A method is proposed for the synthesis of micro-mesoporous SAPO-31 with a high external surface area and large mesopore volume using tetraethoxysilane as a source of silicon. The synthesis of SAPO-31 is based on the principles underlying the Stöber process approach, which allows control of the pore diameter and volume and, hence, the external surface area of the product material. The use of the proposed methods for depositing the hydro-dehydrogenating component on the synthesized micro-mesoporous SAPO-31 made it possible to obtain highly efficient bifunctional hydroisodeparaffinization catalysts with the platinum or palladium content not higher than 0.2 wt.%. As a result, the process temperature can be decreased by 50–60 °C in comparison with the known analogs. Therewith, for example, in the test reaction of n-decane hydroisodeparaffinization at a temperature of 300 °C and feed rate of 1.5 h−1, the conversion above 90%, and the 97–98% yield of liquid products, the 95% selectivity to isomeric products were achieved.

Levulinic acid and its esters (e.g., ethyl levulinate, EL) are platform chemicals derived from biomass feedstocks that can be converted to a variety of valuable compounds. Reductive amination of levulinates with primary amines and H2 over heterogeneous catalysts is an attractive method for the synthesis of N-alkyl-5-methyl-2-pyrrolidones, which are an environmentally friendly alternative to the common solvent N-methyl-2-pyrrolidone (NMP). In the present work, the catalytic properties of the different nickel phosphide catalysts supported on SiO2 and Al2O3 were studied in a reductive amination of EL with n-hexylamine to N-hexyl-5-methyl-2-pyrrolidone (HMP) in a flow reactor. The influence of the phosphorus precursor, reduction temperature, reactant ratio, and addition of acidic diluters on the catalyst performance was investigated. The Ni2P/SiO2 catalyst prepared using (NH4)2HPO4 and reduced at 600 °C provides the highest HMP yield, which reaches 98%. Although the presence of acid sites and a sufficient hydrogenating ability are important factors determining the pyrrolidone yield, the selectivity also depends on the specific features of EL adsorption on active catalytic sites.

Effect of sulfosalicylic acid treatment on the properties of Beta zeolite (BEA and BEA-SA) and performance of NiW/Beta-Al2O3 catalysts in hexadecane hydrocracking have been studied. The acid treatment had almost no effect on porous structure of Beta zeolite while it resulted in significant changes in acidity. The decrease in concentration of Bronsted (35 to 25 mu mol/g) and Lewis acid sites (119 to 54 mu mol/g) was observed that could be related to the removal of extra framework aluminum. NiW/BEA-Al2O3 catalyst having zeolite with higher acidity demonstrated higher activity in hexadecane hydrocracking. The hexadecane conversion was 54.5-95.6% and 32.4-93.9% for NiW/BEA-Al2O3 and NiW/BEA-SA-Al2O3, respectively. However, NiW/BEA-SA-Al2O3 demonstrated higher selectivity to target products (C-5-C-15 hydrocarbons and iso-C-16) than NiW/BEA-Al2O3 (63.8 and 14.4 % vs. 62.4 and 4.5 %, respectively) at similar hexadecane conversion of similar to 95 %. This can be attributed mainly to the effect of sulfosalicylic acid treatment on Beta zeolite acidity.

Two different series of bifunctional hydroisodeparaffinization catalysts with deposited palladium and based on SAPO-11 and SAPO-31 are fabricated and studied, with (1) varied activity of the acidic component at a constant activity of the hydro–dehydrogenating component and (2) varied activity of the hydro–dehydrogenating component at a constant activity of the acidic component. It is shown that the temperature of 90% n-decane conversion on the catalysts with the same hydro–dehydrogenating activity depends linearly on the overall activity of the acidic catalyst component. The character of this dependence is identical for both structural types of SAPO-11 and SAPO-31 silicoalumophosphates. The bifunctional catalysts based on SAPO-31 are much more active than those based on SAPO-11. At the same overall activity of the acidic component, the temperature of 90% n-decane conversion on the Pd/SAPO-31 catalysts is 50°C lower than on the Pd/SAPO-11 catalysts. Ways of controlling the overall activity and selectivity of a hydroisodeparaffinization catalyst by varying the activity of the acidic and/or hydro–dehydrogenating component of a bifunctional catalyst are shown. An increase in the hydro–dehydrogenating activity of the catalyst enhances the hydroisomerizing activity of a bifunctional catalyst with virtually no changes in selectivity toward isomers. An increase in the overall activity of the acidic component also enhances the hydroisomerizing activity of a bifunctional catalyst, but appreciably alters its selectivity toward isomers.

Palladium-containing catalyst based on binder-free granular sulfated zirconium oxide for n-butane isomerization has been investigated. It has been found that Pd content of 0.2–1.0 wt % slightly influences textural characteristics and other physicochemical properties of bifunctional catalysts; however, it determines their activity and selectivity in the reaction studied, with the optimal palladium content being 0.5 wt %. Parameters of the isomerization process have been studied depending on the composition of industrial n-butane fractions. It has been shown that impurities of isobutane, propane, neopentane, isopentane and pentane in an amount of no more than 2% do not exert a effect on isobutane production; nonetheless, the conversion of n-butane and selectivity for isobutane both increase when more pure n-butane fractions are used. It has been found that the process for isobutane production by isomerization of the n-butane fraction under the optimal conditions at H2 /n-C4 = 0.1 and 140–150°C makes it possible to obtain a high isobutane yield (up to 52 wt %) and avoid the undue formation of С1–С3 alkanes.

Two series of bifunctional hydroisodeparaffinization catalysts containing palladium supported on SAPO-11 and SAPO-31 were prepared and characterized. These were catalysts: 1) With different activities of the acidic component at the constant activity of the hydro-dehydrogenating component; 2) With different activities of the hydro-dehydrogenating components at the constant activity of the acidic component. With the catalysts with identical hydro-dehydrogenating activities, the temperature of eaching 90 % conversion of n -decane was shown to depend linearly on a total of the activity of the acidic component of the catalyst. Similar profiles of the dependencies were characteristic of both SAPO-11 and SAPO-31. The bifunctional catalysts based on SAPO-31 were much more active than the catalysts on SAPO-11. At identical total activities of the acidic components, the temperature of reaching 90 % conversion of n -decane was 50 °C lower over Pd/SAPO-31 than over Pd/SAPO-11. Ways to controlling the total activity and selectivity of the hydroisodeparaffinization catalyst by varying the activity of the acidic and/or hydro-dehydrogenating components of the bifunctional catalyst were demonstrated. An increase in the hydro-dehydrogenating activity led to an increase in the hydroisomerization activity of the bifunctional catalyst but practically not to changes in the selectivity to isomers. An increase in the toital activity of the acidic component also led to an increase in the hydroisomerization activity of the bifunctional catalyst, while the selectivity to isomers changed considerably.

Part III of this work continues the study of the catalytic properties of new molybdenum carbide based hydroisomerization catalysts, which are resistant to sulfur compounds and allow the synthesis of waxy diesel fuels with the same quality characteristics as those of platinum-containing catalysts. The catalytic properties of such bifunctional catalysts as 7%Mo 2 C/SAPO-31 (LCCH-2) and 7%Mo 2 C/SAPO-11 (LCCH-2-2) in diesel fraction hydroisomerization in the temperature range of 320–400°C are compared. It is shown that LCCH-2 ensures a higher yield of the hydroisomerized diesel fraction with a lower freezing point as compared to LCCH-2-2 at temperatures above 320°C. The ratio between mono- and di-isomers in reaction products is analyzed. It is concluded that SAPO-31 based catalyst is more selective to the formation of terminal monosubstituted alkanes than SAPO-11 based catalyst. The resistance of both catalysts to deactivation with coke deposits (tests over 100 h at 320 and 360°C in hydroisomerization) is studied. It is established that LCCH-2-2 is less resistant to deactivation than LCCH-2. These findings are due to differences in acidity, the degree of uniformity in the distribution of acidic hydrogenating/dehydrogenating sites in the catalysts, and the structural type of their acidic supports.

The effect of support nature, SiO2 and γ-Al2O3, on physicochemical and catalytic properties of nickel phosphide catalysts in methyl palmitate hydrodeoxygenation (HDO) has been considered. Firstly, alumina-supported nickel phosphide catalysts prepared by temperature-programmed reduction method starting from different precursors (phosphate–Ni(NO3)2 and (NH4)2HPO4 or phosphite–Ni(OH)2 and H3PO3) were compared using elemental analysis, N2 physisorption, H2-TPR, XRD, TEM, NH3-TPD, 27Al and 31P MAS NMR techniques and catalytic experiments. The mixture of nickel phosphide phases was produced from phosphate precursor on alumina while using of phosphite precursor provides Ni2P formation with the higher activity in methyl palmitate HDO. Besides, the comparative study of the performances of Ni2P/SiO2 and Ni2P/Al2O3 catalysts demonstrates the apparent superiority of alumina-supported Ni2P in the methyl palmitate hydrodeoxygenation. Considering the tentative scheme of methyl palmitate transformation, we proposed that cooperation of Ni2P and acid sites on the surface of alumina provides the enhanced activity of alumina-supported Ni2P through the acceleration of acid-catalysed hydrolysis.

The aim of this work is to develop a new hydroisomerization catalyst based on molybdenum carbides that is resistant to the influence of sulfur compounds and applicable for the synthesis of low-pour-point diesel fuels that are similar in parameters to the fuel synthesized using platinum-containing catalysts. In the first part of the work, supports with different porous structures and acidities (Beta, ZSM-5, ZSM-12, and SAPO-31) are synthesized and studied. In the second part of the work, bifunctional catalysts prepared by modifying these supports with nanosized molybdenum carbides are studied. All samples contain the same amount of Mo 2 C (10% in terms of the equivalent amount of MoO 3 ). The catalysts are tested using a model isomerization reaction of n -decane. The catalyst based on silicoaluminophosphate ATO (SAPO-31) proves to be the most effective one. In order to optimize its composition, larger batches of samples with different Mo 2 C contents (5, 7 and 10% in terms of the equivalent amount of MoO 3 ) are prepared. The catalytic properties are studied using the hydroisomerization of actual diesel fractions. The optimum content of Mo 2 C (7 wt %) in the bifunctional catalyst is determined.

The Ni2P/SiO2 catalyst, which was prepared by in situ temperature-programmed reduction and in the mixture with the inert (SiC, SiO2) or acidic (γ-Al2O3) material was studied in methyl palmitate hydrodeoxygenation (HDO). Methyl palmitate HDO was carried out at temperatures of 270–330 °C, H2/feed volume ratio of 600 Nm3/m3, and H2 pressure of 3.0 MPa. Ni2P/SiO2 catalyst, diluted with γ-Al2O3 showed a higher activity than Ni2P/SiO2 catalyst diluted with SiC or SiO2. The conversion of methyl palmitate increased significantly in the presence of γ-Al2O3 most probably due to the acceleration of the acid-catalyzed reaction of ester hydrolysis. The synergism of Ni2P/SiO2 and γ-Al2O3 in methyl palmitate HDO can be explained by the cooperation of the metal sites of Ni2P/SiO2 and the acid sites of γ-Al2O3 in consecutive metal-catalyzed and acid-catalyzed reactions of HDO. The obtained results let us conclude that the balancing of metal and acid sites plays an important role in the development of the efficient catalyst for the HDO of fatty acid esters over supported phosphide catalysts.

Hydroisomerization catalysts based on nanosized molybdenum carbides are developed. Such catalysts are resistant to sulfur compounds and can be used for the synthesis of waxy diesel fuels with the same characteristics as on platinum-containing catalysts. In the first part of this work, acidic supports with different types of porous structure and concentrations and strengths of Brønsted acidic sites (e.g., silicoaluminophosphate SAPO-31, zeolite ZSM-12, modified zeolite Beta, and desiliconized zeolite ZSM-5) are synthesized for a new type of catalysts. Their physicochemical properties are studied by means of adsorption, temperature- programmed desorption of ammonia (TPD-NH 3 ), nuclear magnetic resonance (NMR) spectroscopy, and scanning electron microscopy (SEM).

Part 3 of the studies dealt with catalytic properties of the new catalysts based on molylbdenum carbides, resistant to sulfur compounds and providing manufacturing of low pour point diesel fuel with the quality indices identical to those obtained with platinum-containing catalysts. Catalytic properties of bifunctional catalysts 7%Mo2C/SAPO-31 (LCCH-2) and 7%Mo2C/SAPO-11 (LCCH-2-2) for hydroisomerization of diesel fractions were compared at the temperature range between 320 and 400 °C. It was shown that at above 320 °C the catalyst LCCH-2, against LCCCH-2-2, provided the formation of the hydroisomerized diesel fraction at a higher yield and freezing at a lower temperature. Inspection of the data on the ratio of total quantities of monomers and diisomers in the reaction products led to conclude that the former catalyst is more selective than the latter to the formation of terminal monosubstituted alkanes. Studies of the stability of both catalysts to deactivation with coke deposits (100 hour testing at 320 and 360 °C during hydroisomerization) revealed that LCCH-2-2 is less stable to deactivation than LCCH-2. The observed regularities were accounted for by differences in the acidities, degree of homogeneity of distribution of acid and hydrating-dehydrating centers through the catalysts under study, and types of structures of the acid support.

The studies were aimed at the development of hydroisomerization catalysts based on nanosize molybdenum carbides. These catalysts were expected to be resistant to sulfur compounds and applicable for synthesis of low pour point diesel fuels similar in parameters to the fuel synthesized over platinum catalysts. Acidic supports were synthesized for these catalysts; the supports differ by the type of their porous structures, number and strength of Broensted acid sites; these were silicoaluminophasphate SAPO-31, zeolite ZSM-21, modified zeolite Beta, desalicided zeolite ZSM-5. Adsorption methods, TPD of ammonia, NMR, SEM techniques were used for studying physicochemical properties of the supports.

The studies were aimed at the development of hydroisomerization catalysts based on nanosize molybdenum carbides. These catalysts were expected to be resistant to sulfur compounds and applicable for synthesis of low pour point diesel fuels similar in parameters to the fuel synthesized over platinum catalysts. Part I dealt with synthesis and characterization of supports with different porous structures and acidities (Beta, ZSM-5, ZSM-12, SAPO-31). Part 2 of the work was devoted to studies of bifunctional catalysts prepared by modifying these supports with nanosize molybdenum carbides. All the samples bore identical amounts of Mo 2 C (10 % expressed in terms of the equivalent amount of MoO 3 ). The catalysts were tested using a model reaction of isomerization of n -decane. The catalyst based on silicoaluminophosphate ATO (SAPO-31) was most active to isomerization. Larger batches of the catalysts with different Mo 2 C contents (5, 7 and 10 expressed in terms of the equivalent amount of MoO 3 ) were prepared to optimize the composition. The catalytic properties were studied using hydroisomerization of actual diesel fractions. The optimal content of Mo 2 C (7 wt %) in the bifunctional catalyst was determined.

The effect of phosphorus precursor on the physicochemical and catalytic properties of silica-supported nickel phosphide catalysts in the hydrodeoxygenation (HDO) of aliphatic model compound methyl palmitate (C15H31COOCH3) has been considered.

The increasing the stability of the MFI type zeolite catalysts is actual for creating of high active catalysts for methanol conversion to C2–C4 hydrocarbon gases or hydrocarbons to aromatics – an important industrial processes. Three new approach to improve the stability of zeolite catalysts are proposed in the work: the selective dealumination on the outer surface of the MFI zeolite crystals; the structure-selective ion exchange on the external surface of the crystals, the use of isothermal (tubular) reactor. The influence of conditions of selective dealumination and structurally selective ion exchange on the molar ratio SiO2/Al2O3 of the zeolite and time between regeneration running in the conversion of methanol into hydrocarbons is studied. It is found that the selective dealumination of external surface leads to an increase of between regeneration running up to 3–5 times. Structure-selective ion exchange on the outer surface of the zeolite crystals can increase the time of running in 2–4 times, reduce the temperature and duration of recovery due to changes in the properties of the deposited coke. Application of the tubular reactor allows to facilitate the regeneration process compared with an adiabatic reactor by the formation of less condensed coke.

Increasing the operational stability of MFI-type zeolite catalysts is topical for the creation of highly efficient catalysts for the conversion of methanol or C2-C4 hydrocarbon gases into aromatic hydrocarbons, i.e., important industrial processes. This study proposes three new approaches to increasing the stability of zeolite catalysts: selective dealumination on the outer surface of MFI zeolite crystals, structurally selective ion exchange on the outer surface of crystals, and the application of an isothermal (multitube) reactor. The effect of selective dealumination and structurally selective ion exchange conditions on the SiO2/Al2O3 molar ratio in the zeolite on the interregeneration period duration in the conversion of methanol into hydrocarbons has been studied. It has been established that the selective dealumination of the outer surface increased the interregeneration period duration by 3–5 times. Structurally selective ion exchange on the outer surface of zeolite crystals allows us to increase the interregeneration period duration by 2–4 times and to decrease the regeneration temperature and duration due to the change of the properties of deposited coke. The application of a multitube reactor facilitates the procedure of regeneration in comparison with an adiabatic reactor due to the formation of less condensed coke depositions.