Heterogeneous Catalysis and its Industrial Applications

Heterogeneous Catalysis and its Industrial Applications

Martin Schmal Heterogeneous Catalysis and its Industrial Applications

Martin Schmal Chem.Eng. Dept. Federal University of Rio de Janeiro (UFRJ) Rio de Janeiro, Brazil University of S~ao Paulo (USP) S~ao Paulo, Brazil ISBN 978-3-319-09249-2 ISBN 978-3-319-09250-8 (ebook) DOI 10.1007/978-3-319-09250-8 Library of Congress Control Number: 2016954333 Springer International Publishing Switzerland 2016 This work is subject to copyright. All rights are reserved by the Publisher, whether the whole or part of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation, broadcasting, reproduction on microfilms or in any other physical way, and transmission or information storage and retrieval, electronic adaptation, computer software, or by similar or dissimilar methodology now known or hereafter developed. The use of general descriptive names, registered names, trademarks, service marks, etc. in this publication does not imply, even in the absence of a specific statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use. The publisher, the authors and the editors are safe to assume that the advice and information in this book are believed to be true and accurate at the date of publication. Neither the publisher nor the authors or the editors give a warranty, express or implied, with respect to the material contained herein or for any errors or omissions that may have been made. Printed on acid-free paper This Springer imprint is published by Springer Nature The registered company is Springer International Publishing AG Switzerland

Dedicated To my parents who greatly contributed to my training and life. To my wife, Victoria, who always encouraged me, for her patience and love. To Thaiz and Alice my daughters and Camille, Sophie, Catarina and Hector my grandchildren who made my life more beautiful.

Preface The importance of catalysis is due to the large number of applications in catalytic processes, particularly in the chemical and petrochemical industry, in power generation, in environmental preservation by reducing gas and water pollution, and in the development of new materials. Although many important catalytic processes were mostly resolved, there is great scope for development of new processes and new efficient catalysts in various areas of industry. Known processes for several decades can be optimized by improving their performance and stability. There are good prospects for the development of new catalysts, alternative catalysts, and processes for environmental catalysis, fine chemicals, hydrotreating heavy oils, generation of hydrogen, C1 chemistry, new materials, and biomass. The study of nanostructured materials is of great interest from the standpoint of both basic science and technological applications. The increased process efficiency, substitution of raw materials, the development of cleaner processes, and technologies for environmental control and for alternative energy production are focal areas that illustrate the need for adjustments to existing formulations and/or development of new materials. Specifically in the area of catalysis and materials, progress in the summary field requires a descriptive and theoretical understanding of interface phenomena and an interdisciplinary approach where the physical chemistry, modeling of processes, and surface phenomena appear with an appropriate methodological way to construction of scientific knowledge to minimize the gap between theory and application. The following methods have had an impressive progress in recent years and consequently the basic knowledge in catalysis, facilitating the understanding of surface and interfacial phenomena. In addition to the chemical and physicochemical methods, physical methods of surface and interfaces were those which allowed the greatest advance in the knowledge of phenomena involving the chemical reaction. vii

viii Preface This book aims to present the fundamentals of catalysis and applications illustrated with experiments performed in our laboratory, trying to understand why select the catalysts and processes. We seek to split the text into two parts. The first part presents the fundamentals addressing the activity patterns, adsorption desorption phenomena, and advanced theories (Chaps. 1 5). The second part presents the most important conventional methods of characterizing properties (Chap. 6); the important methods of preparation with pre/posttreatment (Chap. 7); the most important traits (Chap. 8), with examples and practices; spectroscopic characterizations, even in situ (Chaps. 8 12); Nanostructured catalysts (Chap. 13) the microkinetic chemistry and surface mechanisms (Chap. 14), and finally the evaluation of an industrial catalyst process (Chap. 15). Rio de Janeiro, Brazil Martin Schmal

Acknowledgment For contributions and discussions of all my students in Catalysis, Kinetics, and Reactors courses touched for several years at the Federal University of Rio de Janeiro (COPPE and EQ). In particular, to all master s and doctoral students who have contributed to examples, problems, and experiments. To the Nucleus of Catalysis lab (NUCAT) with exceptional infrastructure that allowed us to do research of high level and also to the outstanding students of the Chemical Engineering Program at COPPE. Special thanks to the researchers Carlos André Perez, Deborah Vargas Cezar, Silvia Moya and Sonia Vasconcelos for their contribution in specific chapters to characterizations (XRD, XPS, IR, Nanostructures and TEM). To all research group and technicians of the Nucleus of Catalysis (NUCAT), ensuring results of high quality. Finally to the Chemical Engineering Program PEQ/COPPE, the School of Chemistry/UFRJ, the Polytechnic School/USP, and special funds of CNPq, CAPES, FINEP, FAPERJ and FAPESP, for supporting my work. ix

Contents 1 Introduction... 1 1.1 Nanostructured Systems........ 4 2 Model Catalysts... 5 References... 9 3 Activity Pattern... 11 3.1 Influence of the Structure and of the Surface......... 16 3.1.1 Metals.................................... 16 3.1.2 Oxides... 17 3.1.3 Acid Base Solids... 18 3.2 Model Reactions... 18 3.2.1 Dehydrogenation of Cyclohexane................ 20 3.2.2 Hydrogenolysis of Methylcyclopentane............ 21 3.2.3 Benzene Hydrogenation.... 22 3.2.4 Butadiene Hydrogenation......... 23 3.2.5 Carbon Monoxide Oxidation... 24 References... 25 4 Adsorption Desorption... 27 4.1 Basic Concepts...... 27 4.1.1 Introduction.... 27 4.1.2 Energy Diagram.... 30 4.1.3 Characteristics... 31 4.2 Adsorption Desorption Models........................ 37 4.2.1 Introduction.... 37 4.3 Adsorption on Metals............................... 45 4.3.1 Lennard-Jones Diagram... 47 4.3.2 Mechanisms of Adsorption of Gases.............. 48 4.4 Adsorption on Semiconductor Oxides.... 59 References... 61 xi

xii Contents 5 Basic Concepts... 63 5.1 Geometric Configurations: Steric Effects...... 63 5.2 Electronic Configurations: Electronic Effects Band and Orbital Theories... 67 5.2.1 Band Theory............................... 68 5.2.2 Theory of Molecular Orbitals................... 71 5.2.3 The Electronegativity Theory: The Role of Electrons d... 77 5.2.4 Conclusion................................ 82 5.3 Examples........................................ 82 5.3.1 Design of a Catalyst: Alcohol Route... 82 5.3.2 Deoxygenation of Benzoic Acid to Benzaldehyde.... 86 References... 96 6 Textural and Thermochemical Characterizations... 99 6.1 Part I: Adsorption Methods for Determination of Surface Areas and Pore Volumes..... 99 6.1.1 Physical Adsorption or Physisorption... 99 6.1.2 Chemical Adsorption or Chemisorption............ 100 6.1.3 Porosity...... 101 6.1.4 Specific Surface Area: BET Method.............. 102 6.1.5 Other Adsorption Models...................... 111 6.1.6 Chemisorption... 112 6.1.7 Calculation of Metal Surface Area, Dispersion, and Particle Diameter.... 114 6.2 Part II: Thermal-Programmed Methods..... 120 6.2.1 Introduction.... 120 6.2.2 Apparatus...... 121 6.2.3 Quantitative Analyses...... 122 6.2.4 Temperature Programmed Desorption... 124 6.2.5 Temperature Programmed Reduction... 132 6.2.6 Temperature Programmed Oxidation.............. 144 6.2.7 Differential Scanning Calorimetry... 149 6.2.8 Thermogravimetric and Thermo-Differential Analyses......... 150 6.2.9 Temperature Programmed Surface Reaction... 154 References... 157 7 Catalyst Preparation... 161 7.1 Introduction..... 161 7.1.1 Materials for the Preparation... 163 7.2 Precipitation and Coprecipitation....................... 165 7.2.1 Thermodynamic Analyses.... 165 7.2.2 Kinetics of the Precipitation...... 169 7.2.3 Amorphous Solids.... 172

Contents xiii 7.2.4 Coprecipitation............................. 174 7.2.5 Deposition Precipitation... 175 7.3 Impregnation..................................... 177 7.3.1 Impregnation Methods.... 177 7.3.2 Ion Exchange... 182 References... 186 8 Variables Influencing Final Properties of Catalysts... 189 8.1 Influence of ph.... 189 8.2 Autoclaving..... 189 8.3 Influence of Time, Concentration, and Impregnation Cycles... 191 8.4 Thermal Treatments..................... 191 8.4.1 Drying... 191 8.4.2 Calcination... 193 8.5 Effect of Reduction Temperature on Interaction and Sintering....................... 196 8.6 Influence of the Support and the Metal Concentration on the Reduction.................................. 197 8.7 Influence of the Heating Rate... 198 8.8 Influence of Steam...... 199 8.9 Effect of Temperature and Reaction Time... 199 8.10 Strong Metal Support Interaction... 200 8.11 Conclusion....................................... 202 References... 202 9 Structural Analyses: X-ray Diffraction... 205 Martin Schmal and Carlos André C. Perez 9.1 Concepts and Parameters Influencing X-ray Diffraction...... 205 9.1.1 Instrumentation... 212 9.1.2 Interpretation of X-ray Diffractograms: Phase Identification...... 214 9.1.3 Interpretation of the X-ray Diffractograms: Crystallite Size... 215 9.2 X-ray Diffraction Analyses: In Situ Analyses...... 222 9.2.1 Structure Analyses: XRD...... 222 9.2.2 Reducibility of Oxide (LaCoO 3 ) byinsituxrd... 222 References... 225 10 Spectroscopy in the Infrared Region... 227 Martin Schmal and Deborah Vargas Cesar 10.1 Interpretation of Infrared Spectra....................... 231 10.2 Sample Handling: Analysis of Solids, Liquids, and Gases..... 232 10.3 Surface Characterization of Solids Using Probe Molecules... 234

xiv Contents 10.4 Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS)............................. 239 10.5 Diffuse Reflectance Spectroscopy (DRS) in the Visible UV Region............................ 242 References... 247 11 X-Ray Photoelectron Spectroscopy (ESCA: XPS/ISS)... 251 Martin Schmal and Carlos André C. Perez 11.1 Introduction.... 251 11.2 Concepts........................................ 252 11.3 Surface Chemical Composition... 255 11.4 Oxidation State... 256 11.5 ISS Spectra...... 258 11.6 Surface Analyses XPS In Situ....................... 259 11.6.1 XPS Spectra of Calcined and Reduced Catalyst...... 260 11.6.2 XPS In Situ Reaction: Methane Oxidation.......... 261 11.6.3 ISS: CO Adsorption In Situ.... 263 References... 264 12 Electronic Microscopy: General and Specific Notions... 267 Martin Schmal and Sonia M.R.Vasconcelos 12.1 Imaging in SEM: Basic Principles...................... 268 12.2 Secondary Electrons... 270 12.3 X-Ray Analysis.... 271 12.4 Preparation of Catalyst Samples for SEM Analyses... 272 12.5 Transmission Electronic Microscopy...... 274 12.6 Examples........................................ 277 12.7 Preparation of Catalyst Samples for TEM..... 280 References... 282 13 Nanostructured Catalysts... 285 Martin Schmal and Silvia Moya 13.1 Part I: Introduction.... 285 13.1.1 Synthesis of Nanostructured Catalysts............. 287 13.1.2 In Situ Precipitation of Metal Precursors........... 289 13.1.3 Synthesis of Stabilized Nanoparticles: Colloidal Nanoparticles... 291 13.1.4 Metal Nanostructures [8, 17 53]... 295 13.1.5 Oxide Nanocrystals [18, 19, 24, 44, 51, 53, 63, 72 152]...... 304 13.1.6 Mixed Oxides: Perovskite Structures Perovskites..... 309 13.2 Part II: Graphenes... 314 13.2.1 Syntheses of Graphenes..... 314 13.2.2 Syntheses of Metals on Graphene Nanosheets... 316

Contents xv 13.2.3 Structure..... 317 13.3 Conclusion....................................... 320 References... 321 14 Kinetics and Mechanisms... 329 14.1 Kinetics of the Carbon Monoxide Oxidation on Pt/TiO 2 Catalyst... 333 14.2 Kinetics of a Bifunctional Model: Methane Dry Reforming with CO 2... 335 14.3 Mathematical Modeling of Microkinetics... 337 14.3.1 Statistical Analyses: Influence of Independent Variables on Reaction Rates... 337 14.4 Conclusions... 337 References... 338 15 Evaluation of Industrial Catalysts... 341 15.1 Hydrogenation in Petrol Pyrolysis Unit.... 341 15.1.1 Introduction... 341 15.2 1,3-Butadiene Conversion at High Pressure............... 347 15.2.1 Butadiene Hydrogenation Reaction at 25 atm....... 349 15.3 Production of Polyalcohol at High-Pressure Hydrogenation of Cane Sugar and Hydrolyzed Amides.... 350 15.3.1 Introduction... 350 15.3.2 Experimental... 351 15.3.3 Conclusions..... 354 References... 354 Nomenclature... 357 Index... 369