RESUMO
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.
RESUMO
The kinetics of 18O/16O isotopic exchange over CeO2-ZrO2-La2O3 and Pt/CeO2-ZrO2 catalysts have been investigated under the conditions of dynamic adsorption-desorption equilibrium at atmospheric pressure and a temperature range of 650-850 degrees C. The rates of oxygen adsorption-desorption on Pt sites, support surface, oxygen transfer (spillover) from Pt to the support as well as the amount of oxygen accumulated in the oxide bulk, and oxygen diffusion coefficient were estimated. The nanocrystalline structure of lanthana-doped ceria-zirconia prepared via the Pechini route with a developed network of domain boundaries and specific defects guarantees a high oxygen mobility in the oxide bulk (D = (1.5 / 2.0).10-18 m2 s-1 at 650 degrees C) and allows accumulation of over-stoichiometric/excess oxygen. For Pt/CeO2-ZrO2, oxygen transfer from Pt to support (characteristic time < 10-2 s) was shown to be responsible for the fast exchange between the gas-phase oxygen and oxygen adsorbed on the mixed oxide surface. The rate of direct exchange between the gas phase and surface oxygen is increased as well due to the increased concentration (up to 2 monolayers) of surface/near subsurface oxygen species accumulated on the oxygen vacancies (originated from the incorporation of highly dispersed Pt atoms). The characteristic time of diffusion of the oxygen localized in the subsurface layers is about 1 s. The overall quantity of over-stoichiometric oxygen and/or hydroxyl groups accumulated in the bulk can reach the equivalent of 10 monolayers, and characteristic time of oxygen diffusion within the bulk is about 20 s. All these kinetic data are required for the further step of modeling partial oxidation of hydrocarbons under steady- and unsteady-state conditions.
