Biobased biodegradable polymers (BBP) derived from different renewable resources are commonly considered as attractive alternative to petroleum-based polymers, such as polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), etc. It is because they can address the issues of serious environmental problems resulted from accumulation of plastic wastes. In the review current methods of obtaining of most abundant BBP, polylactic acid (PLA) and polyhydroxybutyrate (PHB), have been studied with an emphasis on the toxicity of compounds used for their production and additives improving consumer characteristics of PLA and PHB based market products. Substantial part of additives was the same used for traditional polymers. Analysis of the data on the response of different organisms and plants on exposure to these materials and their degradation products confirmed the doubts about real safety of BBP. Studies of safer additives are scarce and are of vital importance. Meanwhile, technologies of recycling of traditional petroleum-based polymers were shown to be well-developed, which cannot be said about PLA or PHB based polymers, and their blends with petroleum-based polymers. Therefore, development of more environmentally friendly components and sustainable technologies of production are necessary before following market expansion of biobased biodegradable products.

Abstract In the last decade, there was observed a growing demand for both n-butanol as a potential fuel or fuel additive, and propylene as the only raw material for production of alcohol and other more bulky propylene chemical derivatives with faster growing outputs (polymers, propylene oxide, and acrylic acid). The predictable oilfield depletion and the European Green Deal adoption stimulated interest in alternative processes for n-butanol production, especially those involving bio-based materials. Their commercialization will promote additional market penetration of n-butanol for its application as a basic chemical. We analyze briefly the current status of two most advanced bio-based processes, i.e. ethanol–to-n-butanol and acetone–butanol–ethanol (ABE) fermentation. In the second part of the review, studies of n-butanol and ABE conversion to valuable products are considered with an emphasis on the most perspective catalytic systems and variants of the future processes realization.

MeOx/CeO2 (Me = Fe, Co, Ni) samples were tested in an 18O2 temperature-programmed isotope exchange and N2O decomposition (deN2O). A decrease in the rate of deN2O in the presence of oxygen evidences the competitive adsorption of N2O and O2 on the same sites. A study of isotope oxygen exchange revealed dissociative oxygen adsorption with the subsequent formation of surface oxygen species. The same species, more probably, result from N2O adsorption and the following N2 evolution to the gas phase. We supposed the same mechanism of O2 formation from surface oxygen species in both reactions, including the stages responsible for its mobility. A detailed analysis of the kinetics of isotope exchange has been performed, and the rates of one-atom (RI) and two-atom (RII) types of exchange were evaluated. The rate of the stage characterizing the mobility of surface oxygen was calculated, supposing the same two-step mechanism was relevant for both types of exchange. The effect of oxygen mobility on the kinetics of deN2O was estimated. An analysis of the possible pathways of isotope transfer from MeOx to CeOx showed that direct oxygen exchange on the Me–Ce interface makes a valuable contribution to the rate of this reaction. The principal role of the Me–Ce interface in deN2O was confirmed with independent experiments on FeOx/CeO2 samples with a different iron content.

Research was carried out on the application of the spent vanadium catalyst from the production of sulfuric acid and solid residuals after sulfuric acid leaching of vanadium as a support for the vanadium catalyst in the same process. The results of studying the characteristics of the obtained supports and catalysts were presented. The possibility of setting up non-waste processing of spent catalysts was shown.

CeO2-Al2O3 oxides prepared by co-precipitation (Ce+Al) or CeOx precipitation onto Al2O3 (Ce/Al) to obtain dispersed CeO2 and samples with further supported FeOx (2.5–9.9 weight% in terms of Fe) were characterized by XRD, XPS, DDPA and Raman. Fe/Ce/Al samples with lower surface concentrations of Fe3+ were substantially more active in N2O decomposition at 700–900 °C. It was related to higher oxygen mobility, as estimated from 16O/18O exchange experiments and provided by preferential exposing of (Fe-)Ce oxides. Stabilization of some Ce as isolated Ce3+ in Fe-Ce-Al mixed oxides dominating in the bulk and surface layers of Fe/(Ce + Al) samples retards the steps responsible for fast additional oxygen transfer to the sites of O2 desorption.

The level of the main catalysts and industrial technologies for the conversion of natural gas into syngas further convrted into ammonia, methanol, and H 2 was analyzed. The main trends in their development, aimed at reducing the energy and resources consumption, were described including process flowsheets, catalysts, and sorbents at different stages of methane reforming and CO steam reforming.

The review presents an analysis of the scientific and technical level and tendencies in the development of modern imported and Russian catalysts for the main hydroprocesses of oil refining—hydrocracking of vacuum gas oil and hydrotreatment of various distillates (catcracked gasoline, diesel fuel, vacuum gas oil). Forecasts were made on prospects for the industrial production and mass use of Russian catalysts for hydroprocesses.

Existing (production of urea, dimethyl carbonate, polypropylene carbonate) and promising (production of methanol, synthesis gas, monomers dedicated to synthesis of polyurethanes and polycarbonate) chemical technologies which any, time soon, may become CO2based economy for producing motor fuels and basic chemicals have been overviewed. Based on estimates of CO2removals in these processes, it has been concluded that there is a potential for developing technologies to produce methanol from CO2to a competitive cost of the target product. It is expected that interest in this process will decrease if stable carbon dioxide conversion catalysts for methane are introduced into the market.

The paper presents an analysis of the main catalysts and technologies applied for industrial conversion of natural gas to syngas, which is further used to produce ammonia, methanol and hydrogen. The analysis reveals the major trends in their development aimed to reduce the consumption of energy and resources; technological schemes of the processes as well as the catalysts and sorbents used in different steps of methane reforming and steam conversion of CO are described.

The paper presents an analysis of literature data on the catalysts employed in the industrial processes of propylene conversion to the most bulky oxygen-containing products – propylene oxide (PO), acrylonitrile (AN), acrolein and n-/isobutyric aldehydes. Main trends and prospects in their development are considered. Catalytic systems for the promising processes of their production using more inexpensive propane or alternative oxidants are also analyzed; their characteristics are estimated in terms of acceptability for future commercialization.

The paper presents an analysis of literature data on the catalysts employed in the industrial processes of propylene conversion to the most bulky oxygen-containing products – propylene oxide (PO), acrylonitrile (AN), acrolein and n-/isobutyric aldehydes. Main trends and prospects in their development are considered. Catalytic systems for the promising processes of their production using more inexpensive propane or alternative oxidants are also analyzed; their characteristics are estimated in terms of acceptability for future commercialization.

The main stages of the development of industrial Ag–Al2O3catalysts for the gas-phase epoxidation of ethylene are considered. The greatest attention is paid to the methods of preparation aimed at increasing the productivity of the last-generation catalyst systems. The results of the studies of alternative heterogeneous systems based on silicates modified by Ti, Nb, and W for liquid-phase epoxidation of ethylene with H2O2 are also summarized. The reasons and methods for solving the problem of their low activity/productivity and stability are analyzed, the directions of increasing the H2O2 utilization efficiency are evaluated.

An analysis is performed for the literature data on catalysts used in industrial processes of the conversion of propylene to the most widely used oxygen-containing products: propylene oxide, acrylonitrile, acrolein, andn- andiso-butyraldehydes. The main trends and the prospects for their development are identified. Catalytic systems for promising processes of synthesizing the above products using less expensive propane or alternative oxidants are also considered, and the similarity between their characteristics and values suitable for embarking on their commercialization is determined.

Mn-Cr-O mixed oxide (SP) and 2%Pt/SP and 2%Ru/SP samples prepared by incipient wetness impregnation of SP with RuCl3 or H2PtCl6 water solutions were tested in ethanol oxidation (ORE, 1.6%C2H5OH+0.58%O2 in He) and water gas shift (WGSR, 1.2%CO+1.2%H2O in He) reactions at 400°C and 550°C. At close ethanol conversion over all samples, 2%Ru/SP exhibited the highest selectivity towards CO and H2 and the best activity in WGSR. Analysis of isotope responses during C2H5OH+16O2/C2H5OH+18O2 and C2H5OH+16(18)O2/16(18)O2 switches revealed formation of both CO and CO2 from the same intermediate – CH3CHO. At this, oxygen in CO comes from CH3CHO, while in CO2 – from the catalyst. Final CO/CO2 and H2/H2O ratios are determined by WGSR which obeys redox mechanism. It is faster reoxidation of Run+ by H2O (and probably, CO2) that is responsible for highest yield of syngas products on 2%Ru/SP sample.

The literature data on the direct catalytic conversion of methane into useful chemical products (Н 2 , С 2+ hydrocarbons, methanol, formaldehyde, and higher oxygenates) were analyzed. Processes based on these reactions have not yet been commercialized. For each reaction, the catalytic systems were revealed on which the characteristics (primarily, the yield of the desired product) are maximum, and the degree of their approximation to the level at which commercialization is possible was determined. Currently, the most suitable processes for pilot and industrial production may be the syntheses of С 2+ and alkylaromatic hydrocarbons by oxidative condensation (dimerization) of methane and by the reaction of methane with С 3 –С 6 alkanes, respectively. The problem of fast deactivation of catalysts in the synthesis of hydrocarbons of the gasoline fraction by methylation of olefins can be solved due to significant progress in the development of new modifications of zeolites and aluminosilicates. The main limitations on the implementation of methane pyrolysis into carbon and H 2 are the insufficient demand for the types of carbon materials produced and low strength characteristics of the available catalysts in the case of the process performed in the moving bed. For some products (methanol, formaldehyde), the yields are too low for commercialization, while for others (higher oxygenates) only the possibility of their production was shown.

(1.2–8.3)%FeO х /Al 2 O 3 monolith catalysts have been prepared by impregnating alumina with aqueous solutions of iron(III) nitrate and oxalate and have been tested in NH 3 oxidation and in the selective decomposition of N 2 O in mixtures resulting from ammonia oxidation over a Pt–Rh gauze pack under conditions of nitric acid synthesis (800–900°C). In the case of the support calcined at 1200°C, the catalyst is dominated by bulk Fe 2 O 3 particles localized on the Al 2 O 3 surface. The activity of these samples in both reactions decreases with a decreasing active component content, thus limiting the potential of Fe 2 (C 2 O 4 ) 3 · 5H 2 O, an environmentally friendlier but poorly soluble compound, as a substitute for Fe(NO 3 ) 3 · 9H 2 O. Decreasing the support calcination temperature to 1000°C or below leads to the formation of a highly defective Fe–Al–O solid solution in the (1.2–2.7)%FeO х /Al 2 O 3 catalysts. The surface layers of the solid solution are enriched with iron ions or stabilize ultrafine FeO х particles. The catalytic activity of these samples in both reactions is close to the activities measured for ~8%FeO х /Al 2 O 3 samples prepared using iron nitrate.

Literature data are reviewed in the field of catalytic reaction of the direct transformation of methane into marketable chemicals (H 2 , C 2+ hydrocarbons, methanol, formaldehyde and higher oxygenates). At present the processes based on these reactions are not implemented in industry. Catalytic systems providing achievement of the maximal parameters (in the first, the yields of target products) were identified for each of the reactions, and the proximity to their potential commercialization was determined. The processes of synthesis of C 2+ and alkylaromatic hydrocarbons via oxidative condensation (dimerization) of methane and by the reaction of methane with C 3 –C 6 alkanes, respectively, are considered most promising for the semicommercial production in the nearest future. A considerable progress in the development of new zeolite and aluminosilicate modifications makes it possible to solve the problem of the fast catalyst deactivation during olefin methylation to produce hydrocarbons of the gasoline fraction. Implementation of the process of methane pyrolysis to carbon and H 2 is mainly limited by insufficient demand for the obtained types of carbon materials and by the low strength of the available catalysts for fixed catalyst bed processes. The yields of a number of products (methanol, formaldehyde) are not as high as the ones required for the process commercialization. As to the other products (higher oxygenates), a general possibility of their synthesis is only so far demonstrated.

Efficient oxygen transfer through Me–CeO2 interface explains higher activity of MeOx/CeO2 (Me = Fe, Co, Ni) samples in deN2O and NH3 oxidation compared with MeOx/Al2O3 ones.