DOCSLIB.ORG

Jaime Gómez Díaz

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Jaime Gómez Díaz FIRST-PRINCIPLES MECHANISTIC STUDIES OF AMMONIA-RELATED INDUSTRIAL PROCESSES Jaime Gómez Díaz ISBN: 978-84-694-1247-3 Dipòsit Legal: T-317-2011 ADVERTIMENT. La consulta d’aquesta tesi queda condicionada a l’acceptació de les següents condicions d'ús: La difusió d’aquesta tesi per mitjà del servei TDX (www.tesisenxarxa.net) ha estat autoritzada pels titulars dels drets de propietat intel·lectual únicament per a usos privats emmarcats en activitats d’investigació i docència. No s’autoritza la seva reproducció amb finalitats de lucre ni la seva difusió i posada a disposició des d’un lloc aliè al servei TDX. No s’autoritza la presentació del seu contingut en una finestra o marc aliè a TDX (framing). Aquesta reserva de drets afecta tant al resum de presentació de la tesi com als seus continguts. En la utilització o cita de parts de la tesi és obligat indicar el nom de la persona autora. ADVERTENCIA. La consulta de esta tesis queda condicionada a la aceptación de las siguientes condiciones de uso: La difusión de esta tesis por medio del servicio TDR (www.tesisenred.net) ha sido autorizada por los titulares de los derechos de propiedad intelectual únicamente para usos privados enmarcados en actividades de investigación y docencia. No se autoriza su reproducción con finalidades de lucro ni su difusión y puesta a disposición desde un sitio ajeno al servicio TDR. No se autoriza la presentación de su contenido en una ventana o marco ajeno a TDR (framing). Esta reserva de derechos afecta tanto al resumen de presentación de la tesis como a sus contenidos. En la utilización o cita de partes de la tesis es obligado indicar el nombre de la persona autora. WARNING. On having consulted this thesis you’re accepting the following use conditions: Spreading this thesis by the TDX (www.tesisenxarxa.net) service has been authorized by the titular of the intellectual property rights only for private uses placed in investigation and teaching activities. Reproduction with lucrative aims is not authorized neither its spreading and availability from a site foreign to the TDX service. Introducing its content in a window or frame foreign to the TDX service is not authorized (framing). This rights affect to the presentation summary of the thesis as well as to its contents. In the using or citation of parts of the thesis it’s obliged to indicate the name of the author. UNIVERSITAT ROVIRA I VIRGILI FIRST-PRINCIPLES MECHANISTIC STUDIES OF AMMONIA-RELATED INDUSTRIAL PROCESSES Jaime Gómez Díaz ISBN:978-84-694-1247-3/T-317-2011 UNIVERSITAT ROVIRA I VIRGILI FIRST-PRINCIPLES MECHANISTIC STUDIES OF AMMONIA-RELATED INDUSTRIAL PROCESSES Jaime Gómez Díaz ISBN:978-84-694-1247-3/T-317-2011 UNIVERSITAT ROVIRA I VIRGILI FIRST-PRINCIPLES MECHANISTIC STUDIES OF AMMONIA-RELATED INDUSTRIAL PROCESSES Jaime Gómez Díaz ISBN:978-84-694-1247-3/T-317-2011 First-principles mechanistic studies of ammonia-related industrial processes Jaime G´omezD´ıaz Doctoral Thesis supervised by: Dra. N´uria L´opez Alonso Departament de Qu´ımica F´ısica i Inorg`anica Tarragona 2010 UNIVERSITAT ROVIRA I VIRGILI FIRST-PRINCIPLES MECHANISTIC STUDIES OF AMMONIA-RELATED INDUSTRIAL PROCESSES Jaime Gómez Díaz ISBN:978-84-694-1247-3/T-317-2011 UNIVERSITAT ROVIRA I VIRGILI FIRST-PRINCIPLES MECHANISTIC STUDIES OF AMMONIA-RELATED INDUSTRIAL PROCESSES Jaime Gómez Díaz ISBN:978-84-694-1247-3/T-317-2011 Institute of Chemical Research of Catalonia Avgda. Pa¨ısos Catalans 16 43007 Tarragona (Spain) I STATE that the present work entitled “First-principles mechanistic studies of ammonia-related processes” presented by Jaime G´omez D´ıaz to opt to the title of European Doctor, has been carried out under my su- pervision at the Institute of Chemical Research of Catalonia (ICIQ) and that it fulfils all the necessary requirements. Tarragona, November 2010 Dr. N´uria L´opez UNIVERSITAT ROVIRA I VIRGILI FIRST-PRINCIPLES MECHANISTIC STUDIES OF AMMONIA-RELATED INDUSTRIAL PROCESSES Jaime Gómez Díaz ISBN:978-84-694-1247-3/T-317-2011 UNIVERSITAT ROVIRA I VIRGILI FIRST-PRINCIPLES MECHANISTIC STUDIES OF AMMONIA-RELATED INDUSTRIAL PROCESSES Jaime Gómez Díaz ISBN:978-84-694-1247-3/T-317-2011 Acknowledgments Esta tesis no hubiera sido posible sin su directora, N´uria L´opez, y sin la beca que me concedi´opara trabajar en un centro con recursos tan ex- traordinarios como los del ICIQ. Haluan kiitt¨a¨at¨all¨aerityisell¨atavalla FT Karoliina Honkalaa h¨anen vieraanvaraisuudestaan, mutta ennen kaikkea h¨anen yst¨av¨allisest¨aomistautumisestaan ohjaamiselleni. Una altra per- sona que em va ajudar for¸ca a acabar aquesta tesi va ser la N´uria Vendrell i la seva, sempre impecable, feina. Me gustar´ıa tambi´en agradecer a todas las instituciones que han financiado/apoyado mi trabajo de investigaci´on: ante todo el ICIQ, pero tambi´en otras como BSC, CSC, HPC-Europa2 program, etc. Ahora bien, si he llegado a esta etapa del camino en casi aceptables condiciones de salud mental y con pelo por encima de las cejas, es tambi´en culpa de mucha otra gente. No me gustar´ıa imaginarme como hubieran sido estos m´as de 4 a˜nos sin ella en el despacho... ¡Hecho, M´onica! Mucho, much´ısimo han contribuido tambi´en a esta tesis el resto de “los te´oricos”. Gracias, Ata, Gerard, Pere, Torstein, Maria, Eva, Crisa, Mart´ın, Joan y tod@s los dem´as (as´ıno me dejar´ea nadie y no llenar´e8 p´aginas...), con un saludo especial para Carles y Feliu. He de agradecer a mi cocina el regalarme una hora diaria (y alguna extra los fines de semana) de buen humor, conversaciones y sobre todo desconexi´on: ¡muchas gracias, chic@s! Thanks also to Ville, Sergio, Jenni, Riita-Liisa, Vesa, Kaisa, Olga and Lauri; for making me feel as in my own (cold) home at Jyv¨askyl¨aand Helsinki. Gracias tambi´en al resto de gente del ICIQ, de la URV, de Tarragona-city y de la UAM (¡con vosotros empez´otodo esto!) que no formaba parte de ninguno de los subconjuntos anteriores, pero, especial- UNIVERSITAT ROVIRA I VIRGILI FIRST-PRINCIPLES MECHANISTIC STUDIES OF AMMONIA-RELATED INDUSTRIAL PROCESSES Jaime Gómez Díaz ISBN:978-84-694-1247-3/T-317-2011 viii mente, a mis incre´ıbles compa˜neros de los cursos de doctorado y del mas- ter: ¡c´omo nos lo pasamos! Muchas gracias tambi´en a toda la gente que rodea “mi otra vida”. Especialmente a Mar´ıa, Ricardo, Chus y tod@s (nunca olvidados, os lo prometo) los dem´as: Luis, Willy, Kaka, Nuria, Sergio, el Kalvo, Marcos, Robles, Zahara, Berta, Bel´en, Dani, Yolanda, Ana, Alla, Nacho, Desi, la gente del GRM... y muchos, muchos otros. Tengo mucho que agradecer a mi familia: mis padres (¡todav´ıa me acuerdo de lo de la gasolinera!), mi hermana, Nena y Diana; y por ´ultimo, a Laura. Espero que el dejarla en ´ultimo lugar represente de alguna manera todas las cosas que le tengo que agradecer y que no creo que se pudieran expresar en papel (ni en formato electr´onico). UNIVERSITAT ROVIRA I VIRGILI FIRST-PRINCIPLES MECHANISTIC STUDIES OF AMMONIA-RELATED INDUSTRIAL PROCESSES Jaime Gómez Díaz ISBN:978-84-694-1247-3/T-317-2011 Nada habr´ıa podido suceder si alguien no lo hubiera imaginado primero, Reinhold Messner UNIVERSITAT ROVIRA I VIRGILI FIRST-PRINCIPLES MECHANISTIC STUDIES OF AMMONIA-RELATED INDUSTRIAL PROCESSES Jaime Gómez Díaz ISBN:978-84-694-1247-3/T-317-2011 UNIVERSITAT ROVIRA I VIRGILI FIRST-PRINCIPLES MECHANISTIC STUDIES OF AMMONIA-RELATED INDUSTRIAL PROCESSES Jaime Gómez Díaz ISBN:978-84-694-1247-3/T-317-2011 Contents I Introduction 1 1 Introduction 3 1.1 Catalysis ............................ 3 1.1.1 Heterogeneous catalysis . 4 1.2 Ostwald process: HNO3 production.............. 5 1.2.1 HNO3:propertiesanduses . 5 1.2.2 Production ....................... 6 1.3 Degussa and Andrussow processes: HCN production . 9 1.3.1 HCN:propertiesanduses . 9 1.3.2 Production ....................... 10 1.4 MacArthur-Forrest process: gold ore extraction . 13 1.4.1 Gold: properties and uses . 13 1.4.2 Extraction........................ 14 1.5 Thesisoutline.......................... 16 2 Theoretical background 17 2.1 Introduction........................... 17 2.2 Density Functional Theory . 18 2.3 Formalism............................ 18 2.4 Approximations......................... 21 2.5 Implementation......................... 22 2.5.1 Pseudopotentials . 22 2.5.2 Plane waves as basis sets . 24 2.5.3 Realspacemethods . 24 2.5.4 k-points ......................... 26 2.5.5 Electronic minimization . 27 xi UNIVERSITAT ROVIRA I VIRGILI FIRST-PRINCIPLES MECHANISTIC STUDIES OF AMMONIA-RELATED INDUSTRIAL PROCESSES Jaime Gómez Díaz ISBN:978-84-694-1247-3/T-317-2011 xii CONTENTS 2.6 Ionicrelaxation......................... 27 2.6.1 Supercells........................ 29 2.7 Baderanalysis ......................... 30 2.8 Electron Localization Function . 30 2.9 Transition state searching . 32 2.9.1 RegularNEBmethod . 33 2.9.2 Climbing Image NEB method . 34 2.10 Ab-Initio thermodynamics. .. .. .. .. .. 35 2.11 Linearrelationships. 36 2.11.1 Brønsted-Evans-Polanyi relations . 37 2.11.2 Adsorption energy with binding energy of an atom relations......................... 37 II Results 39 3 HNO3 synthesis: Results 41 3.1 Computational details . 41 3.2 A particular case: Au(111) . 42 3.2.1 Previousworks ..................... 43 3.2.2 Ammonia dehydrogenation on Au(111) . 44 3.2.3 NO and N2 formation on Au(111) . 48 3.2.4 Kineticmodeling . 50 3.2.5 Kinetic model for the Au(111) surface. 53 3.3 A more general case: Transition Metals . 56 3.3.1 Previousworks ..................... 56 3.3.2 NO and N2 formation on transition metals . 58 3.3.3 Reactivity on Me(111) flat surfaces . 59 3.3.4 Reactivity on Me(211) stepped surfaces .
Load more

Recommended publications
  • Appendix Supplied to Complement Draslovka's Application to the New
    Appendix supplied to complement Draslovka’s application to the New Zealand EPA to import and use EDN (ethanedinitrile) Appendix Sections Appendix 1 Applicant details 1.1. Applicant pg 4 1.2 Draslovka background pg 4 1.3 The history of EDN pg 11 1.4 Background on STIMBR pg 12 1.5. Research undertaken by STIMBR to identify alternatives, tools and technologies to manage methyl bromide emissions pg 16 Appendix 4 Life cycle of EDN 4.1 Manufacturing and Importation pg 24 4.2 Packaging pg 25 4.3 Storage pg 28 4.4 Disposal pg 37 4.5 Safety data sheets pg 38 Appendix 5 Use 5.1 Phytosanitary treatments for export logs pg 47 5.2 Where EDN is applied pg 47 5.3 Details on the use of EDN pg 48 5.4 NZ ports and their suitability for fumigation activities pg 50 5.5 Fumigation with EDN pg 60 Sub appendix 5.1 Phytosanitary Treatments for logs exported from New Zealand pg 71 5.1.1 The need for Phytosanitary Treatments pg 71 5.1.2 The Phytosanitary Tool Box pg 72 5.1.3 Market Access Negotiations pg 76 Sub appendix 5.2 Draeger cyanogen circular letter pg 78 Page 1 Appendix 6 Toxicology and HSNO 6.1 Classification pg 79 hazard classifications of the formulated 6.2 Toxicology pg 87 substance 6.2.1 Mode of action and toxic kinetic pg 87 6.2.2 Acute toxicity pg 88 Acute inhalation Oral toxicity Dermal toxicity Eye irritancy 6.2.3 Systemic toxicity pg 90 6.2.4 Reproductive and developmental toxicity pg 90 6.2.5 Neurotoxicity pg 91 6.2.6 Chronic toxicity pg 92 6.2.7 Genotoxicity pg 93 6.2.8 Carcinogenicity pg 95 6.2.9 WES and TEL values pg 96 6.3 Eco-toxicology 6.3.1 Fate in the environment pg 111 6.3.2 Ecotoxicological Classifications pg 113 Appendix 7 7.2 Risks costs and benefits analysis of 7.2.1 Risks pg 114 Introduction Proposed use Product description: and approach to risk analysis Physical characteristic assessment Human toxicological assessment Ecotoxicology risk assessment 7.2.2 Costs pg 137 Associated with a new chemical.
    [Show full text]
  • Cyanide Process
    Cyanide Process The cyanide antidote kit consists of three medications given together: amyl nitrite, sodium nitrite, and sodium thiosulfate. Sodium cyanide solution in water is a strong base; it reacts violently with acid and is corrosive. How is cyanide waste treated at your facility? Chemically speaking it looks like this CN + 2H20 -> NH3 + HCOO in laymen's terms we destroy cyanide using Thermal Hydrolysis. Liquid – vapor diagram of the system H 2O– HCN at atmospheric. The process was invented in 1887 by the Scottish chemists John S. 1 word related to cyanide process: industrial process. net dictionary. txt) or read online for free. Separate the process into half reactions.. 7k points). Australia is a major global manufacturer and exporter of sodium cyanide, with manufacturing facilities in western Australia. Orica's world leading cyanide analysers have been designed to optimise cyanide usage and lower costs, whilst maintaining precious metal recovery rates. Cyanide in fruits and vegetables is in the form of cyanogenic glycosides (cyanoglycosides). A cyanide is a compound, known simply as a 'cyanide', that contains a cyanide group (CN-) 1,3-6. After the door is sealed, and when the warden gives the signal, the executioner in a separate room operates a lever that releases the cyanide into the liquid. Whilst hanging is one of the most reliable methods of suicide, as for firearms, it is not 100% effective - studies would suggest 77% - 88% effective 1. 1 word related to cyanide process: industrial process. For the gold concentrate cyanide plant, the CaO concentration of the general control leaching process is between 2 and 5/10,000.
    [Show full text]
  • The Structure of Catalyst Gauzes After Hydrogen Cyanide Production
    The Structure of Catalyst Gauzes J after Hydrogen Cyanide Production A POSSIBLE EXPLANATION FOR THE FACETED FEATURES By A. G. Knapton Group Research Centre, Johnson Matthey and Co Limited During hydrogen cyanide production by the Andrussow process con- siderable redistribution of the surface of the rhodium-platinum gauze catalyst occurs, resulting in the formation of a porous mass of well-faceted metal crystallites. The phenomenon is illustrated in this paper, and some possible mechanisms to account for its formation are discussed. Rhodium-platinum alloy gauzes feature surface that occurs during operation. Much prominently in two important manufacturing has already been written in this journal (3, processes, the catalytic oxidation of ammonia 4, 5) on the surface effects on gauzes used for to nitric oxide in the production of nitric ammonia oxidation, but little attention has acid, and the Andrussow process for making been paid to gauze packs used in hydrogen hydrogen cyanide from methane and ammonia. cyanide production. At the Johnson Matthey Although direct reaction of the latter con- Research Centre we have recently had occa- stituents is possible via: sion to examine in detail gauzes that had been used in long campaigns in the Andrussow CH4 + NH, + HCN -1 3H, 4 100 kcal process. These gauzes showed some unusual and has been employed on a large scale (I), features, not found in those from ammonia the reaction is strongly endothermic, and oxidation and which have not been satisfac- supplying the heat to maintain the reaction torily explained by earlier workers (6, 7, 8, 9) temperature of 1000 to 1200T makes it on rhodium-platinum catalysts.
    [Show full text]