Search

The aim of this work was to separate ethanol in an experimental adsorption–desorption device. We focused on concentrating ethanol by adsorption onto granulated activated carbon in its gaseous phase, which was produced by stripping a matrix with different ethanol concentrations (2, 5, 10, and 15% v/v). For adsorption, three kinds of granulated activated carbon (GAC) were used, marked as GAC1, GAC2, and GAC3. The separation product had a higher ethanol concentration than the initial ethanol concentration before the adsorption–desorption process. The enrichment factor was, in the case of the initial ethanol concentration, 2% v/v at the level of 10. With our new adsorption–desorption device, it is possible to achieve a product with an ethanol concentration of 59.0% v/v with stripping, adsorption, desorption, and condensation. To verify the separation efficiency, a real matrix (fermentation broth) was used. The ethanol concentration in the real matrix was, at the beginning of the separation process, 0.65% v/v; after using our separation device, it was 11.35% v/v. Using a real matrix, the enrichment factor was at the level of 18. The main advantage is the use of our new adsorption–desorption device for the continuous separation of ethanol from fermentation broth. A mathematical model was created, based on which it is possible to calculate the ethanol concentration in the product of the separation process with high accuracy. [ABSTRACT FROM AUTHOR]

The bromate-aniline oscillatory reaction was discovered 4 decades ago, but neither the detailed mechanism nor the key products or intermediates of the reaction were described. We report herein a detailed study of this reaction, which yielded new insights. We found that oscillatory oxidation of aniline by acidic bromate proceeds, to a significant extent, via a novel reaction pathway with the periodic release of carbon dioxide. Several products were isolated, and their structures, not described so far, were justified on the basis of MS and NMR. One of the main products of the reaction associated with the CO 2 release route can be assigned to 2,2-dibromo-5-(phenylimino)cyclopent-3-en-1-one. A number of known compounds produced in the studied reaction, including unexpected brominated 1-phenylpyrroles and 1-phenylmaleimides, were identified by comparison with standards. A mechanism is suggested to explain the appearance of the detected compounds, based on coupling of the anilino radical with the produced 1,4-benzoquinone. We assume that the radical adduct reacts with bromine to form a cyclopropanone intermediate that undergoes a Favorskii-type rearrangement. Further oxidation and bromination steps including decarboxylation lead to the found brominated phenyliminocyclopentenones. The detected derivatives of 1-phenylpyrrole could be produced by a one-electron oxidation of a proposed intermediate 2-phenylamino-5-bromocyclopenta-1,3-dien-1-ol followed by β-scission with the abstraction of carbon monoxide. Such a mechanism is known from the combustion chemistry of cyclopentadiene. The proposed mechanism of this reaction provides a framework for understanding the observed oscillatory kinetics.