[ES] La presente tesis doctoral tiene como objetivo la utilidad de restos vegetales de origen agrícola y no agrícola para la eliminación de fósforo de las aguas residuales, y con ello reducir la eutroficación del lago de l'Albufera de Valencia, en el este de España. Bajo el concepto de Economía Circular, la cual se basa en reducir la entrada de materiales y la generación de desechos en sistemas productivos, los restos vegetales son utilizados para la producción de energía renovable en plantas de biomasa, una vez incinerados en estas plantas los restos vegetales pasan a ser un residuo, la ceniza. Se han estudiado las cenizas de materiales vegetales agrícolas como es la paja de arroz y los restos de podas de vegetación invasora como es el carrizo, ambos procedentes del Parque Natural de l'Albulfera de Valencia. Además, se han utilizado cenizas de una planta de biomasa de la comarca del Rincón de Ademuz, en el interior de la provincia de Valencia, alimentada con restos vegetales agrícolas como son la paja de trigo, paja de cebada y madera de plantaciones de paulonia cultivadas para la producción de bioenergía. Para poder reducir la concentración de fósforo del agua, se ha seleccionado el proceso que hoy en día más posibilidades tiene de ser un sistema de bajo coste y alta eficiencia como es la adsorción. Mediante las isotermas de adsorción de Langmuir, Freundlich y Tempkin se han determinado las capacidades de adsorción de fósforo, llegando a una reducción de fosforo de hasta casi del 99%, siendo la isoterma de Langmuir la que mejor ajuste posee al proceso de adsorción de fósforo. Por último, el residuo producido en el proceso de depuración, que es la ceniza con alta concentración de fosforo, puede ser utilizada para la fertilización de campos agrícolas. / [CAT] La present tesi doctoral té com a objectiu la utilitat de restes vegetals d'origen agrícola i no agrícola per a l'eliminació de fòsfor de les aigües residuals, i amb això reduir l'eutrofització del llac de l'Albufera de València, en l'est d'Espanya. Sota el concepte d'Economia Circular, la qual es basa a reduir l'entrada de materials i la generació de deixalles en sistemes productius, les restes vegetals són utilitzats per a la producció d'energia renovable en plantes de biomassa, una vegada incinerats en aquestes plantes les restes vegetals passen a ser un residu, la cendra. S'han estudiat les cendres de materials vegetals agrícoles com és la palla d'arròs i les restes de podes de vegetació invasora com és el canyís, tots dos procedents del Parc Natural de l'Albulfera de València. A més, s'han utilitzat cendres d'una planta de biomassa de la comarca del Racó d'Ademús, a l'interior de la província de València, alimentada amb restes vegetals agrícoles com són la palla de blat, palla d'ordi i fusta de plantacions de paulonia cultivades per a la producció de bioenergia. Per a poder reduir la concentració de fòsfor de l'aigua, s'ha seleccionat el procés que hui dia més possibilitats té de ser un sistema de baix cost i alta eficiència com és l'adsorció. Mitjançant les isotermes d'adsorció de Langmuir, Freundlich i Tempkin s'han determinat les capacitats d'adsorció de fòsfor, arribant a una reducció de fòsfor de fins a quasi del 99%, sent la isoterma de Langmuir la que millor ajust posseeix al procés d'adsorció de fòsfor. Finalment, el residu produït en el procés de depuració, que és la cendra amb alta concentració de fòsfor, pot ser utilitzada per a la fertilització de camps agrícoles. / [EN] The objective of this doctoral thesis is the use of vegetable remains of agricultural and non-agricultural origin for the elimination of phosphorus from wastewater, and thereby reduce the eutrophication of the lagoon of l'Albufera de Valencia, in eastern Spain. Under the concept of Circular Economy, which is based on reducing the entry of materials and the generation of waste in production systems, plant remains are used for the production of renewable energy in biomass plants, once the remains are incinerated in these plants. Vegetables become a residue, the ash. The ashes of agricultural plant materials such as rice straw and the remnants of pruning of invasive vegetation such as reed have been studied, both from the Natural Park of l'Albulfera de Valencia. In addition, ashes from a biomass plant from the Rincón de Ademuz region, in the interior of the province of Valencia, have been used, fed with agricultural plant remains such as wheat straw, barley straw and wood from cultivated paulownia plantations for the bioenergy production. In order to reduce the phosphorus concentration of the water, the process that today has the most possibilities of being a low-cost and high-efficiency system, such as adsorption, has been selected. By means of the adsorption isotherms of Langmuir, Freundlich and Tempkin, the phosphorus adsorption capacities have been determined, reaching a reduction of phosphorus of up to almost 99%, being the Langmuir isotherm the one that best fits the phosphorus adsorption process. Finally, the residue produced in the purification process, which is ash with a high concentration of phosphorus, can be used for the fertilization of agricultural fields. / Carricondo Antón, JM. (2020). Utilización de residuos vegetales para la eliminación de fósforo en aguas residuales mediante procesos de adsorción [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/158614 / TESIS

<p>To improve the adsorption capacity of polyacrylonitrile (PAN) fibres, hydrophilic amidoxime fibres were prepared by subsequent conversion of the cyano groups to an amidoxime group by reacting with hydroxylamine at 80&deg / C at an optimum amidoximation time of 2 hrs. The amidoxime fibre was hydrolyzed/alkali treated in a solution of sodium hydroxide to enhance or improve the adsorption properties. This was followed by characterization of the amidoxime and hydrolyzed fibres using Scanning electron microscopy (SEM) / Fourier transform Infrared Spectroscopy (FTIR) and exchange capacity (cationic and anionic). SEM showed that the hydrolysis process made the surface of Amidoxime fibre rougher than that of Polyacrylonitrile fibre. FTIR revealed that the hydrolyzed Amidoxime fibres contained conjugated imine (-C=N-) sequences. Functionalization enhanced the sorption of amidoxime fibres by an increase of 20 % in the cationic exchange capacity. This was achieved by the part conversion of the cyano groups into the carboxylic acid groups. The fibres showed faster kinetics largely due the available exchange sites on the surface of the fibres hence the equilibration was achieved much quicker.</p>

The results of this study show that novel mesoporous carbons were obtained as inverse replica of SBA-15, HMS and MCM-41 silica templates, with a large pore diameter (2-4 nm), a BET surface area of 1867, 874 and 910 m2g –1 respectively for CA_SBA-15_LPG_105, CA_HMS_LPG_80 and CA_MCM- 41_LPG_80 with bimodal pore size distribution (PSD) in the mesopores range. The results obtained show that mesoporous carbon with graphitic structures can be synthesized via the LPG route.

<p>To improve the adsorption capacity of polyacrylonitrile (PAN) fibres, hydrophilic amidoxime fibres were prepared by subsequent conversion of the cyano groups to an amidoxime group by reacting with hydroxylamine at 80&deg / C at an optimum amidoximation time of 2 hrs. The amidoxime fibre was hydrolyzed/alkali treated in a solution of sodium hydroxide to enhance or improve the adsorption properties. This was followed by characterization of the amidoxime and hydrolyzed fibres using Scanning electron microscopy (SEM) / Fourier transform Infrared Spectroscopy (FTIR) and exchange capacity (cationic and anionic). SEM showed that the hydrolysis process made the surface of Amidoxime fibre rougher than that of Polyacrylonitrile fibre. FTIR revealed that the hydrolyzed Amidoxime fibres contained conjugated imine (-C=N-) sequences. Functionalization enhanced the sorption of amidoxime fibres by an increase of 20 % in the cationic exchange capacity. This was achieved by the part conversion of the cyano groups into the carboxylic acid groups. The fibres showed faster kinetics largely due the available exchange sites on the surface of the fibres hence the equilibration was achieved much quicker.</p>

The results of this study show that novel mesoporous carbons were obtained as inverse replica of SBA-15, HMS and MCM-41 silica templates, with a large pore diameter (2-4 nm), a BET surface area of 1867, 874 and 910 m2g –1 respectively for CA_SBA-15_LPG_105, CA_HMS_LPG_80 and CA_MCM- 41_LPG_80 with bimodal pore size distribution (PSD) in the mesopores range. The results obtained show that mesoporous carbon with graphitic structures can be synthesized via the LPG route.

Magister Scientiae - MSc / To improve the adsorption capacity of polyacrylonitrile (PAN) fibres, hydrophilic amidoxime fibres were prepared by subsequent conversion of the cyano groups to an amidoxime group by reacting with hydroxylamine at 80°C at an optimum amidoximation time of 2 hrs. The amidoxime fibre was hydrolyzed/alkali treated in a solution of sodium hydroxide to enhance or improve the adsorption properties. This was followed by characterization of the amidoxime and hydrolyzed fibres using Scanning electron microscopy (SEM); Fourier transform Infrared Spectroscopy (FTIR) and exchange capacity (cationic and anionic). SEM showed that the hydrolysis process made the surface of Amidoxime fibre rougher than that of Polyacrylonitrile fibre. FTIR revealed that the hydrolyzed Amidoxime fibres contained conjugated imine (-C=N-) sequences. Functionalization enhanced the sorption of amidoxime fibres by an increase of 20 % in the cationic exchange capacity. This was achieved by the part conversion of the cyano groups into the carboxylic acid groups. The fibres showed faster kinetics largely due the available exchange sites on the surface of the fibres hence the equilibration was achieved much quicker. / South Africa

Philosophiae Doctor - PhD / The results of this study show that novel mesoporous carbons were obtained as inverse replica of SBA-15, HMS and MCM-41 silica templates, with a large pore diameter (2-4 nm), a BET surface area of 1867, 874 and 910 m2g–1 respectively for CA_SBA-15_LPG_105, CA_HMS_LPG_80 and CA_MCM- 41_LPG_80 with bimodal pore size distribution (PSD) in the mesopores range. The results obtained show that mesoporous carbon with graphitic structures can be synthesized via the LPG route. / South Africa

In this research, the adsorptive capacities of kenaf in the forms of chopped whole stalk, chopped core, and bast materials were evaluated for the removal of lead, zinc, and toluene from contaminated synthetic waste streams using traditional adsorption isotherm techniques. The effect of surface oxidation using ozone was observed with respect to the adsorption of metals. Hydraulic conductivity experiments were conducted to evaluate the head loss associated with packing a column with kenaf fibers and to determine the suitability of its use in dynamic packed column systems. B.E.T. surface areas were determined as well. Under increasingly stringent regulatory requirements, even low level organic and inorganic contamination (under 100 ppm) in surface and ground waters must be treated. This study is part of an ongoing multi-year research effort aiming to develop a kenaf-based biosorptive process to improve treatment of contaminated aqueous streams at reduced costs and technical complexity.

No description available.

The work described in this thesis focuses on the effects that adsorption processes on catalytic surfaces pose in controlling key steps that can affect and control reaction pathways. To that, the development of Nuclear Magnetic Resonance (NMR) relaxometry methods and the comparison with traditional catalytic was performed with a series of C5 and C6 unsaturated hydrocarbons on two different alumina supports, γ- and θ-Al2O3. The developed techniques were applied in the study of liquid phase selective hydrogenation of citral on 5% Pt/SiO2. Infrared (IR) spectroscopy, volumetric adsorption isotherms, dynamic isotherms via a Tapered Element Oscillating Microbalance (TEOM), temperature programmed desorption (TPD) as well as 13C T1 NMR and 1H 2D T1-T2 relaxometry methods were employed. Energies of adsorption as a function of coverage were obtained via adsorption isotherms and the particular surface adsorbate interactions were described with IR spectroscopy. For example, 1-pentyne showed the strongest interaction with the alumina (94 kJ mol-1) while 1-pentene presented a weaker interaction (46 kJ mol-1) on θ-Al2O3. Desorption energies obtained from TPD ranged 85 – 130 kJ mol-1, irrespective of the adsorbate. Reactivity of the aluminas was captured with TPD, TEOM and NMR relaxometry. Interaction of adsorbates with hydrocarbon occurred predominantly on weak adsorption sites. 13C NMR T1 relaxometry provided in addition atom-specific adsorbate-adsorbent interaction strengths, showing the molecular geometry of adsorption, and applied in co adsorption measurements. The selective hydrogenation of citral as a model α,β-unsaturated aldehyde and the effect of different solvents on the activity and product distribution was studied at 298 and 373 K. A series of polar protic, polar aprotic and non polar solvents was investigated. Results showed higher initial reaction rates in non polar solvents but higher selectivities towards desired products on polar protic solvents. Solvent used also affected by product formation. The strong variations in reaction rates and selectivities reported were related with adsorbate catalyst interactions, as well as solvent reactant interactions. For example, adsorption isotherms showed that ethanol notably reduced the adsorption capacity of citral as compared with hexane, related with the rate differences observed. ATR-IR measurements indicated solvent citral interactions were solely present in polar protic solvents in line with higher yields of geraniol and nerol. Finally, 13C T1 NMR and 1H 2D T1-T2 correlation experiments determined that the geometry of adsorption of citral, influenced by solvent, affected product selectivity, and that product adsorption affected selectivity and deactivation.