A method for sol-gel synthesis of micro-meso- and mesoporous aluminosilicates (MAS) was developed using the commercially available raw materials (a mixture of ethylsilicate-40 type oligoesters of ortho-silicic acid and alcohol water solutions of aluminium nitrate). The influence of pH on the porous structure of aluminosilicates with various Si/Al ratios was studied. A variation in pH at the hydrolysis stage was shown to allow both microporous and mesoporous aluminosilicate with a narrow pore size distribution to be synthesized, the specific surface area being varied from 341 to 684 m2/g, specific pore volume from 0,2 to 0,95 cm3/g, pore diameter from 0,17 to 40 nm, total ammonia acidity from 226 to 405 μmol/g. The acidic properties of the samples with different SiO2/Al2O3 ratios and their catalytic activities were studied using the model reaction of α-methylstyrene dimerization (80 °C, 10 wt.% MAC, the initial α-methylstyrene concentration 3.3 mol/l in chlorobenzene). The maximal α-methylstyrene conversion (99,8 %) was observed over the catalysts at the SiO2/Al2O3 ratios equal to 5 and 20 when the concentrations of acid sites are maximal. The micro-mesoporous aluminosilicates are promising catalysts for acid-base transformations of various organic compounds.

There was performed brief analysis of state of research activities and commercial development in the world and Russia in selective and nonselective oligomerization of ethylene into higher olefins, including linear α-olefins: butene-1, hexene-1 and octene-1.

The process of C2–C4 olefin production by catalytic high-destruction
cracking and thermocontact pyrolysis of vacuum gasoil, technical cottonseed oil and a mixture of vacuum gasoil and cottonseed oil (90:10) at 600–800 °C was studied using natural halloysite, which consists of nanosize circinate aluminosilicate plates, extracted from kaolinite deposits. In the process of high-destruction catalytic cracking of pure vacuum gasoil at 600 °C, the ethylene yield was 6,4–10,1 wt.% higher over halloysite catalyst than over ZSM-5. The addition of technical cottonseed oil (10 %) to vacuum gasoil resulted in an increase in the ethylene yield by another 2.2 wt % and an increase in the propylene yield by 3,3 wt.%. Cracking of the pure cottonseed oil under identical conditions provided 16,1 wt.% and 9,2 wt.% yields of ethylene and propylene, respectively. A possibility was established to use halloysite nanotubes as the heating surface for thermal pyrolysis of the above said raw materials at 700–800 °C to produce C2–C3 olefins at higher yields than those achieved in the industrial processes. The full regeneration of halloysites makes it possible to recycle them for thermal transformation of the raw materials under study.

The data on liquid-phase oxidation of naphthene-isoparaffin hydrocarbons (216–360 °C fraction) of Azerbaijanian oil in the presence of constant (Zn) and variable (Cr, Mn) valence metal salts of natural petroleum acids (NPA) were reported. The dependence of the yields of synthetic naphthenic acids (SNA) on the catalyst nature and concentration (0,2–1,0 wt.%) was studied. The highest SNA yields were observed at the concentrations of 0,2 wt.% Cr(NPA) and 1,0 wt.% Mn(NPA). The synergistic effect was observed with a combination of Cr and Mn salts. The results obtained were recommended for application of the new stabilizer package for commercial production of synthetic naphthenic acids.

In 2005–2006, experimental studies on synthesis of methylethyl ketone (MEK) were aimed at the technological adoption of high-selective oxidation of n-butylene into MEK with air in the presence of a new homogeneous catalyst. The catalyst was a chlorine-free aqueous solution Pd(II) + HPA-7’, where HPA-7’ was a high-vanadium Mo-V-P acid of the modified (non-Keggin) total composition H12P3Mo18V7O85. The fire and explosion safety of the pilot plant (PP) was achieved by arranging two stage MEK process (1) + (2) in different reactors, while the catalyst solution was made close-circuit flowing. Target reaction (1) was conducted at 60 °C and 9 bar of n-butylene pressure in a plug-flow reactor 1 in the absence of oxygen. The high oxidative potential of the HPA-7’ solution provided the high rate of the reaction that took less than 20 min. MEK was separated from the reduced catalyst using a film evaporator (steaming column) at 100 °C. Stage (2) was the catalyst regeneration with air oxygen in a unique plug-flow reactor 2; it took 40–50 min at 160–190 °C and 20 bar (PO2 = 4 bar). The regenerated catalyst was fed again to reactor 1 for the next catalytic cycle. Thus, the two-stage catalytic  reaction of n-butylene oxidation with oxygen was conducted in PP with the continuous isolation of MEK. The experimental studies demonstrated viability of non-stationary catalysis for the two-stage MEK process. The developed catalyst composition, Pd(II) + HPA-7’, seemed to be close to optimal. Inspection of the PP design drawbacks allowed the way of its reconstruction to be identified in order to drive up to the rated capacity of 250 kg MEK/day. The results obtained by pilot testing of the MEK process will be taken into consideration to develop two-stage technologies for oxidation of various organic compounds with oxygen in the presence of HPA solutions.

An engineering basis was developed for the pilot plant (PP) for production of synthetic hydrocarbons from natural gas according to the three-stage process including generation of synthesis-gas, synthesis of wide hydrocarbon fraction (WHF), isolation and cleaning of ceresin. It was reasonable to use the partial oxidation of methane (natural gas) with air to produce synthesis-gas. To synthesize WHF, the range of stable operation of tube reactors with a cobalt catalyst and diluted synthesis gas was determined as follows: t ≤ 230 °C, Р ≤ 2,0 MPa, gas flow rate ≤1500 h–1. The target products including ceresin 100 were isolated via stepwise fractioning at atmospheric and low (down to 10 mm Hg) pressures, t ≤ 360 °C. The suggested concept provided flexible and reliable PP operation and the possibility to optimize operational regimes over a wide range of process parameters.

Industrially available reagents and preparation methods were used for synthesis of nickel-molybdenum catalysts for hydrocracking based on amorphous aluminosilicates (AAS) with the Si/Al ratio from 0,3 to 1,5. Acidic properties of the AAS surface were determined from CO adsorption using IR spectroscopic technique. The Si/Al ratio was shown to influence the concentration and strength of Broensted and Lewis acid sites in AAS. The studies using low temperature nitrogen adsorption and TEM revealed that the Si/Al ratio affects the catalyst textural parameters but practically not the dispersion of the active sulfide component. The catalysts for hydrocracking of vacuum gasoil were tested using a laboratory high-pressure flow installation under conditions typical of the industrial process. The highest yield of the diesel fraction (more than 60 wt.% at 400 °C) was observed with the catalyst based on AAS with Si/Al = 0,9 which bore the strongest Broensted acid sites. A considerably lower yield of the diesel fraction obtained at Si/Al = 0,3 and 1,5 was accounted for by lower concentrations and strengths of the acid sites in these catalysts, as well as by their lower specific surface areas. The data obtained allow the NiMo catalyst based on AAS with Si/Al ≈ 0,9 to be recommended for the refineries to produce mainly lowsulfur high-cetane diesel fuel.

Platinoid losses were monitored during oxidation of ammonia in industrial UKL-7 type units bearing one- and two-step catalytic systems. Twelve units at the Acron Co. and eleven units at the Nevinnomysskiy Azot Co. were inspected. Approximately equal platinoid losses along the gas flow were observed from the first five woven gauzes in the 1,70 m diameter reactors and from the first three gauzes in the 1,93 m diameter reactors, while the losses from the following gauzes decreased considerably. The concepts of mechanochemical losses (MCL) and reduced mechanochemical losses (related to the amount of produced nitric acid) were introduced as dependent on the intensity of the catalytic reaction and on the specific gasdynamic conditions in the catalytic reactor. It was established that the reactor diameter and arrangement of the gauzes in the reactor determine the ratio of platinoid weight losses from the catalyst woven gauzes; the data obtained were used for estimation of the previously unknown thermal losses. The demonstrated linear dependence of the specific losses of platinoids on reduced MCL allows MCL to be calculated for any UKL-7 unit. Experimental dependences of the ammonia conversion over the platinoid gauze on the gauze arrangement in the catalyst cartridge were determined to indicate the necessity of correcting the applied mathematical model. Analysis of MCL makes it possible to reveal regularities of operational damage of platinoid woven gauzes in various reactors and to predict the degree and type of the catalyst destruction in catalytic reactors bearing new effective catalytic systems.

Main problems related to the operation of high strength impregnated microspherical aluminochromium catalysts in the process of dehydrogenation of isoparaffins are discussed. A focus is made on the problem of erosive wear of the walls of overflow pipelines during operation of the mixture of the impregnated isobutane dehydrogenation catalyst (IDC) with the traditional IM-2201C catalyst and on the ways to resolve the problem. It is established that the main reason for intensifying the erosive wear is the rise of the catalyst particle pulse due to an increase in the average particle size and an increase in the transport gas flow rate: Upon substitution of the mixture of IM-2201C and IDC (70:30) for IM-2201C, the average particle size of the equilibrium catalyst increases from 68 to 74 μm. The optimal fraction composition of the high-strength catalytic system is calculated to provide no increase in the abrasion activity but a decrease in the feeding rate of the transport gas and preservation of the 20–30 wt.% proportion of particles of 20–40 μm in size. It is recommended to manufacture a commercial batch of the highstrength catalyst with the optimal fraction composition in order to use it without addition of IM-2201C for the industrial isobutane production.

New palladium-containing catalysts on the base of hypercrosslinked polystyrene (HPS) were studied in the hydrodeoxygenation (HDO) reaction of stearic acid as model compound. The physics-chemical and kinetics investigation of synthesized catalytic systems in the comparison of industrial catalysts on the base of activated carbon was conducted. The structure of palladium-containing catalysts on the base of HPS was explored by the methods of low-temperature nitrogen physical adsorption, X-ray photoelectron spectroscopy, IR-Furies spectrometry and thermogravimetric analysis. Kinetic investigations
were carried out with continuous stirring (700 rpm), using dodecane as solvent, under the hydrogen pressure 0,6 МPа. The influence of temperature (230–255 °С) and initial stearic acid concentration (0,05–0,20 mol/l) on the HDO process was studied. It was found that that the system 1%-Pd/HPS is the most active (W20 % = 0,013 molSA/(molPd·min)) and selective (Sн–С17 = 99 %) in
the stearic acid hydrodeoxygenation process among the studied catalysts. The estimation of influence of temperature and initial substrate concentration revealed that the process rate increases with increasing of temperature, and the increase of the initial stearic cid concentration leads the increasing the GDO duration. The use of palladium catalysts based on HPS can improve the efficiency of GDO, and the present research forms the basis for modification of Greendiesel production technology.