UNIVERSIDAD DE CANTABRIA ESCUELA TÉCNICA SUPERIOR DE INGENIEROS INDUSTRIALES Y DE TELECOMUNICACIÓN DEPARTAMENTO DE INGENIERÍA QUÍMICA Y QUÍMICA INORGÁNICA Membrane technologies for hydrogen and carbon monoxide recovery from residual gas streams (Tecnologías de membranas para la recuperación de hidrógeno y monóxido de carbono de gases residuales) Memoria de Tesis Doctoral presentada para optar al título de Doctora por la Universidad de Cantabria. Programa de Doctorado en Ingeniería Química y de Procesos Directores de Tesis: Dra. Ane Miren Urtiaga Mendia Dr. Eugenio Daniel Gorri Cirella Oana Cristina David Santander, Mayo 2012 Agradecimientos Me gustaría expresar mi gratitud a mis directores de tesis, la Dra. Ane Miren Urtiaga y el Dr. Daniel Gorri, por la confianza el esfuerzo y tiempo dedicados para que este trabajo saliera adelante. Gracias por haberme dado la oportunidad de trabajar en el fascinante mundo de la investigación. También me gustaría agradecer a la responsable del grupo de investigación “Procesos avanzados de separación”, dentro de cual este trabajo ha sido llevado a cabo, a la Dra. Inmaculada Ortiz por su exigencia y profesionalidad que determinó la calidad de este trabajo. Gracias a la Dra. Kitty Nijmeijer por la oportunidad de trabajar en el grupo de investigación “Membrane Science and Technology Group”, University of Twente y a todo el personal de dicho departamento por la calurosa acogida y por dedicarme una buena parte de su tiempo en transferir sus conocimientos y experiencia en el campo de las membranas. “I want to express my acknowledgments to Prof. Dr. Kitty Nijmeijer for giving me the opportunity to work in Membrane Science and Technology Group, University of Twente. I am also grateful to the people from this group for dedicating important part of their time in sharing their knowledge and experience in the membrane field” Gracias a la Dra. Nazely Diban por animarme en los momentos difíciles y por ser un ejemplo a seguir de dedicación y trabajo. Gracias a Dra. Clara Casado por ayudarme en los primeros pasos en el campo de las membranas y de las instalaciones de gases. También quiero agradecer a todos los compañeros de trabajo, entre ellos a Alfredo, Marcos, Gabriel, Mariana, Marisol, Sonia, Hala, Vanesa, Elia, Karima, Bea, Esther, Antía el que hayan compartido estos años conmigo y haber recibido su atención. También quiero agradecer al personal de mantenimiento, Felix, Elena y Rafa y al personal administrativo, Inmaculada y Pilar. Quiero expresar mis agradecimientos a mis padres, mi hermana y mis abuelas por apoyarme incondicionalmente en todas las decisiones tomadas durante mi vida y por soportar estar tan lejos de mí. “Vreau să mulţumesc părinţilor, surorii şi bunicilor pentru sprijinul necondiţionat ce mi l-au acordat în toate deciziile luate pe parcursul vieţii şi pentru faptul că au suportat sa fie atât de departe de mine” Por último agradezco al Ministerio de Educación Cultura y Deporte la concesión de la beca FPU que ha permitido la elaboración de este trabajo de Tesis Doctoral. Reconocimiento Nuestro agradecimiento a Huntsman Corporation por la autorización para la reproducción del documento Matrimid® 5218/ Matrimid® 9725 SUMMARY (RESUMEN) SUMMARY This PhD thesis work is aimed to the separation and recovery of valuable gases, hydrogen and carbon monoxide, from industrial residual gas streams by means of membrane technology. The work has been developed within the Research Group Advanced Separation Processes of the Department of Chemical Engineering of the University of Cantabria (Spain) under the frame of the projects: ENE 2010-15585, CTQ 2008-00690/PPQ and CTM 2006-00317 supported by the Ministry of Science and Innovation of Spain. Also, the PhD candidate has been granted with a FPU postgraduate research fellowship with the reference AP2008-04646 from the Ministry of Education, Culture and Sport (Spain). The training period has been completed by a short stage period in the Membrane Science & Technology Group, University of Twente, The Netherlands under, the supervision of Dr. Kitty Nijmeijer. Sustainable industrial growth is based on the development of new industrial processes able to solve global important problems like greenhouse gas emissions, energy efficiency and toxic waste. Many academic and industrial efforts are being made in order to reach the zero discharge goal. The separation and valorization of industrial flue gases with complex composition allows approaching sustainability by means of different routes. The production of streams concentrated in valuable components can include (i) a reuse in the same industrial process to increase the energy efficiency of the overall process or (ii) the further use as reactants in the synthesis of various chemicals. In this thesis, a case of study is defined as the tail gas generated in the manufacturing of carbon black, a commodity whose global production reaches 80 million tons, in medium - high sized installations. The tail gas is formed, in a dry basis, by the following gas mixture, in vol %: 60.5% N2, 17.9 % CO, 16.4 % H2 and 5.3 % CO2. Hydrogen and carbon monoxide are identified as major valuable components. It is envisaged that membrane technology will allow to obtain H2 enriched permeate stream when polymeric membranes are used and CO can be obtained as permeate gas stream when facilitated transport - supported liquid membranes are used. Chapter I of this thesis gives a brief introduction over different gas separation methods and shows the industrial sources and importance of H2 and CO. The first part of chapter I focuses on more detailed aspects of polymeric membrane-based H2 separation, including the transport mechanism, the selection of the polymeric material for the manufacturing of membranes, and the mixed gas permeation through polymeric membranes. Also, a description of the production process of carbon black is included. In the second part the CO separation by means of π - complexation is exposed showing the particular aspects involved when facilitated transport - supported liquid membranes are used. Also, an overlook on room temperature ionic liquids is given with the principal focus on their potential use as liquid phase in facilitated transport - supported ionic liquid membranes. Chapter II and III of this thesis deal with the study of polymeric membrane based separation of hydrogen from mixed gas streams composed of H2, CO, N2 and CO2 at different operation conditions, using membranes prepared with a commercial glassy polymer, Matrimid. The methodologies used to prepare both planar and asymmetric hollow fiber membranes are described in detail. In chapter II the use of a planar Matrimid membrane allowed to describe H2 and CO2 permeation behavior of pure, binary, ternary and quaternary mixtures using the “dual-mode sorption, partial immobilization” model. Non-ideal effects, such as competitive sorption between permeants, have been characterized, providing the mass transfer parameters for the systems. These results provide useful knowledge related to the intrinsic material properties. In chapter III the use of a asymmetric hollow fiber membrane made of the same polymeric material allowed to determine the major differences between the gas permeation (pure and mixed) through an dense isotropic structure (planar membrane) and an asymmetric structure (hollow fiber). Also, a comparative permeation performance with another asymmetric hollow fiber made from a much more permeable glassy polymer, polyphenylene oxide, was made. Chapter IV is focused on the design of a liquid phase system to be used in facilitated transport-supported ionic liquid membranes for the recovery of carbon monoxide. A comprehensive look at the reaction mechanism and the equilibrium parameters obtained from the experimental characterization of the physical and chemical solubility of carbon monoxide in pure ionic liquid 1-Hexyl-3- methylimidazolium chloride ([hmim][Cl]) and 1-Hexyl-3-methylimidazolium chlorocuprate obtained by mixing copper chloride with [hmim][Cl] is presented. The latter one presented excellent solubility selectivity properties for the separation of the mixture CO/N2. Finally, in Chapter V overall conclusions of the entire work are made. Also prospects for further research are included. RESUMEN Esta tesis doctoral está enfocada hacia la separación y recuperación de hidrogeno y monóxido de carbono de efluentes gaseosos residuales procedentes de procesos industriales de combustión mediante la tecnología de membranas. El presente trabajo ha sido llevado a cabo en el grupo de investigación Procesos Avanzados de Separación del Departamento de Ingeniería Química y Química Inorgánica de la Universidad de Cantabria (España), en el marco de los proyectos ENE 2010-15585, CTQ 2008-00690/PPQ y CTM 2006-00317 financiados por el Ministerio de Ciencia e Innovación de España. Asimismo, la candidata a doctora Oana C. David disfruto de una Beca del Programa de Formación de Profesorado Universitario (FPU) con la referencia AP2008-04646, financiada por el Ministerio de Educación, Cultura y Deporte de España. La formación ha sido completada mediante una estancia de 4 meses en el grupo de investigación Membrane Science & Technology de la University of Twente (Países Bajos) bajo la supervisión de la Dra. Kitty Nijmeijer. El crecimiento industrial sostenible está basado en el desarrollo de nuevos procesos industriales capaces de resolver problemas globales como la emisión de gases residuales, la eficiencia energética y la generación de residuos tóxicos. En la actualidad,