A new method for processing the results of the temperature-programmed desorption (TPD) of ammonia from heterogeneous catalyst surfaces and an approach for automatic deconvolution of TPD kinetic curves were proposed. This method uses the Polanyi–Wigner kinetic model with formal kinetics approaches for simple reactions, which imposes restrictions on the observed first, second, or third orders. The parameters of the TPD curves were selected based on the inverse simulation using the Runge–Kutta method and fitting them to experimental points using dynamic model parameter changes. As an example, several heterogeneous catalysts were presented in this work. TPD-NH3 of titanium silicalite-1 and silicalite-1 was obtained using one third-order desorption kinetic equation. TPD-NH3 of three γ-alumina samples was obtained using two desorption peaks with similar kinetic parameters.

This paper focuses on the key factors contributing to pore formation in hard-templated macroporous alumina. Special attention is paid to the formation of a connected pore structure. Two series of samples were prepared, each with different content of the polymeric template. The pore structure of alumina was designed using polystyrene and acrylic copolymers as hard templates. Alumina differed in crystallite morphology (round-like and rod-like) and pore structure (bottleneck-like and slit-like). The templates differed in particle size (100 and 250 nm) and physical state (powder and suspension). All the samples were characterized by N2 adsorption, Hg porosimetry, XRD, and SEM. The data obtained indicate that a hard template made of polymeric particles has the following functions: fixing the pore size and shape, sintering small pores of the material, and creating additional channels to connect macropores. Regardless of the type of polymeric template and Al2O3 precursor, a connected pore system can be formed by adding more than 20 wt% of the template.

The study is devoted to the tests of hierarchical meso-macroporous catalysts for three-stage atmospheric and vacuum residues hydroprocessing. A special attention is paid to properties of fresh and spent catalysts, the results of experiments on the selection of the optimal parameters (T, p and LHSV) for the three-stage hydroprocessing of residues, as well as the properties of petroleum products produced under optimal conditions. Catalysts were characterized with XRD, nitrogen adsorption-desorption, Hg-intrusion, SRXRF, TPD-NH3 and SEM. The proposed technology of the hydroprocessing of residues over the catalysts with hierarchical porosity makes it possible to obtain valuable oil products and MARPOL marine fuel, which meets modern technical and environmental requirements. Based on the laboratory experiments, a pilot setup for three-stage hydroprocessing of residues has been developed, and is tested at the moment.

•The possibility of using SAPO-5 and SAPO-11 in hydrocracking process has been shown.•Lifetime of catalyst depends on support pore hierarchy.•Hierarchical porosity of SAPO makes the catalyst highly active and stable.•The necessity of high-resolved pore hierarchy for such supports has been shown.

This paper reports on a novel method for the preparation of monolith catalysts using a 3D-printed matrix. The development included an investigation into potential approaches to improving the strength of alumina catalysts, 3D printing of a polymer matrix (template) with a specific channel structure, preparation of templated monolith catalysts, an examination of their physicochemical properties, and testing of these catalysts in hydroconversion of tar. Using an indirect template method, this study is the first to prepare a Al 2 O 3 monolith catalyst with a Schwartz surface microstructure. The extrudate drying rate was found to be the most important parameter for the synthesis of high-strength catalysts. The activity of the monolith catalyst proved to be comparable—and in some parameters even markedly superior—to that of similar granular samples. The tar hydroconversion product consisted of super heavy oil with 2.8 wt % of sulfur.

A technology for catalytic hydroprocessing of oil residues – atmospheric residue and vacuum residue – aimed to obtain high value added petrochemicals, particularly marine fuel complying with modern technical and environmental requirements, is reported. The technologyis based on the use of catalysts supported on alumina with a hierarchical structure of meso- and macropores, which are highly active and stable under severe conditions of the process. Data obtained by physicochemical analysis of the chemical composition, textural and phase properties of fresh and spent catalysts for the three-step hydroprocessing of atmospheric residue and vacuum residue are presented. A material balance for each step of the processes and a comprehensive analysis of the properties of produced petrochemicals were used to propose variants of implementing and integrating the technology at Russian oil refineries in order to increase the profit from oil refining. The introduction of the hydroprocessing of atmospheric residue at oil refineries without secondary processes will improve the economic efficiency due to selling the atmospheric residue by 84–170 % depending on a chosen scheme of the process and a required set of products. It is reasonable to integrate the catalytic hydroprocessing of vacuum residue with the delayed coking, catalytic cracking and hydrocracking processes in order to increase the depth of refining to 95 % and extend the production of marketable oil refining products: gasoline, diesel fuel, marine fuel with the sulfur content below 0.5 %, and low-sulfur refinery coke for the electrode industry. The integration of the hydroprocessing of vacuum residue with the secondary processes will increase the economic efficiency from selling the vacuum residue by a factor of 2–2.5 in comparison with its production in delayed coking units.

The dependence of porosity and durability of Al2O3 on various organic additives (ethylene glycol, diethylene glycol, glycerin, industrial oil and their combinations) was shown. Some of results were used to synthesize 3D-structured catalysts.

In the present study, we have reconstructed glacier dynamics based on the high (1-0.5 mm) resolution X-ray fluorescence spectrometry scanning, the Fourier-transform infrared technique and C-14-dating used in the analyses of the lake bottom sediments, fluvioglacial deposits and a peat bog situated on East Siberian Mountains (East Sayan, Baikal, Barguzin and Kodar Ridges) between 51.723 degrees N, 100.601 degrees E and 56.885 degrees N, 117.580 degrees E. We have found what the largest glacier deposits on the Baikal shoreline, so-called Tompuda end moraine, formed in two stages. The first stage occurred until ca. 12 cal ka BP; then, there was a short pause. The second stage ended by 9.5 cal ka BP. Azarova glacier (Kodar Ridge) retreated upwards the Kodar Ridge by ca. 11 cal ka BP. It may indicate that the Bolling-Allerod warming was very evident, and it was a trigger for these deglacial events in East Siberia. It is most likely that "remains" of the Late Pleistocene glaciers were cardinally shrunk or fully disappeared during the Holocene Thermal Optimum in the southern part of East Siberia. Climate conditions were suitable for glacier formation after 3 cal ka BP. However, if there were new glaciers in the Middle Holocene, their sizes were likely to be less than 1 km(2). For this reason, these glaciers should have completely melted during the Roman and Medieval Warm Periods. It is most likely, small glaciers observed at present in the south of East Siberia were mainly formed during the Little Ice Age.

A new absorption-catalytic method of sample preparation for AMS C-14 analysis has been designed. The semi-automatic graphitization equipment consists of catalytic combustion, selective absorption/desorption of CO2 and graphitization zones. Sample combustion followed by CO2 separation takes less than 30 min that allows plenty of samples to be processed in a short time. The average CO2 conversion to graphite turned out to be 75%. Achieved value of background induced by contamination with contemporary carbon is about 1.2 pMC. The proposed method is reproducible according to results for the OX-I and OX-II oxalic acid standards measured from 2015 to 2018 and has been successfully used for dating lake sediments. The results agree with the data of other laboratories. The penetration of model aerosol particles inhaled at low dose by mice has been studied by means of the designed method. (c) 2018 Elsevier B.V. All rights reserved.