One-Pot Transformation of Citronellal to Menthol Over H-Beta Zeolite Supported Ni Catalyst: Effect of Catalyst Support Acidity and Ni Loading

Citronellal was converted to menthol in a one-pot approach using H-Beta zeolite-based Ni catalyst in a batch reactor at 80 °C, under 20 bar of total pressure. The effects of H-Beta acidity (H-Beta-25 with the molar ratio SiO2/Al2O3 = 25 and H-Beta-300 with SiO2/Al2O3 = 300) and Ni loading (5, 10 and 15 wt %) on the catalytic performance were investigated. Ni was impregnated on H-Beta support using the evaporation-impregnation method. The physico-chemical properties of the catalysts were characterized by XRD, SEM, TEM, ICP-OES, N2 physisorption, TPR, and pyridine adsorption–desorption FTIR techniques. Activity and selectivity of catalysts were strongly affected by the Brønsted and Lewis acid sites concentration and strength, Ni loading, its particle size and dispersion. A synergetic effect of appropriate acidity and suitable Ni loading in 15 wt.% Ni/H-Beta-25 catalyst led to the best performance giving 36% yield of menthols and 77% stereoselectivity to (±)-menthol isomer at 93% citronellal conversion. Moreover, the catalyst was successfully regenerated and reused giving similar activity, selectivity and stereoselectivity to the desired (±)-menthol isomer as the fresh one. Graphical Abstract: [Figure not available: see fulltext.

Hydrothermal Decarboxylation and Hydrogenation of Fatty Acids over Pt/C

We report herein on the conversion of saturated and unsaturated fatty acids to alkanes over Pt/C in high-temperature water. The reactions were done with no added H 2 . The saturated fatty acids (stearic, palmitic, and lauric acid) gave the corresponding decarboxylation products ( n -alkanes) with greater than 90 % selectivity, and the formation rates were independent of the fatty acid carbon number. The unsaturated fatty acids (oleic and linoleic acid) exhibited low selectivities to the decarboxylation product. Rather, the main pathway was hydrogenation to from stearic acid, the corresponding saturated fatty acid. This compound then underwent decarboxylation to form heptadecane. On the basis of these results, it appears that this reaction system promotes in situ H 2 formation. This hydrothermal decarboxylation route represents a new path for using renewable resources to make molecules with value as liquid transportation fuels.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/83752/1/481_ftp.pd

Hydrodeoxygenation of Isoeugenol over Ni- and Co-Supported Catalysts

Hydrodeoxygenation (HDO) of isoeugenol was investigated over several Ni (Ni/SiO2, Ni/graphite) and Co (Co/SBA-15, Co/SiO2, Co/TiO2, Co/Al2O3) catalysts at 200 and 300 degrees C under 30 bar hydrogen pressure in a batch reactor. The catalysts were prepared by an impregnation method and systematically characterized by X-ray diffraction, transmission electron microscopy, scanning electron microscopy and energy dispersive analysis, organic elemental, and thermogravimetrical analysis before and after the reaction. Analysis of the liquid, solid, and gaseous products was performed to identify isoeugenol transformation pathways. The maximum yield of the desired propylcyclohexane (PCH) (63%) and the highest sum of masses of reactants and products in the liquid phase based on GC results (GCLPA) (79%) were obtained over 10 wt % Co/SBA-15. HDO of isoeugenol over 11 wt % Co/SiO2 resulted in 50% PCH yield with a rather similar GCLPA of 73%. Low yields of PCH and the liquid phase mass balance closure were obtained over highly dispersed 15 wt % Co/Al2O3 and 15 wt % Co/TiO2. PCH yield was 60% over Ni/graphite and 44% over Ni/SiO2 after 4 h with GCLPA values of 73 and 70%, correspondingly. Overall PCH yields increased in the following order: Co/TiO2 < Co/Al2O3 < Ni/SiO2 < Co/SiO2 < Ni/graphite < Co/SBA-15. Regeneration and reuse of industrially relevant 11 wt % Co/SiO2 was succesfully demonstrated

Hydrodeoxygenation of Isoeugenol over Alumina-Supported Ir, Pt, and Re Catalysts

Hydrodeoxygenation (HDO) of isoeugenol (IE) was investigated using bimetallic iridium rhenium and platinum rhenium catalysts supported on alumina in the temperature and pressure ranges of 200-250 degrees C and 17-40 bar in nonpolar dodecane as a solvent. The main parameters were catalyst type, hydrogen pressure, and initial concentration. Nearly quantitative yield of the desired product, propylcyclohexane (PCH), at complete conversion in 240 min was obtained with Ir-Re/Al2O3 prepared by the deposition-precipitation method using 0.1 mol/L IE initial concentration. High iridium dispersion together with a modification effect of rhenium provided in situ formation of the IrRe active component with reproducible catalytic activity for selective HDO of IE to PCH. The reaction rate was shown to increase with the increasing initial IE concentration promoting also HDO and giving a higher liquid phase mass balance. Increasing hydrogen pressure benefits the PCH yield

Selectivity control in Pt-catalyzed cinnamaldehyde hydrogenation

Chemoselectivity is a cornerstone of catalysis, permitting the targeted modification of specific functional groups within complex starting materials. Here we elucidate key structural and electronic factors controlling the liquid phase hydrogenation of cinnamaldehyde and related benzylic aldehydes over Pt nanoparticles. Mechanistic insight from kinetic mapping reveals cinnamaldehyde hydrogenation is structure-insensitive over metallic platinum, proceeding with a common Turnover Frequency independent of precursor, particle size or support architecture. In contrast, selectivity to the desired cinnamyl alcohol product is highly structure sensitive, with large nanoparticles and high hydrogen pressures favoring C=O over C=C hydrogenation, attributed to molecular surface crowding and suppression of sterically-demanding adsorption modes. In situ vibrational spectroscopies highlight the role of support polarity in enhancing C=O hydrogenation (through cinnamaldehyde reorientation), a general phenomenon extending to alkyl-substituted benzaldehydes. Tuning nanoparticle size and support polarity affords a flexible means to control the chemoselective hydrogenation of aromatic aldehydes

Recent developments in the production of liquid fuels via catalytic conversion of microalgae: experiments and simulations

Due to continuing high demand, depletion of non-renewable resources and increasing concerns about climate change, the use of fossil fuel-derived transportation fuels faces relentless challenges both from a world markets and an environmental perspective. The production of renewable transportation fuel from microalgae continues to attract much attention because of its potential for fast growth rates, high oil content, ability to grow in unconventional scenarios, and inherent carbon neutrality. Moreover, the use of microalgae would minimize ‘‘food versus fuel’’ concerns associated with several biomass strategies, as microalgae do not compete with food crops in the food chain. This paper reviews the progress of recent research on the production of transportation fuels via homogeneous and heterogeneous catalytic conversions of microalgae. This review also describes the development of tools that may allow for a more fundamental understanding of catalyst selection and conversion processes using computational modelling. The catalytic conversion reaction pathways that have been investigated are fully discussed based on both experimental and theoretical approaches. Finally, this work makes several projections for the potential of various thermocatalytic pathways to produce alternative transportation fuels from algae, and identifies key areas where the authors feel that computational modelling should be directed to elucidate key information to optimize the process