2NPA) results in further enhancement of the catalytic stability with the yield of more than 95% at the fourth run of the repetitive experiments.

Catalytic activity and mechanism of fluorinated MgO film supported on 3D nickel mesh for ozonation of gaseous toluene

The fluorination of a MgO catalyst could suppress acid-caused catalytic deactivation and promote toluene degradation efficiency during catalytic ozonation.

THE GLYCEROL´S WAY. A BRIEF REVIEW OF OPPORTUNITIES

In this paper, the recent state of the art, for about the last 4 years, of glycerol revalorization is presented. The study is focused on the vast opportunities associated to glycerol transformation. The operating conditions related to catalytic or biological conversion of crude glycerol such as catalytic deactivation, use of solvents, reaction type, selectivity yields and production cost are also analyzed. It was found that crude glycerol is a promising sustainable source of commodities such as hydrogen, solketal, ethanol, methanol, acrolein, carbonate, epichlorohydrin, among others. Also, the main challenges related to glycerol revalorization such as catalytic stability, selectivity and conversion yields, as well as cost on catalyst regeneration and novel processes are identified.

Influence of the Incorporation of Basic or Amphoteric Oxides on the Performance of Cu-Based Catalysts Supported on Sepiolite in Furfural Hydrogenation

Cu-based catalysts supported on sepiolite have been tested in vapor-phase hydrogenation of furfural. The incorporation of basic or amphoteric metal oxides (magnesium oxide, zinc oxide, or cerium oxide) improves the catalytic behavior, reaching a maximum furfural conversion above 80% after 5 h of reaction at 210 °C. In all cases, the main product is furfuryl alcohol, obtaining 2-methylfuran in lower proportions. The incorporation of these metal oxide species ameliorates the dispersion of metallic Cu nanoparticles, increasing the number of available Cu0-sites, which enhances the catalytic performance. The presence of acid sites favors the hydrogenolysis of furfuryl alcohol towards 2-methylfuran, although it also causes an increase of carbon species on its surface, which is associated with the catalytic deactivation of the catalyst along the time-on-stream.