<p><strong>Apstrakt je obrađen tehnologijama za optičko prepoznavanje teksta (OCR).</strong></p><p>Cilj ovog rada je teorijska (računarska) analiza primenljivosti dvomembranskog reaktora za izvodenje povratnih gasnih reakcija. Specijalno, analizira se primenljivost dvomern- branske konhguracije za termolizu vode. Rezultati simulacije su pokazali značajnu pred- nost, u pogledu povečanja konverzije reaktanta iznad ravnotežne, dvomembranske u odnosu na jednomembransku konhguraciju, u slučaju kada su membrane najmanje pro- pustljive za reaktant. Rezultati neizotermske analize dvomembranskog reaktora su pokazali da je efekat energije aktivacije u odnosu na efekat toplote reakcije zanemarljiv, u oblasti vehkih Damk&ouml;hler-ovih brojeva (odnos maksimalne brzine reakcije i protoka reaktanta u napoju). I za endotermne i za egzotermne reakcije, konverziona efikasnost opada sa porastom indeksa generisanja toplote (odnos toplotnog efekta reakcije i toplotnog kapaciteta reaktanta), a raste sa intenzitetom dovodenja odnosno odvodenja toplote. &Scaron;to se tiče uticaja temperature napoja, kod endotermnih reakcija postoji optimum ako permeabilnosti komponenata opadaju sa temperaturom. Na bazi raspoloživih literaturnih podataka formulisan je izotermski model dvomembranskog reaktora za termolizu vode sa jednom membranom propustljivom za vodonik, a drugom propustljivom za kiseonik. Pokazano je da se pri dovoljno velikim vrednostima Damk&ouml;hler-ovih broja i odnosa brzina (odnos maksimalne brzine permeacije za membranu i maksimalne brzine reakcije) u reaktoru može postići potpuna disocijacija vode. Zapaženo je postojanje optimalne raspodele ukupnog odnosa brzina izmedu dve membrane kao i, u slučaju uvodenja inerta u separacionu zonu, optimalne raspodele inerta između dve zone. Analiza je pokazala da dvomembranski reaktor predstavlja perspektivno re&scaron;enje problema termolize vode koje zaslužuje dalja teorijska i eksperimentaina istraživanja.</p> / <p><strong>Abstract was processed by technology for Optical character recognition (OCR).</strong></p><p>The aim of this study is a theoretical (computer) analysis of the applicability of a double-membrane reactor for reversible gas phase reactions. Particulaidy, the applicability of double-membrane configuration for the direct thermal water splitting is studied. The double-membrane configuration proved to be significantly superior over the single membrane configuration with respect to the equilibrium shift, in the case when the reac- tant is the slowest permeating component. By the non-isothermal analysis, it is shown that, in the region of high Damk&ouml;hler numbers (the ratio of the maximal reaction rate to the feed reactant flow), the effect of activation energy is negligible when compared to the effect of reaction heat. The conversion efficiency is decreasing by the increase of the heat generation index (the ratio of reaction heat to reactant heat capacity) and increasing by the increase of the added or removed heat, for both endo- and exothermic processes. As to the feed temperature, an optimal value exists for endothermic reactions, if component permeabilities are decreasing functions of temperature. On the basis of the available literature data, the isothermal model of double-membrane reactor (one membrane permeable for hydrogen an the other for oxygen) for direct thermal splitting of water is formulated. It is shown that the complete water dissociation could be achieved at the high enough values of Damk&ouml;hler number and of the rate ratio (the ratio of maximal permeability of membrane to the maximal reaction rate). The optimal distribution of the total rate ratio between the membranes as well as the optimal inert flow distribution could be determined. Double-membrane configuration seems to be a promising solution for the problem of direct thermal water splitting, deserving further theoretical and experimental investigations.</p>

The hydrogen economy is a possible component of an energy future based on use of alternative and renewable energy sources, deemed desirable from the general consensus of the worldwide community that we do not want to further exacerbate the climate problems that we have introduced over the last two centuries from burning fossil fuels. The burning of fossil fuels emits toxic pollutants into the air, such as sulfur compounds and oxidized forms of nitrogen (NOx) but also emit copious amounts of the inert carbon dioxide. The latter is widely recognized as the major cause of the global warming phenomenon. For a hydrogen economy to develop, efficient means of hydrogen generation are required. Thermochemical cycles were conceived in the 1960s but only one operating pilot plant and no commercial installations based on the processes have been built. In the present work the use of a membrane reactor to enable the newly conceived Sulfur-Sulfur cycle, based on equations 1 - 3 is modeled. / 4H₂O+4SO₂ -> H₂S + 3H₂SO₄ Eq. 1 / H₂SO₄ -> SO₂ + H₂O + 1/2O₂ Eq. 2 / H₂S + 2H₂O -> SO₂ + 3H₂ Eq. 3 / The rationale for the use of a membrane reactor to enable the cycle is based on enhancing extent of reaction beyond its predicted equilibrium point due to the severely unfavorable thermochemical parameters for the steam reforming of hydrogen sulfide reaction (Eq. 3 above) which has a low equilibrium concentration of products. The membrane reactor will employ a molybdenum sulfide catalyst driving the steam reformation of hydrogen sulfide reaction and simultaneous extraction of hydrogen (one of the products) will allowing for the reaction to occur to higher extent. A computational model of a catalytic membrane reactor was constructed using the well-known finite element model package Comsol v4.1 in which a catalytic microchannel reactor separated from a sweep gas by a thin hydrogen permeable membrane is built and parametric sweeps to evaluate the effect of membrane transport parameters, pressure and gas feed velocities are calculated. Though the steam reforming of hydrogen sulfide reaction has a competing thermal cracking reaction, the present work focuses on modeling one reaction only (the steam reformation reaction) for simplicity. Fully dense metallic membranes with chemselective permeability to hydrogen are modeled with transport parameters derived from reported literature values for similar applications. The results show that employing a membrane reactor does significantly affect the completeness of the reaction by product extraction (if you do run the model with membrane transport set to zero, compare the extent at zero with extent at 3.6x10⁻⁶ mol.s⁻¹.m⁻²). The effect of changing sweep gas velocity is contingent on membrane properties, and membranes with small diffusion coefficients severely limit the ability of extraction of hydrogen from the feed. Therefore, it is more important that membranes with very high hydrogen permeability be employed in designing a reactor to implement this process, allowing for effective hydrogen separation and high conversion of the reactants in the process. Reactor pressure has minimal effect on the extent of reaction and therefore reactors designed to implement the process may be designed to operate at close to ambient pressure. / Graduation date: 2012

[ES] La presente tesis doctoral se enmarca en el ámbito de la producción de hidrógeno renovable, y en el estudio metodologías de intensificación de procesos para la producción de hidrógeno mediante reactores de membrana y reactores que operan a alta presión. Para la producción de hidrógeno renovable, se estudió en detalle el proceso de reformado autotérmico (ATR) de bioetanol. Se diseñó y construyó un sistema de reacción de escala de laboratorio, que se operó bajo condiciones reales de operación industrial. En una primera etapa, se realizó la evaluación de distintos catalizadores comerciales para el ATR de etanol. Tras la selección del tipo de catalizador con mejor rendimiento, se probaron distintas variaciones sobre el mismo, añadiendo dopantes a la fase activa y al soporte. Los catalizadores con mejores resultados se probaron durante más de 100 h manteniendo su rendimiento. Una vez seleccionados la composición primara de los catalizadores, se hicieron pruebas para el escalado y optimización de los catalizadores fabricados mediante un proceso industrial. Se estudiaron los efectos de las condiciones de operació, siendo el parámetro de mayor relevancia la relación O/C. El mejor de los catalizadores desarrollados aumentó el rendimiento y disminuyó la producción de hidrocarburos en estas condiciones, alcanzándose un rendimiento de hasta 3.1 mol H2 / mol etanol. Este catalizador se probó durante 200 horas, manteniendo su estabilidad en todo el periodo, validando su aplicación en un reformador de etanol para la producción de hidrógeno. En otro apartado, se estudió la utilización de membranas de transporte de oxígeno como elemento distribuidor de oxígeno para el sistema de reacción de ATR, permitiendo alimentar al reactor oxígeno de alta pureza producido in-situ. Se probaron membranas capilares de BSCF. En el sistema de reacción de ATR, las membranas mostraron una permeación acorde a los valores habituales para este material. Se estudió el comportamiento de las membranas de BSCF en una atmósfera con vapor, en la que la permeación alcanzada disminuyó en presencia de vapor. La utilización de estas membranas en la reacción de ATR requeriría de un escalado correcto, pues el flujo de oxígeno aportado por la membrana sería bajo respecto a las necesidades de oxígeno de la reacción de ATR. Seguidamente, se probaron los efectos de la aplicación de capas protectoras porosas sobre los capilares de BSCF, para mejorar su estabilidad química en ambientes de rección. Mediante la técnica de dip-coating se aplicaron capas porosas de BSCF, CTO-CMO (Ce0.8Tb0.2O2--δ- MnCo2O4) y CTO. La aplicación de estas capas aumentó la permeación por la mejora en el área superficial de intercambio y de las reacciones superficiales, alcanzándose 3 - 3.6 NmL·min-1·cm-2 para las membranas recubiertas, frente a 2.4 NmL·min-1·cm-2 para la membrana sin recubrimiento. Estas mismas membranas se probaron en un reactor de membrana, en reacción con CH4. Las capas aporataron efectos catalíticos y protectores respecto a la membrana sin tratamiento superficial. Las capas de CTO y CTO-CMO aumentaron la permeación de oxígeno y la conversión de CH4, que alcanzó valores del 100%, y además, resultaron estables en las condiciones de reacción, mientras que las membranas con capa de BSCF y sin recubrimiento tuvieron conversiones más bajas y su estructura quedó degradada por la atmósfera de la reacción. Finalmente, se llevó a cabo el diseño y construcción de un sistema de reacción de alta presión para el estudio de procesos de producción de hidrógeno a alta presión a presiones de hasta 300 barg. En esta unidad, se podrán llevar a cabo reacciones de producción de hidrógeno a partir de biomasa en agua supercrítica. Adicionalmente, se diseñó un reactor de membrana que permitirá el trabajo con membranas de permeación de gases en condiciones de alta severidad, con potencial aplicación en la producción de hidrógeno a partir de reacciones de reformado con una alta eficiencia. / [CA] La present tesi doctoral s'emmarca en l'àmbit de la producció d'hidrogen renovable, i en l'estudi metodologies d'intensificació de processos per a la producció d'hidrogen mitjançant reactors de membrana i reactors que operen a alta pressió. Per a la producció d'hidrogen renovable, es va estudiar detalladament el procés de reformat autotérmico (ATR) de bioetanol. Es va dissenyar i va construir un sistema de reacció d'escala de laboratori, que es va operar sota condicions reals d'operació industrial. En una primera etapa, es va realitzar l'avaluació de diferents catalitzadors comercials per al ATR d'etanol. Després de la selecció de la mena de catalitzador amb millor rendiment, es van provar diferents variacions sobre aquest, afegint dopants a la fase activa i al suport. Els catalitzadors amb millors resultats es van provar durant més de 100 h mantenint el seu rendiment. Una vegada seleccionats la composició prevalguera dels catalitzadors, es van fer proves per a l'escalat i optimització dels catalitzadors fabricats mitjançant un procés industrial. Es van estudiar els efectes de les condicions de operació, sent el paràmetre de major rellevància la relació O/C. El millor dels catalitzadors desenvolupats va augmentar el rendiment i va disminuir la producció d'hidrocarburs en aquestes condicions, aconseguint-se un rendiment de fins a 3.1 mol H2 / mol etanol. Aquest catalitzador es va provar durant 200 hores, mantenint la seua estabilitat en tot el període, validant la seua aplicació en un reformador d'etanol per a la producció d'hidrogen. En un altre apartat, es va estudiar la utilització de membranes de transport d'oxigen com a element distribuïdor d'oxigen per al sistema de reacció de ATR, permetent alimentar al reactor oxigen d'alta puresa produït in-situ. Es van provar membranes capil·lars de BSCF. En el sistema de reacció de ATR, les membranes van mostrar una permeación concorde als valors habituals per a aquest material. Es va estudiar el comportament de les membranes de BSCF en una atmosfera amb vapor, en la qual la permeación aconseguida va disminuir en presència de vapor. La utilització d'aquestes membranes en la reacció de ATR requeriria d'un escalat correcte, perquè el flux d'oxigen aportat per la membrana seria baix respecte a les necessitats d'oxigen de la reacció de ATR. Seguidament, es van provar els efectes de l'aplicació de capes protectores poroses sobre els capil·lars de BSCF, per a millorar la seua estabilitat química en ambients de recció. Mitjançant la tècnica de dip-coating es van aplicar capes poroses de BSCF, CTO-CMO i CTO. L'aplicació d'aquestes capes va augmentar la permeación per la millora en l'àrea superficial d'intercanvi i de les reaccions superficials, aconseguint-se 3 - 3.6 NmL·min-1·cm-2 per a les membranes recobertes, enfront de 2.4 NmL·min-1·cm-2 per a la membrana sense recobriment. Aquestes mateixes membranes es van provar en un reactor de membrana, en reacció amb CH4. Les capes aporataron efectes catalítics i protectors respecte a la membrana sense tractament superficial. Les capes de CTO i CTO-CMO van augmentar la permeación d'oxigen i la conversió de CH4, que va aconseguir valors del 100%, i a més, van resultar estables en les condicions de reacció, mentre que les membranes amb capa de BSCF i sense recobriment van tindre conversions més baixes i la seua estructura va quedar degradada per l'atmosfera de la reacció. Finalment, es va dur a terme el disseny i construcció d'un sistema de reacció d'alta pressió per a l'estudi de processos de producció d'hidrogen a alta pressió a pressions de fins a 300 barg. En aquesta unitat, es podran dur a terme reaccions de producció d'hidrogen a partir de biomassa en aigua supercrítica. Addicionalment, es va dissenyar un reactor de membrana que permetrà el treball amb membranes de permeación de gasos en condicions d'alta severitat, amb potencial aplicació en la producció d'hidrogen a partir de reaccions de reformat amb una alta eficiència. / [EN] This doctoral thesis is framed in the field of renewable hydrogen production, and in the study of process intensification methodologies for the production of hydrogen through membrane reactors and reactors that operate at high pressure. For the production of renewable hydrogen, the bioethanol autothermal reforming (ATR) process was studied in detail. He designed and built a laboratory scale reaction system, which was operated under real industrial operating conditions. In a first stage, the evaluation of different commercial catalysts for ethanol ATR was carried out. After selecting the type of catalyst with the best performance, different variations were tested on it, adding dopants to the active phase and to the support. The catalysts with the best results were tested for more than 100 h maintaining their performance. Once the primary composition of the catalysts had been selected, tests were carried out for the scaling and optimization of the catalysts manufactured by means of an industrial process. The effects of operating conditions were studied, the most relevant parameter being the O / C ratio. The best of the developed catalysts increased the yield and decreased the production of hydrocarbons under these conditions, reaching a yield of up to 3.1 mol H2 / mol ethanol. This catalyst was tested for 200 hours, maintaining its stability throughout the period, validating its application in an ethanol reformer for the production of hydrogen. In another section, the use of oxygen transport membranes as an oxygen distributor element for the ATR reaction system was studied, allowing the reactor to be fed high-purity oxygen produced in-situ. Capillary membranes from BSCF were tested. In the ATR reaction system, the membranes showed a permeation according to the usual values for this material. The behavior of the BSCF membranes was studied in an atmosphere with steam, in which the permeation achieved decreased in the presence of steam. The use of these membranes in the ATR reaction would require correct scaling, since the flow of oxygen provided by the membrane would be low compared to the oxygen needs of the ATR reaction. Next, the effects of the application of porous protective layers on the BSCF capillaries were tested, to improve their chemical stability in rection environments. By means of the dip-coating technique, porous layers of BSCF, CTO-CMO and CTO were applied. The application of these layers increased the permeation due to the improvement in the surface area of exchange and of the surface reactions, reaching 3 - 3.6 NmL · min-1 · cm-2 for the coated membranes, compared to 2.4 NmL · min-1 · cm-2 for the uncoated membrane. These same membranes were tested in a membrane reactor, in reaction with CH4. The layers supported catalytic and protective effects with respect to the membrane without surface treatment. The CTO and CTO-CMO layers increased oxygen permeation and CH4 conversion, which reached values of 100%, and were also stable under the reaction conditions, while the membranes with BSCF layer and without coating had conversions. lower and its structure was degraded by the atmosphere of the reaction. Finally, the design and construction of a high pressure reaction system was carried out for the study of high pressure hydrogen production processes at pressures up to 300 barg. In this unit, hydrogen production reactions can be carried out from biomass in supercritical water. Additionally, a membrane reactor was designed that will allow work with gas permeation membranes under conditions of high severity, with potential application in the production of hydrogen from reforming reactions with high efficiency. / Represa Bullido, Á. (2022). Desarrollo de sistemas catalíticos e intensificación de procesos para la producción de hidrógeno comprimido y productos de interés [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/183153 / TESIS

Thesis (M.Tech.: Chemical Engineering)-Dept. of Chemical Engineering, Durban University of Technology, 2005 1 v. (various pagings) / In bubble-less aeration oxygen diffuses through the membrane in a molecular form and dissolves in the liquid. Oxygen is fed through the lumen side of silicone rubber tube. On the outer surface of the membrane there is a boundary layer that is created by oxygen. This then gets transported to the bulk liquid by convective transport created by water circulation through the pump. The driving force of the convective transport is due to concentration difference between the dissolved oxygen in water and oxygen saturation concentration in water at a particular temperature and pressure. The design of a membrane aerated bioreactor needs an understanding of the factors that govern oxygen mass transfer. It is necessary to know the effects of operating conditions and design configurations. Although various methods of bubble-less aeration have been reported, there still exists a lack of knowledge on the immersed membrane systems. This study is aiming at contributing to the development of an immersed membrane bioreactor using silicone rubber tubular membrane as means of providing oxygen. The secondary objective was to investigate the influence that the operating conditions and module configuration have on the system behaviour. From the experimental study, the characteristic dissolved oxygen -time curve show that there is a saturation limit equivalent to the equilibrium dissolved oxygen concentration, after which there is no increase in dissolved oxygen with time. At ambient conditions the equilibrium dissolved oxygen is approximately 8 mg/L. This is when water is in contact with air at one atmospheric pressure. At the same conditions the equilibrium dissolved oxygen concentration when water is in contact with pure oxygen is approximately 40 mg/L. This is why all the experiments were conducted from 2mg/L dissolved oxygen concentration in water, to enable enough time to reach equilibrium so as to determine mass transfer coefficient. The most important parameters that were investigated to characterise the reactor were, oxygen supply pressure, crossflow velocity, temperature and module orientation. Observations from the experimental study indicated that when the system is controlled by pressure, crossflow does not have a significant effect on mass transfer. When the system is controlled by the convective transport from the membrane surface to the bulk liquid, pressure does not have a significant effect on mass transfer. All four effects that were investigated in the study are discussed.

A comprehensive process intensification analysis was performed for the integration of the Pd-based membrane reactor technology into IGCC power plants by designing effective process control strategies as well as identifying and optimally characterizing inherently safe operational conditions to achieve the most favorable economic outcomes. Experimental results indicated that Pd-based composite membranes supported on porous stainless steel tubes, fabricated with H2 permeance values as high as ~50 m3/[m2.h.atm0.5] at 450°C were capable of extra purity H2 production (≥99.99%). Two illustrative process control and performance monitoring cases namely, process regulation and servo mechanism, were considered and quite satisfactory process control was attained by maintaining CO conversion at levels higher than 95% so that the retentate stream could become suitable for high pressure CO2 sequestration. From a process safety standpoint, process parameters and operating conditions were identified and optimized to achieve the target performance level of 98% CO conversion and 95% H2 recovery and at the same time to prevent conditions which could potentially induce hazards and thus compromise process system safety. Furthermore, the average total product cost of a water-gas shift membrane reactor module including manufacturing costs and general expenses was carefully estimated by taking into account the full cost structure and found to be 1464 $/ft2. Moreover, a comprehensive economic assessment was performed for composite Pd/Alloy membrane reactor technology options integrated into IGCC power plants in the presence of market and regulatory uncertainty (possible regulatory action on CO2 emissions) as well as technology risks with the aid of Monte-Carlo simulation techniques. Within such a context, it was demonstrated that an IGCC plant with embedded Pd-based membrane reactors and a stream of revenues coming from electricity and H2 selling (IGCC co-production mode), represented an economically attractive and advantageous option when comparatively assessed against its main competitors namely, an IGCC plant with shift reactors and double stage Selexol units as well as the more traditional supercritical pulverized coal power plant option with an Econamine unit installed for CO2 capture purposes.

Thesis (M.Tech.: Chemical Engineering)-Dept. of Chemical Engineering, Durban University of Technology, 2005 1 v. (various pagings) / In bubble-less aeration oxygen diffuses through the membrane in a molecular form and dissolves in the liquid. Oxygen is fed through the lumen side of silicone rubber tube. On the outer surface of the membrane there is a boundary layer that is created by oxygen. This then gets transported to the bulk liquid by convective transport created by water circulation through the pump. The driving force of the convective transport is due to concentration difference between the dissolved oxygen in water and oxygen saturation concentration in water at a particular temperature and pressure. The design of a membrane aerated bioreactor needs an understanding of the factors that govern oxygen mass transfer. It is necessary to know the effects of operating conditions and design configurations. Although various methods of bubble-less aeration have been reported, there still exists a lack of knowledge on the immersed membrane systems. This study is aiming at contributing to the development of an immersed membrane bioreactor using silicone rubber tubular membrane as means of providing oxygen. The secondary objective was to investigate the influence that the operating conditions and module configuration have on the system behaviour. From the experimental study, the characteristic dissolved oxygen -time curve show that there is a saturation limit equivalent to the equilibrium dissolved oxygen concentration, after which there is no increase in dissolved oxygen with time. At ambient conditions the equilibrium dissolved oxygen is approximately 8 mg/L. This is when water is in contact with air at one atmospheric pressure. At the same conditions the equilibrium dissolved oxygen concentration when water is in contact with pure oxygen is approximately 40 mg/L. This is why all the experiments were conducted from 2mg/L dissolved oxygen concentration in water, to enable enough time to reach equilibrium so as to determine mass transfer coefficient. The most important parameters that were investigated to characterise the reactor were, oxygen supply pressure, crossflow velocity, temperature and module orientation. Observations from the experimental study indicated that when the system is controlled by pressure, crossflow does not have a significant effect on mass transfer. When the system is controlled by the convective transport from the membrane surface to the bulk liquid, pressure does not have a significant effect on mass transfer. All four effects that were investigated in the study are discussed.

Le traitement des déchets alimentaires (FW) par digestion anaérobie peut conduire à une production d'énergie couplée à une réduction des émissions de volume et de gaz à effet de serre à partir de ce type de déchets. Néanmoins, l'obtention de la récupération du méthane la plus élevée possible dans un temps plus court avec un fonctionnement stable est difficile. Pour surmonter les obstacles de la MA de divers procédés de pré-traitement FW, la supplémentation en oligo-éléments, bioaugmentation utilisant la bouse des animaux de zoo et la comparaison des configurations de réacteurs, y compris une étape ou en deux réacteurs à cuve agités en continu (CSTR) et un réacteur à membrane anaérobie (AnMBR ) ont été étudiées dans le cadre de la présente recherche. Sur la base des résultats des expériences de traitement par lots, de pré-traitement thermique à 80 ° C pendant 1,5 heure cédés> 50% augmentation de la production de biométhane, et il a été trouvé à être plus économe en énergie que l'ozonation ou prétraitements de choc thermophiles. Parmi les différentes concentrations testées et les oligo-éléments, Fe (II) et Se (VI) des concentrations de 25 à 50 ug / L ont donné lieu à 39 et 35% d'augmentation de la production de biométhane, respectivement. Une meilleure solubilisation des protéines (6,96 ± 2,76% de plus) et de glucides récalcitrants (344,85 ± 54,31 mg / L par rapport à zéro) pourrait être obtenue avec bioaugmentation de girafe fumier (30% en volume), qui a donné un 11,24 ± 4,51% de plus production de biométhane. Un CSTR à deux étages avec digestat re-circulation de meilleurs résultats que d'un stade en raison de sa (i) une meilleure capacité d'auto-ajustement du pH; (ii) une plus grande résistance aux chocs de charge organique; (iii) de près de 100% de matières solides volatiles a été destryoed par rapport à 71% en CSTR une étape; (iv) 50 à 60% de teneur en méthane a été obtenu, alors qu'il était de 40 à 50% en une seule étape CSTR; (c) une petite quantité d'hydrogène a également été détectée à partir de la première étape du réacteur à deux étages qui en fait un système attrayant pour la production de biohythane. Bien que la séparation physique des méthanogènes rendus plus sensibles à des facteurs inhibiteurs, tels que l'ammonium et l'acide propionique. En outre, le temps de rétention hydraulique (HRT) est encore une chute de ces systèmes, d'où une AnMBR équipé d'une membrane de fluorure de vinylidène courant latéral a été proposé et exploité avec succès pour 100 d. Merci de membranes HRT a pu être réduite de 20 d à 1d, tout en conservant un rendement global d'élimination de> 97% de la demande en oxygène influent chimique (COD) et a abouti à une production de biogaz supérieure à 70% de teneur en méthane / Treatment of food waste by anaerobic digestion can lead to an energy production coupled to a reduction of the volume and greenhouse gas emissions from this waste type. Nevertheless, obtaining the highest possible methane recovery in a shorter time with a stable operation is challenging. To overcome the hurdles of AD of FW various pretreatment methods, supplementation of trace elements, bioaugmentation using zoo animals' dung and comparison of reactor configurations including one-stage and two-stage continuously stirred tank reactors (CSTR) as well as anaerobic membrane reactor (AnMBR) were studied in the scope of this research. Based on the results of the batch experiments, thermal pretreatment at 80°C for 1.5 hours yielded 46 – 52% higher biomethane production, and it is more energy efficient than ozonation or thermophilic shock pretreatments. Among the various tested concentrations and trace elements Fe (II) and Se (VI) concentrations of 25-50 ug/L resulted in 39 and 35% increase of biomethane production, respectively. A better solubilization of proteins (6.96 ± 2.76% more) and recalcitrant carbohydrates (344.85 ± 54.31 mg/L as compared to zero) could be obtained with bioaugmentation of giraffe dung (30% by volume), which yielded a 11.24 ± 4.51% higher biomethane production. A two-stage CSTR with digestate re-circulation performed better than one-stage with (i) a better pH self-adjusting capacity; (ii) a higher resistance to organic loading shocks; (iii) almost 100% volatile solids was destroyed as compared to 71% in one-stage CSTR; (iv) 50-60% methane content was obtained, while it was 40-50% in one-stage CSTR; (v) a small amount of hydrogen was also detected from the first stage of the two-stage reactor making it an attractive biohythane production system. Although physically separating the methanogens made them more sensitive to inhibitory factors, such as ammonium and propionic acid. Moreover, the long hydraulic retention time (HRT) is still the problem with these systems, hence an AnMBR equipped with a side-stream polyvinylidene fluoride membrane was proposed and a successful operation was achieved. Thanks to the membranes the HRT was able to be reduced from 20 d to 1d, while maintaining an overall removal efficiency of >97% of the influent chemical oxygen demand (COD) and yielded a higher biogas production with 70% methane content

[ES] La presente tesis doctoral se centra en el desarrollo de nuevas membranas de separación de gases, así como su empleo in-situ en reactores catalíticos de membrana para la intensificación de procesos. Para este propósito, se han sintetizado varios materiales, como polímeros para la fabricación de membranas, catalizadores tanto para la metanación del CO2 como para la reacción de síntesis de Fischer-Tropsch, y diversas partículas inorgánicas nanométricas para su uso en membranas de matriz mixta. En lo referente a la fabricación de las membranas, la tesis aborda principalmente dos tipos: orgánicas e inorgánicas. Con respecto a las membranas orgánicas, se han considerado diferentes materiales poliméricos, tanto para la capa selectiva de la membrana, así como soporte de la misma. Se ha trabajado con poliimidas, puesto que son materiales con temperaturas de transición vítrea muy alta, para su posterior uso en reacciones industriales que tienen lugar entre 250-300 ºC. Para conseguir membranas muy permeables, manteniendo una buena selectividad, es necesario obtener capas selectivas de menos de una micra. Usando como material de soporte otro tipo de polímero, no es necesario estudiar la compatibilidad entre ellos, siendo menos compleja la obtención de capas finas. En cambio, si el soporte es de tipo inorgánico, un exhaustivo estudio de la relación entre la concentración y la viscosidad de la solución polimérica es altamente necesario. Diversas partículas inorgánicas nanométricas se estudiaron para favorecer la permeación de agua a través de los materiales poliméricos. En segundo lugar, en cuanto a membranas inorgánicas, se realizó la funcionalización de una membrana de paladio para favorecer la permeación de hidrógeno y evitar así la contaminación por monóxido de carbono. El motivo por el cual se dopó con otro metal la capa selectiva de la membrana metálica fue para poder emplearla en un reactor de Fischer-Tropsch. Con relación al diseño y fabricación de los reactores, durante esta tesis, se desarrolló el prototipo de un microreactor para la metanación de CO2, donde una membrana polimérica de capa fina selectiva al agua se integró para evitar la desactivación del catalizador, y a su vez desplazar el equilibrio y aumentar la conversión de CO2. Por otro lado, se rediseñó un reactor de Fischer-Tropsch para poder introducir una membrana metálica selectiva a hidrogeno y poder inyectarlo de manera controlada. De esta manera, y siguiendo estudios previos, el objetivo fue mejorar la selectividad a los productos deseados mediante el hidrocraqueo y la hidroisomerización de olefinas y parafinas con la ayuda de la alta presión parcial de hidrógeno. / [CAT] La present tesi doctoral es centra en el desenvolupament de noves membranes de separació de gasos, així com el seu ús in-situ en reactors catalítics de membrana per a la intensificació de processos. Per a aquest propòsit, s'han sintetitzat diversos materials, com a polímers per a la fabricació de membranes, catalitzadors tant per a la metanació del CO2 com per a la reacció de síntesi de Fischer-Tropsch, i diverses partícules inorgàniques nanomètriques per al seu ús en membranes de matriu mixta. Referent a la fabricació de les membranes, la tesi aborda principalment dos tipus: orgàniques i inorgàniques. Respecte a les membranes orgàniques, diferents materials polimèrics s'ha considerat com a candidats prometedors, tant per a la capa selectiva de la membrana, així com com a suport d'aquesta. S'ha treballat amb poliimides, ja que són materials amb temperatures de transició vítria molt alta, per al seu posterior ús en reaccions industrials que tenen lloc entre 250-300 °C. Per a aconseguir membranes molt permeables, mantenint una bona selectivitat, és necessari obtindre capes selectives de menys d'una micra. Emprant com a material de suport altre tipus de polímer, no és necessari estudiar la compatibilitat entre ells, sent menys complexa l'obtenció de capes fines. En canvi, si el suport és de tipus inorgànic, un exhaustiu estudi de la relació entre la concentració i la viscositat de la solució polimèrica és altament necessari. Diverses partícules inorgàniques nanomètriques es van estudiar per a afavorir la permeació d'aigua a través dels materials polimèrics. En segon lloc, quant a membranes inorgàniques, es va realitzar la funcionalització d'una membrana de pal¿ladi per a afavorir la permeació d'hidrogen i evitar la contaminació per monòxid de carboni. El motiu pel qual es va dopar amb un altre metall la capa selectiva de la membrana metàl¿lica va ser per a poder emprar-la en un reactor de Fischer-Tropsch. En relació amb el disseny i fabricació dels reactors, durant aquesta tesi, es va desenvolupar el prototip d'un microreactor per a la metanació de CO2, on una membrana polimèrica de capa fina selectiva a l'aigua es va integrar per a així evitar la desactivació del catalitzador i al seu torn desplaçar l'equilibri i augmentar la conversió de CO2. D'altra banda, un reactor de Fischer-Tropsch va ser redissenyat per a poder introduir una membrana metàl¿lica selectiva a l'hidrogen i poder injectar-lo de manera controlada. D'aquesta manera, i seguint estudis previs, el objectiu va ser millorar la selectivitat als productes desitjats mitjançant el hidrocraqueix i la hidroisomerització d'olefines i parafines amb l'ajuda de l'alta pressió parcial d'hidrogen. / [EN] The present thesis is focused on the development of new gas-separation membranes, as well as their in-situ integration on catalytic membrane reactors for process intensification. For this purpose, several materials have been synthesized such as polymers for membrane manufacture, catalysts for CO2 methanation and Fischer-Tropsch synthesis reaction, and inorganic materials in form of nanometer-sized particles for their use in mixed matrix membranes. Regarding membranes manufacture, this thesis deals mainly with two types: organic and inorganic. With regards to the organic membranes, different polymeric materials have been considered as promising candidates, both for the selective layer of the membrane, as well as a support thereof. Polyimides have been selected since they are materials with very high glass transition temperatures, in order to be used in industrial reactions which take place at temperatures around 250-300 ºC. To obtain highly permeable membranes, while maintaining a good selectivity, it is necessary to develop selective layers of less than one micron. Using another type of polymer as support material, it is not necessary to study the compatibility between membrane and support. On the other hand, if the support is inorganic, an exhaustive study of the relation between the concentration and the viscosity of the polymer solution is highly necessary. In addition, various inorganic particles were studied to favor the permeation of water through polymeric materials. Secondly, as regards to inorganic membranes, the functionalization of a palladium membrane to favor the permeation of hydrogen and avoid carbon monoxide contamination was carried out. The membrane selective layer was doped with another metal in order to be used in a Fischer-Tropsch reactor. Regarding the design and manufacture of the reactors used during this thesis, a prototype of a microreactor for CO2 methanation was carried out, where a thin-film polymer membrane selective to water was integrated to avoid the deactivation of the catalyst and to displace the equilibrium and increase the CO2 conversion. On the other hand, a Fischer-Tropsch reactor was redesigned to introduce a hydrogen-selective metal membrane and to be able to inject it in a controlled manner. In this way, and following previous studies, the aim is to enhance the selectivity to the target products by hydrocracking and hydroisomerization the olefins and paraffins assisted by the presence of an elevated partial pressure of hydrogen. / I would like to acknowledge the Spanish Government, for funding my research with the Severo Ochoa scholarship. / Escorihuela Roca, S. (2019). Novel gas-separation membranes for intensified catalytic reactors [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/121139 / TESIS

Thesis submitted in the requirements for the degree Doctor Technologiae: Chemical Engineering in the Faculty of Engineering at the CAPE PENINSULA UNIVERSITY OF TECHNOLOGY, 2013 / To date, limited information has been published on textile wastewater treatment, for re-use, in South Africa (SA), with treatment processes focusing on conventional wastewater treatment methods. A large contributor to the contamination of water within textile industries is from dyehouse processes. A major concern in textile wastewater treatment is the release of azo dyes and their metabolites, some of which are carcinogenic and mutanogenic, into the environment since they are xenobiotic and aerobically recalcitrant to biodegradation. A necessity therefore exists to find an effective treatment method capable of removing both the strong colour and the toxic organic compounds from textile wastewater. Membrane bioreactors (MBRs) are favoured when treating high-strength wastewater, since the membrane area is determined by the hydraulic throughput and not the biological load; no sludge is wasted and all bacteria are retained within the reactor, including specific bacteria capable of degrading the toxic, non-biodegradable constituents present in textile wastewater. MBR systems, using various configurations have been utilised extensively in the rest of the world to treat textile wastewater at both lab and pilot-scale. This DTech project formed part of a collaborative Water Research Commission (WRC) funded project K5/1900 - Pilot application of a dual-stage membrane bioreactor (dsMBR) for industrial wastewater treatment. The main purpose of this study was the on-site evaluation of a pilot-scale dsMBR incorporating two ultrafiltration (UF) sidestream membrane modules for the treatment, recovery and re-use of textile wastewater. The objectives of this project were to determine the treatment efficiency of the system; to evaluate the degree of colour removal from the textile wastewater; to improve residual colour removal within the system using treatment processes, such as NF and RO, as well as to propose a design and cost for a full-scale plant. A textile industry located in Bellville, Western Cape, was chosen as the industrial partner for the on-site evaluation of a semi-automated pilot wastewater treatment MBR plant using two 5.1 m2 Norit X-flow AirliftTM membrane modules. Since the wastewater treatment system was located on the premises, real continuously changing industrial wastewater was being treated. The industrial textile wastewater was treated in a series of tanks: 1) an anaerobic tank, which cleaved the azo bonds of the reactive dyes; 2) an anoxic tank containing reduced amounts of dissolved oxygen, in which denitrification occurred; and 3) an aerobic tank, in which i) nitrification, as well as ii) mineralisation of the aromatic amines occurred. The UF-membrane modules would account for the removal of any organic material. The wastewater stream was characterised by a chemical oxygen demand (COD) range of between 45 to 2,820 mg/L and an average biological oxygen demand (BOD) of 192.5 mg/L. The dsMBR achieved an average COD reduction of 75% with a maximum of 97% over the 220 day test period. The COD concentration obtained after dsMBR treatment averaged at 191 mg/L, which was well within the City of Cape Town industrial wastewater discharge standard. The average reduction in turbidity and TSS was 94% and 19.6%, respectively, during the UF-MBR stage of the system. Subsequent treatment of the UF permeate with nanofiltration (NF) for 4 days, alternated with reverse osmosis (RO) for 14 days removed both the residual colour and salt present in the UF permeate. A consistent reduction in the colour of the incoming wastewater was evident. The colour in the wastewater was reduced from an average of 659 ADMI units to ~12 ADMI units in the NF permeate, a lower American dye manufacturing index (ADMI) (i.e. method of colour representation) compared to the potable water (~17 ADMI units) utilised by the industrial partner in their dyeing processes. The colour was reduced from an average of 659 to ~20 ADMI units in the RO permeate, a lower ADMI and therefore colour when compared to the potable water. An average conductivity rejection of 91% was achieved with conductivity being reduced from an average of 7,700 to 693 μS/cm and the TDS reduced from an average of 5,700 to 473 mg/L, which facilitated an average TDS rejection of 92%. Based on the composition of the UF permeate fed to the RO membrane a maximum removal of 98.7% was achieved for both conductivity and total dissolved solids (TDS). The proposed full-scale plant would incorporate a UF-MBR system, followed by NF, RO, flocculation and a filter press. Therefore, the two waste products produced during operation of the proposed full-scale plant, would be the solid filter cakes and the liquid filtrate from the filter press. Implementing the proposed full-scale plant it would cost the industrial partner an operating cost of ZAR 113.85 and ZAR 3,415.49 to treat 97.1 m3 and 2,913 m3 of textile wastewater, respectively, per day and per month. This results in an annual saving of ZAR 845,848 on potable water expenses. This research, would provide SA textile industries, with an option to: 1) reduce their water consumption, thereby utilising less of a valuable decreasing commodity; 2) meet the SA government discharge standards and reduce their discharge costs; 3) reduce their carbon footprint (i.e. reduce their impact on the environment) by re-using their treated wastewater and therefore using less water from the municipality; and 4) decrease their annual expenditure on water, since the treated wastewater would be available for re-use.