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UNIVERSITAT ROVIRA I VIRGILI HYDRODECHLORINATION OF CHLORINATED ORGANIC WASTES OVER PD SUPPORTED MIXED OXIDE CATALYSTS Beteley Tekola Meshesha DL: T.1347-2011 Doctoral thesis Beteley Tekola Meshesha Hydrodechlorination of chlorinated organic wastes over Pd supported mixed oxide catalysts Universitat Rovira i Virgili UNIVERSITAT ROVIRA I VIRGILI HYDRODECHLORINATION OF CHLORINATED ORGANIC WASTES OVER PD SUPPORTED MIXED OXIDE CATALYSTS Beteley Tekola Meshesha DL: T.1347-2011 Universitat Rovira i Virgili Departament d’Enginyería Química Escola Técnica Superior d’Enginyería Química Hydrodechlorination of chlorinated organic wastes over Pd supported mixed oxide catalysts Presented by Beteley Tekola Meshesha To acquire the grade for the European degree of Doctor from Universitat Rovira I Virgili Supervised by Dr. Francisco Medina and co-supervised by Dr. Jesús E. Sueiras and Dr. Ricardo J. Chimenton UNIVERSITAT ROVIRA I VIRGILI HYDRODECHLORINATION OF CHLORINATED ORGANIC WASTES OVER PD SUPPORTED MIXED OXIDE CATALYSTS Beteley Tekola Meshesha DL: T.1347-2011 Prof. Francesc Medina Cabello, Prof. Jesús E. Sueiras Dr. Ricardo J. Chimenton Professors and researchers of the department of Chemical Engineering at the Universitat Rovira i Virgili, certify that the doctoral thesis entitled “Hydrodechlorination of chlorinated organic wastes over Pd supported mixed oxide catalysts” by Beteley Tekola Meshesha for the award of the European degree doctor has been carried out under our supervision in the Department of Chemical Engineering, Universitat Rovira i Virgili. Tarragona, Spain, April 2011 Supervisor F. Medina Co-Supervisor Jesús.E.Sueiras Ricardo .J. Chimenton UNIVERSITAT ROVIRA I VIRGILI HYDRODECHLORINATION OF CHLORINATED ORGANIC WASTES OVER PD SUPPORTED MIXED OXIDE CATALYSTS Beteley Tekola Meshesha DL: T.1347-2011 THESIS TRIBUNAL Prof. Bernard Coq Institut Charles Gerhardt Montpellier UMR 5253 CNRS/ENSCM/UM2/UM1, 8, rue de l'Ecole Normale, 34296 Montpellier cedex 5, France Prof. Francisco López Bonilla Departament Enginyería Química, Universidad Rovira i Virgili, Spain Dr. Jordi Llorca Institut de Tècniques Energètiques, Universitat Politècnica de Catalunya, Barcelona, Spain Dr. Karin Föttinger Institute of Materials Chemistry, Vienna University of Technology, Vienna, Austria Dr. Anton Dafinov Department Enginyería Química, Universidad Rovira i Virgili, Tarragona, Spain RESERVE Dr. Sònia Abelló L’Institut de Recerca en Energia de Catalunya, Bioenergy and Biofuels, Tarragona, Spain Dr. Sandra Contreras Department Enginyería Química, Universidad Rovira i Virgili, Spain EXTERNAL REFEREES Dr. Didier Tichet Laboratoire de Materiaux Catalytiques et Catalysi en Chimie Organique, CNRS Montpelier (Francia) Dr. Noelia Barrabés Vienna University of Technology, Vienna, Austria UNIVERSITAT ROVIRA I VIRGILI HYDRODECHLORINATION OF CHLORINATED ORGANIC WASTES OVER PD SUPPORTED MIXED OXIDE CATALYSTS Beteley Tekola Meshesha DL: T.1347-2011 Acknowledgement I am heartily thankful to my supervisor, Professor Francisco Medina, whose encouragement, guidance and support from the initial to the final level enabled me to develop an understanding. I would like to extend my gratitude to Professor Jesus E. Sueiras. I am grateful to my co-advisor, Dr. Ricardo J. Chimenton, whom I started to work with and received an endless help and support. Throughout my thesis-writing period, they provided encouragement, sound advice, good company, and lots of good ideas. I would like to thank Professor G. Rupprechter and Dr. Karin Föttinger for making possible my research stay in the institute of material chemistry, Technical university of Vienna. Especial thank goes to Dr. Noelia Barrabes for her ideas and concepts that have had a remarkable influence on our joint research. I am also indebted to many of my colleagues. I will never forget the good times, coffee breaks, conferences especially with Noe, Anton, Abel, Vero, Mayra, Sandra R., Biniam, and Kike which are my invaluable memories. Special thank goes to all my Ethiopian colleagues especially to Berhane, Nigus, Ashu, Belay, Asfaw, Fiteha, Messi and all the others. I also wish to express my special thank for Vienna’s group, Karin, Katy, Christians, Andy, Andreas and Nikki. The time I spent together initiated and nurtured my maturity both as a researcher and person. Thank you for priceless experiences. My appreciation will also go to Urko and all my fortuny friends for the good times we have passed together. My humble gratitude also goes to my group mates Anna, Sandra C., Iuliana, Kaveh, Adriana and Alex for the time we had together in laboratories. I would like to thank also Universitat Rovira I Virgili, Spanish ministry of education and AMIC for financial and material support throughout the thesis. Finally I would like to offer my gratitude with respect to my father whose ideals and dedication in life has nourished my success in all the way. I also wish to thank my entire family for providing a loving and supportive environment. UNIVERSITAT ROVIRA I VIRGILI HYDRODECHLORINATION OF CHLORINATED ORGANIC WASTES OVER PD SUPPORTED MIXED OXIDE CATALYSTS Beteley Tekola Meshesha DL: T.1347-2011 Table of contents Acknowledgement Table of content Figure caption Resumn Summary Background and Motivation 1. General introduction……………………………..….…………..……1 1.1.Chlorinated organic compounds (COCs)………………………...3 1.2.Catalytic Hydrodechlorination of COCs.……..……………….10 2. Aim and Objectives………………………..……………….….........31 3. Experimental…………………..…………………..…………………35 3.1.Catalyst preparation…………..………………………………...37 3.2.Characterization techniques..…………………………………...40 3.3.Catalytic test……...………..……………………..…………….64 4. Results and Discussion....…………………………………………..69 4.1.Catalytic HDC of 1,2,4-trichlorobenzene over Pd/Mg(Al)O catalyst………………………………………………………….71 4.2.Performance of Alkali modified Pd/Mg(Al)O catalysts for HDC of 1,2,4-trichlorobenzene …………...……………………..…...93 4.3.Catalytic HDC of 1,2,4-Trichlorobenzene over Pd/Mg(Al)O catalyst: effect of calcination temperature...………………..…123 4.4.Gas-phase HDC of trichloroethylene over Pd/NiMgAlO catalysts……………………………………………………..…135 4.5.Nanoparticle synthesis and application in HDC of trichloroethylene……………………………………………....169 5. Conclusion...………………..………..……………………..…….…201 References………………………………………………..……………207 Publication….…………………………………………………………..221 UNIVERSITAT ROVIRA I VIRGILI HYDRODECHLORINATION OF CHLORINATED ORGANIC WASTES OVER PD SUPPORTED MIXED OXIDE CATALYSTS Beteley Tekola Meshesha DL: T.1347-2011 Figure caption 1. General introduction Fig. 1. Structure of some chlorinated organic compounds. Fig. 2. Structure of some of toxic species produces after incineration of COCs. Fig. 3. Schematic representation for HDC of 1,2,4-trichlorobenzene Fig. 4. Idealized structure of a Mg(OH)2 brucite structure. Fig. 5. Structure of a layered double hydroxide with interlayer water and carbonate anions. Fig. 6. Possible reaction pathway for hydrodechlorination of TCE. 2. Aim and objectives 3. Experimental Fig. 1. The different radiation emitted during excitation of a solid surface. Fig. 2. The five types of van der Waals adsorption isotherms. Fig. 3. Typical hydrogen chemisorption at 373 K temperature