Thermodynamics and remediation techniques for fuel oxygenates

Resumen

In the last years, due to an increasing concern about the possible harmful effects of the gas emissions of the continuous gasoline use, their compositions have changed considerably. The lead additives ban and the aromatic compounds content limitation has caused the worldwide expansion of the use of fuel oxygenates. These compounds are mainly molecules with an atom of oxygen inside its structure. Usually they are ethers or alcohols. The most used worldwide is methyl tert-butyl ether (MTBE) followed by ethyl tert-butyl ether (ETBE). These compounds because of their physical and chemical properties have become persistent and recalcitrant pollutants in the groundwaters of the entire world.Due to the problem generate by the contamination of water resources is important to go deeper in the knowledge of the behaviour of fuel oxygenates in the environment in order to obtain tools that let us model and study their environmental dispersion and remediation. This doctoral thesis offers an important thermodynamical study of these compounds and analyzes different remediation techniques.The work is structured in four chapter well differentiated. The first one consists of an introduction to the problem, the current situation of thermodynamical information and the existent techniques for the water treatment.The second chapter is focused on obtaining and improving the thermodynamical information. It is studied how temperature affect to the interactions of fuel oxygenates with different gasoline compounds such us BTEX (benzene, toluene, ethylbenzene and xylenes), alcans or degradation products like tert-butyl alcohol. In this chapter is included new thermodynamical information in terms of physical properties (density and speed of sound), vapor-liquid equilibria and liquid-liquid equilibria (as water solubility). As a result have been characterized 25 binary systems and their pure compounds in terms of physical property, 3 vapor liquid equilibria and finally the study of water solubility of the ethers most used in gasoline blending as temperature function.The third chapter is focused from a technological point of view. Here it is studied thermodynamically, different conventional remediation techniques fort he MTBE and ETBE like the adsorption onto activated carbon and batch air stripping. It is observed that the temperature increases the efficiency in both processes and that ETBE is easier treated. On the other hand, it has been analyzed the use of new solvents, in this case ionic liquids, in order to dehydrate fuel oxygenates obtaining satisfactory results. Finally, studies of advanced oxidation processes have been carried out using Fe-zeolites as catalyst. The use of these materials let oxidize MTBE and their most problematic degradation products, like tert-butyl alcohol and tert-butyl formate at environmental conditions and neutral pH in reasonable times.Finally in the fourth and last chapter are summarized the conclusions obtained during the development of this work and the research directions to follow in the future.