Heterogeneous Catalysis and its Industrial Applications

Transcription

1 Heterogeneous Catalysis and its Industrial Applications

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3 Martin Schmal Heterogeneous Catalysis and its Industrial Applications

4 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 ISBN (ebook) DOI / Library of Congress Control Number: 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

5 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.

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7 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

8 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

9 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

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11 Contents 1 Introduction Nanostructured Systems Model Catalysts... 5 References Activity Pattern Influence of the Structure and of the Surface Metals Oxides Acid Base Solids Model Reactions Dehydrogenation of Cyclohexane Hydrogenolysis of Methylcyclopentane Benzene Hydrogenation Butadiene Hydrogenation Carbon Monoxide Oxidation References Adsorption Desorption Basic Concepts Introduction Energy Diagram Characteristics Adsorption Desorption Models Introduction Adsorption on Metals Lennard-Jones Diagram Mechanisms of Adsorption of Gases Adsorption on Semiconductor Oxides References xi

12 xii Contents 5 Basic Concepts Geometric Configurations: Steric Effects Electronic Configurations: Electronic Effects Band and Orbital Theories Band Theory Theory of Molecular Orbitals The Electronegativity Theory: The Role of Electrons d Conclusion Examples Design of a Catalyst: Alcohol Route Deoxygenation of Benzoic Acid to Benzaldehyde References Textural and Thermochemical Characterizations Part I: Adsorption Methods for Determination of Surface Areas and Pore Volumes Physical Adsorption or Physisorption Chemical Adsorption or Chemisorption Porosity Specific Surface Area: BET Method Other Adsorption Models Chemisorption Calculation of Metal Surface Area, Dispersion, and Particle Diameter Part II: Thermal-Programmed Methods Introduction Apparatus Quantitative Analyses Temperature Programmed Desorption Temperature Programmed Reduction Temperature Programmed Oxidation Differential Scanning Calorimetry Thermogravimetric and Thermo-Differential Analyses Temperature Programmed Surface Reaction References Catalyst Preparation Introduction Materials for the Preparation Precipitation and Coprecipitation Thermodynamic Analyses Kinetics of the Precipitation Amorphous Solids

13 Contents xiii Coprecipitation Deposition Precipitation Impregnation Impregnation Methods Ion Exchange References Variables Influencing Final Properties of Catalysts Influence of ph Autoclaving Influence of Time, Concentration, and Impregnation Cycles Thermal Treatments Drying Calcination Effect of Reduction Temperature on Interaction and Sintering Influence of the Support and the Metal Concentration on the Reduction Influence of the Heating Rate Influence of Steam Effect of Temperature and Reaction Time Strong Metal Support Interaction Conclusion References Structural Analyses: X-ray Diffraction Martin Schmal and Carlos André C. Perez 9.1 Concepts and Parameters Influencing X-ray Diffraction Instrumentation Interpretation of X-ray Diffractograms: Phase Identification Interpretation of the X-ray Diffractograms: Crystallite Size X-ray Diffraction Analyses: In Situ Analyses Structure Analyses: XRD Reducibility of Oxide (LaCoO 3 ) byinsituxrd References Spectroscopy in the Infrared Region Martin Schmal and Deborah Vargas Cesar 10.1 Interpretation of Infrared Spectra Sample Handling: Analysis of Solids, Liquids, and Gases Surface Characterization of Solids Using Probe Molecules

14 xiv Contents 10.4 Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) Diffuse Reflectance Spectroscopy (DRS) in the Visible UV Region References X-Ray Photoelectron Spectroscopy (ESCA: XPS/ISS) Martin Schmal and Carlos André C. Perez 11.1 Introduction Concepts Surface Chemical Composition Oxidation State ISS Spectra Surface Analyses XPS In Situ XPS Spectra of Calcined and Reduced Catalyst XPS In Situ Reaction: Methane Oxidation ISS: CO Adsorption In Situ References Electronic Microscopy: General and Specific Notions Martin Schmal and Sonia M.R.Vasconcelos 12.1 Imaging in SEM: Basic Principles Secondary Electrons X-Ray Analysis Preparation of Catalyst Samples for SEM Analyses Transmission Electronic Microscopy Examples Preparation of Catalyst Samples for TEM References Nanostructured Catalysts Martin Schmal and Silvia Moya 13.1 Part I: Introduction Synthesis of Nanostructured Catalysts In Situ Precipitation of Metal Precursors Synthesis of Stabilized Nanoparticles: Colloidal Nanoparticles Metal Nanostructures [8, 17 53] Oxide Nanocrystals [18, 19, 24, 44, 51, 53, 63, ] Mixed Oxides: Perovskite Structures Perovskites Part II: Graphenes Syntheses of Graphenes Syntheses of Metals on Graphene Nanosheets

15 Contents xv Structure Conclusion References Kinetics and Mechanisms Kinetics of the Carbon Monoxide Oxidation on Pt/TiO 2 Catalyst Kinetics of a Bifunctional Model: Methane Dry Reforming with CO Mathematical Modeling of Microkinetics Statistical Analyses: Influence of Independent Variables on Reaction Rates Conclusions References Evaluation of Industrial Catalysts Hydrogenation in Petrol Pyrolysis Unit Introduction ,3-Butadiene Conversion at High Pressure Butadiene Hydrogenation Reaction at 25 atm Production of Polyalcohol at High-Pressure Hydrogenation of Cane Sugar and Hydrolyzed Amides Introduction Experimental Conclusions References Nomenclature Index