Catalysts based on Ru and Pd nanoparticles on mesoporous hybrid supports consisting of mesoporous phenol–formaldehyde polymers and silica were synthesized. The catalysts were tested in furfural hydrogenation at 150–250°С and hydrogen pressure of 3 MPa. In furfural hydrogenation in the presence of the Pd catalyst, the yield of tetrahydrofurfuryl alcohol was 99

A ruthenium catalyst based on hexagonal mesoporous silica modified with aluminum (Al-HMS structural type) of a Si/Al ratio equal to 10 was studied in the hydrodeoxygenation reaction of bio-oil components containing a guaiacol fragment. The catalyst was tested in the hydrodeoxygenation of guaiacol, methoxyguaiacol, formylguaiacol, and propylguaiacol in the presence of water at a hydrogen pressure of 6.0 MPa and a temperature of 250°C. The effect of the substrate structure on the conversion and selectivity of hydrotransformation towards fully hydrogenated and deoxygenated products is shown. The effect of temperature in the range of 210–290°C on the conversion and distribution of guaiacol hydrodeoxygenation products at various hydrogen pressures (2.5 and 6.0 MPa) is demonstrated. Experiments were carried out on the hydrodeoxygenation of guaiacol in a mixture with water, n -dodecane, and methanol at a hydrogen pressure of 6.0 MPa and a temperature of 250°C. The effect of the model mixture composition on the conversion and distribution of guaiacol hydrodeoxygenation products is shown.

Pt- and Pd-containing catalysts based on the mesoporous aluminosilicate Al–HMS (Hexagonal Mesoporous Silica) with the Si/Al ratio of 10 were synthesized. The catalysts were tested in furfural hydrogenation in an aqueous medium at a hydrogen pressure of 1–5 MPa in the temperature interval 100–200°С. At 100°C, furfural transformed mainly into furfuryl alcohol, and at 200°С, into cyclopentanone (3 MPa of Н2, 1 h). In the presence of the Pd/Al–HMS catalyst, the conversion and selectivity of formation of tetrahydrofurfuryl alcohol increased with an increase in the initial hydrogen pressure or in the catalyst concentration (100°С, 1 h). Pd/Al–HMS is more active in furfural hydrogenation in an aqueous medium: With this catalyst, virtually complete furfural conversion was reached in the temperature interval 150–200°С, whereas with Pt/Al–HMS the conversion did not exceed 23

The paper describes synthesis of ruthenium and nickel catalysts supported on aluminum-modified SBA-15 (Santa Barbara Amorphous-15) mesoporous silicate, designated as Al-SBA-15, with a Si/Al ratio of 20. The catalysts were investigated in aqueous-phase hydrogenation of furfural, a valuable product obtained from lignocellulosic biomass. Elevating the reaction temperature from 200 to 250°C and the hydrogen pressure from 3 to 5 MPa enhanced the selectivity towards methyltetrahydrofuran (MTHF). The ruthenium catalyst outperformed its nickel counterpart in terms of activity in aqueous-phase furfural hydrogenation (250°C, 5 MPa H 2 ).

Mesoporous nanospherical resorcinol-formaldehyde polymers NSMR-1 and NSMR-2 are synthesized. They are characterized by an average material particle size of 289 and 156 nm, respectively. Hybrid catalysts NSMR-Ru-1 and NSMR-Ru-2 were fabricated, which are Ru nanoparticles included in the structure of polymer supports NSMR-1 and NSMR-2. The catalysts were tested in the guaiacol hydrogenation at a temperature of 200°C and a hydrogen pressure of 5.0 MPa in an aqueous medium. It was found that the NSMR-Ru-2 catalyst, which is characterized by a smaller support particle size, exhibits a higher activity compared to the NSMR-Ru-1 catalyst. Experiments were carried out on the hydrogenation of guaiacol in a mixture with methanol, acetic acid, and furfural over the NSMR-Ru-2 catalyst. The influence of oxygenates on the conversion of guaiacol and the selectivity for its hydrogenation products was displayed.

The problems of zeolite catalysis associated with the introduction of domestic technologies are considered. Particular attention is paid to works related to the use of alternative components of catalytic systems, the introduction of new environmentally friendly materials that improve the quality of the fuels produced with their use. The processes of catalytic cracking, processing of heavy petroleum residues, solid-acid alkylation, and synthesis of light olefins and the problems of renewable feedstock processing are discussed in detail.

A ruthenium-containing catalyst on ZSM-5/MCM-41 micro-mesoporous aluminosilicate support was synthesized. The micro-mesoporous support and supported catalyst were characterized by low-temperature nitrogen desorption/adsorption, temperature-programmed ammonia desorption, transmission electron microscopy, X-ray photoelectron spectroscopy, temperature-programmed reduction with hydrogen, and energy-dispersive X-ray fluorescence analysis. Ru/ZSM-5/MCM-41 has high specific surface area (392 m2 g−1) and high acidity (1087 µmol g−1); the mean ruthenium particle size is 1.7 nm. The catalyst was studied in hydrodeoxygenation of a modelbio-oil compound, guaiacol, in the presence of water at a hydrogen pressure of 5 MPa and temperatures in the interval 130–290°C. The catalyst obtained exhibits high activity in guaiacol hydrodeoxygenation: The conversion was 90%, and the selectivity with respect to cycloalkanes was 64% in 3-h reaction performed at a hydrogen pressure of 5 MPa and a temperature of 230°C.

Ruthenium-containing catalyst based on an Al-HMS mesoporous aluminosilicate was synthesized, The mesoporous support and the catalyst on its basis were characterized by the methods of low-temperature desorption/adsorption of nitrogen, temperature-programmed desorption of ammonia, transmission electron microscopy, X-ray photoelectron microscopy, and energy-dispersive X-ray fluorescence analysis. The catalyst obtained was examined in the reaction of hydrodeoxygenation of the model compound of bio-oil, furfural, in the presence of water. The reaction was performed at initial hydrogen pressures of 1–7 MPa in the temperature range 200–300°C. It was shown that the catalyst under study exhibits a high activity in the hydrotransformation of furfural: the conversion was 100% in 1 h at a hydrogen pressure of 5 MPa and temperature of 200°C.

The liquid phase hydrodeoxygenation (HDO) of guaiacol (GUA), a model compound of bio-oil, was studied on bimetallic (PtPd) and monometallic (Ru) catalysts supported on mesoporous aluminosilicate of Al-HMS(X) type with different Si/Al (X) ratios and on mesoporous zirconia modified with silica (m-ZrO2-SiO2) in the presence of methanol as a solvent. The catalysts were characterized by NH3-TPD, TEM, XPS, Al-27 and Si-29 solid-state NMR and N-2 adsorption-desorption methods. The influence of catalyst loading, temperature, solvent/guaiacol ratio and contact time on the catalytic performance was investigated. It was established that, decreasing the Si/Al ratio and, correspondingly, increasing the acidity of the catalysts based on Al-HMS led to increasing conversion of guaiacol. Phenol, catechol, and their methylated derivatives were the main products of guaiacol HDO reaction in methanol at low catalyst loading (guaiacol/metal ratio, 800). It was found that the fraction of completely hydrodeoxygenated products (cyclohexane and methylcyclohexane) greatly increased as the catalyst loading grew (guaiacol/metal ratio, 160). Conversion of guaiacol on PtPd/m-ZrO2-SiO2 catalyst was higher than that on PtPd/Al-HMS(10), in accordance with the larger number of acid sites on the catalyst surface; however, the undesirable heavy fraction of methylated by-products was also higher. Ru-based catalysts exhibited the highest catalytic activity and showed unusually high selectivity toward fully hydrodeoxygenated products (cyclohexane, methylcyclohexane) in the HDO of guaiacol in the presence of methanol. Guaiacol can be efficiently converted into alkanes, with quantitative conversion and selectivity to cyclohexanes of 78% over Ru/Al-HMS(10) catalyst under relatively mild conditions (200 degrees C, 5 MPa H-2). Methylation under the influence of methanol, deoxygenation on acid sites and aromatic ring hydrogenation on metal sites proceeded in a parallel way according to the suggested reaction pathways.

Pt-containing catalysts based on halloysite aluminosilicate nanotubes and ZSM-5 zeolite were synthesized. The structure of the materials was confirmed by low-temperature nitrogen adsorption/desorption and by transmission electron microscopy. The activity and selectivity of the synthesized catalysts based on micromesoporous supports in isomerization of the xylene reforming fraction was studied on a flow-through laboratory installation with a fixed catalyst bed in the temperature interval 360–440°С at elevated hydrogen pressure. The influence exerted by the textural characteristics of the support and acidity of the materials on the catalyst activity in isomerization of o- and m-xylenes and of ethylbenzene with the aim of obtaining p-xylene was studied.