The effective separation of ammonia from the synthesis loop in ammonia synthesis plants is an important step in its manufacture. This work presents the use of nanocomposite MFI zeolite membranes prepared by a pore-plugging method for this separation process. Performance of a zeolite membrane is highly dependent on the operating conditions. Therefore, the influences of differential pressure, temperature, sweep gas flow, feed gas flow and gas composition are studied experimentally. Transport of NH3 in this membrane is by surface diffusion in the intracrystalline (zeolite) pores in parallel with capillary condensation in the intercrystalline (non-zeolite) pores. The separation of NH3 from a mixture with H2 and N2 is by preferential adsorption of NH3, which hinders the permeation of weakly adsorbed H2 and N2. Differential pressure has only relatively small effects in the pressure range 300kPa – 1550kPa. Increase in sweep flow rate has little effect on NH3 gas permeance, but H2 and N2 permeances increase thereby decreasing the selectivities. Increase in feed flowrate also has little effect on NH3 permeance. However, the N2 and H2 permeances increase and there is a subsequent decrease in selectivities. Membrane performance was found to be highly dependent on temperature. NH3 permeance in the mixture increases linearly with temperature. NH3 selectivity was found to increase with temperature up to 353K after which it starts to decrease due to N2 and H2 permeances increasing with temperatures beyond 353K (αNH3/N2 = 46 and αNH3/H2 = 15) and is therefore the optimum temperature for separation. A potential barrier model is developed to describe the hindering effect of NH3 on H2 and N2 permeance. The model fails to predict correctly H2 and N2 permeances in the ternary mixture using pure gas (H2 and N2) permeances. Binary mixture permeation H2/N2 studies showed that there are diffusion effects (single file diffusion) that have not been taken into account in the potential barrier model. When permeances of the individual components in the binary mixture are used in the model instead of the pure gas permeances, there is an improved agreement between experimental and predicted results.

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MFI type zeolites, are the most widely studied zeolites for membrane separations. Conventionally, zeolite membranes are prepared in batch systems by hydrothermal synthesis in autoclaves. This method has several disadvantages for use in industrial scale for the synthesis of membranes with large areas and complex geometries that are commonly used in membrane modules. The objective of this study is to prepare MFI type zeolite membranes on tubular alumina supports in a continuous system where the synthesis solution is circulated through the tubular supports. Syntheses were carried out using clear solutions, at atmospheric pressure and at temperatures below 100&deg / C. The membranes were characterized by N2, SF6, n-butane and isobutane permeances, X-ray diffraction and scanning electron microscopy. A 2-&amp / #956 / m membrane was synthesized using the composition 80SiO2: 16TPAOH: 1536H2O at 95&deg / C in the continuous system. The membrane showed N2 permeance of 4.4 x 10-7 mol/m2.s.Pa and N2/SF6 selectivity of 11. The membrane synthesized in the batch system showed a N2 permeance of 3.4 x 10-7 mol/m2.s.Pa and a N2/SF6 selectivity of 27. Both membranes showed n-butane/isobutane mixture (50%-50%) selectivities of about 6 at temperatures of 150 and 200&deg / C. Among many zeolite membranes reported in literature, these membranes are one of the few zeolite membranes synthesized in a flow system and the first MFI type membranes synthesized in a continuous flow system with circulation of the synthesis solution. The permeances and selectivities of the membranes synthesized in the continuous system are comparable with the MFI type membranes synthesized in batch systems in literature.

[ES] Las zeolitas son materiales cristalinos microporosos con canales y tamaños de poro de dimensiones moleculares. La estructura y composición de las zeolitas les confiere interesantes propiedades que permiten su aplicación en una amplia gama de aplicaciones industriales como adsorción, separación o catálisis. La síntesis de zeolitas es la etapa más importante para el control de la estructura y composición de las zeolitas y, por tanto, crítica para la optimización de sus propiedades. Esta tesis se ha centrado en la síntesis de zeolitas utilizando compuestos que contienen fósforo (cationes fosfonio y aminofosfonio) como Agentes Directores de Estructura (P-ADE). El uso de compuestos fosforados influye en la cristalización y propiedades de las zeolitas obtenidas en comparación con las zeolitas obtenidas con cationes de amonio clásicos. Los compuestos fosforados se eligieron debido a su diferente química y estabilidad con respecto a los cationes de amonio clásicos comúnmente usados en la síntesis de zeolitas. Estos aspectos se estudiaron con un estudio comparativo de diferentes cationes de amonio y fosforados. Los compuestos de fósforo utilizados en este trabajo han dado lugar a nuevas estructuras cristalinas (ITQ-58 e ITQ-66) y han abierto nuevas vías de síntesis de zeolitas ya conocidas (RTH, IWV y DON), ampliando su gama de composiciones químicas. La descomposición térmica de los P-ADE confinados dentro de las zeolitas da lugar a la formación de especies de fósforo extra-red que permanecen dentro de los canales y cavidades de las zeolitas. Estas especies modulan las propiedades ácidas y de adsorción de los materiales finales dependiendo de los tratamientos post-síntesis. En este trabajo se ha estudiado una ruta para la incorporación de cantidades controladas de fósforo durante la etapa de síntesis. Esto ha permitido controlar la adsorción y las propiedades ácidas en las zeolitas de poro pequeño, lo que no se puede lograr mediante metodologías de post-síntesis. / [CA] Les zeolites són materials cristal·lins microporosos amb canals i mides de porus de dimensions moleculars. L'estructura i composició de les zeolites els confereix interessants propietats que permeten la seua aplicació en una àmplia gamma d'aplicacions industrials com adsorció, separació o catàlisi. La síntesi de zeolites és l'etapa més important per al control de l'estructura i composició de les zeolites i, per tant, crítica per a l'optimització de les seues propietats. Aquesta tesi s'ha centrat en la síntesi de zeolites utilitzant compostos que contenen fòsfor (cations fosfoni i aminofosfoni) com a agents directors d'estructura (P-ADE). L'ús de compostos fosforats influeix en la cristal·lització i propietats de les zeolites obtingudes en comparació amb les zeolites obtingudes amb cations d'amoni clàssics. Els compostos fosforats es van triar a causa de la seua diferent química i estabilitat pel que fa als cations d'amoni clàssics utilitzats en la síntesi de zeolites. Aquests aspectes s¿estudiaren amb un estudi comparatiu de diferents cations d'amoni i fosforats. Els compostos de fòsfor utilitzats en aquest treball han donat lloc a noves estructures cristal·lines (ITQ-58 i ITQ-66) i han obert noves vies de síntesi de zeolites ja conegudes (RTH, IWV i DO), ampliant la seua gamma de composicions químiques. La descomposició tèrmica dels P-ADE atrapats dins de les zeolites dona lloc a la for-mació d'espècies de fòsfor extra-xarxa que romanen dins dels canals i cavitats de les zeolites. Aquestes espècies modulen les propietats àcides i d'adsorció dels materials finals depenent dels tractaments post-síntesi. En aquest treball s'ha estudiat una ruta per la incorporació de quantitats controlades de fòsfor durant l'etapa de síntesi. Això ha permés controlar l'adsorció i les propietats àcides en les zeolites de porus petit, el que no es pot aconseguir mitjançant metodologies de post-síntesi. / [EN] Zeolites are microporous crystalline materials with channels and pore openings of molecular dimensions. The structure and composition of zeolites confers them interesting properties that allow their application in a wide range of industrial applications as adsorption, separation or catalysis. The synthesis of zeolites is the most important stage to control the structure and composition of zeolites, and thus, critical to optimize their properties. This thesis has been focused on the synthesis of zeolites using phosphorous containing compounds (phosphonium and aminophosphonium cations) as Organic Structure Directing Agents (P-OSDA). The use of these phosphorous compounds influence the crystallization and properties of the obtained zeolites compared to zeolites obtained with classical ammo-nium cations. Phosphorous compounds were chosen because of their different chemistry and stabil-ity properties respect to classical ammonium cations commonly used in the synthesis of zeo-lites. These aspects were studied in a comparative study with different ammonium and phosphorous cations. The phosphorous compounds used in this work have yielded new crystalline structures (ITQ-58 and ITQ-66) and opened new routes for the synthesis of already known zeolites (RTH, IWV and DON), widening their chemical composition range. The thermal decomposition of the P-OSDAs entrapped inside the zeolites yields to the formation of extra-framework phosphorus species that remain inside the channels and voids of the zeolites. These species modulate the adsorption and acid properties of the final materials depending on the post-synthesis treatments. In this work, a route for the incorporation of controlled amounts of phosphorus during the synthesis stage has been studied. This has allowed to control the adsorption and acid properties in small pores zeolites, which cannot be achieved by post-synthesis methodologies. / I wish to firstly acknowledge the Spanish Government for the necessary funding for the FPI pre-doctoral fellowship (BES-2013-062999). Also, this thesis would not have been possible without the infrastructures provided by the UPV and the CSIC staff, fused into the ITQ. Furthermore, I want to acknowledge the Microscopy Service of the UPV for their support in sample microscopy characterization / Simancas Coloma, J. (2021). Synthesis and Characterization of Zeolitic Materials Using Phosphorous Organic Structure Directing Agents [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/171267