Search

The review is dedicated to the topical field of research aimed at creating catalysts combining several types of active sites. At the same time, the composition of Fischer–Tropsch synthesis (FTS) products can be controlled by changing the strength and concentration of the active sites and inter-site distances. A comparative analysis of the literature data allows to formulate the main principles of catalytic particles formation active in FTS and acid-catalyzed transformations of hydrocarbons: (1) the presence of weak Bronsted acid sites to control the cracking depth, (2) an availability of Bronsted acid sites for re-adsorption hydrocarbons and (3) weak Co-zeolite interaction to reduce methane formation.

Some kinetic parameters of Fischer–Tropsch synthesis (FTS) were determined in the presence of a granular cobalt/zeolite catalyst. Usually, kinetic studies of granular catalysts are considered to be complicated by external and internal diffusion. We managed to obtain a catalyst with a special structure of the active surface, where sites active in FTS are isolated from each other due to the environment of inactive spinel CoAl2O4 and inter-site transport is provided by an extensive intragranular graphitic network serving simultaneously as a heat-conductive medium. As a result, FTS proceeded in the kinetic region. It was found that the reaction kinetics obey the Arrhenius law; whereas, the activation energy is different in different temperature ranges, i.e., 118.2 kJ/mol in the range of 180–210 °C, and 173.6 kJ/mol in the range of 232–243 °C. This behavior is determined by the presence of zeolite, which becomes active in the secondary transformations of FTS products at temperatures beyond 210 °C.

Structured Fischer–Tropsch synthesis catalysts were tested in tubular reactors of industry-standard diameters of 0.5 or 0.75 inches. The structured catalyst bed was manufactured by the obturation of a straight bunch of graphite-based extrudates (D = 1.5 mm, L = 30 mm). A conventional loose bed of granulated catalyst (D = 1.5 mm, L = 3 mm) was tested as a reference. In a 1000–3000 h−1 syngas space velocity range, structured and loose catalyst bed testing showed no significant differences in their main catalytic parameters. Nevertheless, their C5+ hydrocarbon group composition was quite different, i.e., the alkene fraction rose from 9 to 23%, while n-alkanes dropped from 81 to 64%. This could be a result of secondary reaction intensification in the conventional loose bed due to its zeolite acid site's higher availability. Further FTS testing of the structured catalysts in 4000–6000 h−1 manifested distinctive limits in C5+ productivity for 0.5 and 0.75 inches of 512 kg C5+/(m3 reactor·h) and 362 kg C5+/(m3 reactor·h), respectively. This may be explained by limitations in structured bed thermal conductivity. It suggests that the arrangement of extrudates in the structured catalyst can significantly affect the reaction heat and mass transfer conditions and affords new opportunities for group composition control by means of catalyst bed organization. [ABSTRACT FROM AUTHOR]

Epigeic generalist predators play a crucial role in terrestrial ecosystems, connecting aboveground and belowground food webs. Using stable isotope compositions (δ13C and δ15N values), we assessed the trophic niches of the two main groups of generalist predators (ground beetles (Coleoptera, Carabidae) and spiders (Arachnida: Aranei)), as well as their potential prey (phytophagous and saprophagous insects), plants, and soils in the forest, steppe, and transitional ecosystems located in the forest–steppe of southwestern Siberia. We hypothesized that (1) the trophic niche of carabids is wider than that of spiders, because some ground beetles are omnivorous, and (2) the contribution of invertebrates from the detrital food web (saprophages) to the diet of generalist predators is higher in the “detrital” forest ecosystem than in the steppe, which should be reflected in increased δ13C and δ15N values of the predators in the forest. In total, 16 species of carabid and 17 species of spider were analyzed. The δ15N values of ground beetles suggested a wide range of trophic niches corresponding to two or three trophic levels. Omnivorous carabids of the genera Amara and Harpalus had the minimum δ15N values. The carbon isotope compositions of the ground beetles suggests that most predatory species were predominantly involved in grazing food chains. Spiders had on average increased δ15N values compared to ground beetles, and a relatively narrow range of δ15N values. The isotopic niche occupied by spiders hardly overlapped with the isotopic niche of carabids, which may indicate a significant difference in the range of consumed resources. Thus, our data suggest a significant difference in the trophic niches of the key generalist predators, ground beetles and spiders, which was observed both in the forest and the steppe habitats. Spiders appear to be more closely associated with detrital food webs than ground beetles. Contrary to our expectations, we did not find higher δ13C and δ15N values in ground-dwelling generalist predators in the forest compared to the steppe ecosystem.