Handbook of Zeolite Science & Technology
Edited by Scott M. Auerbach, Kathleen A. Carrado and Prabir K. Dutta
…[W]hat is truly needed at this time is both a review of the current stat of the field as well as a guide to where the field is headed. With this in mind, the editors have done a remarkable job. … I would recommend this book to any who work in the fields of zeolite science and technology. It provides an excellent review for graduate students and researchers just starting out in the field and at the same time provides the more established researcher with a fresh vision and introduction to several exciting new applications.
Journal of the American Chemical Society, 2004
The Handbook of Zeolite Science and Technology offers effective analyses ofsalient cases selected expressly for their relevance to current and prospective research. Presenting the principal theoretical and experimental underpinnings of zeolites, this international effort is at once complete and forward-looking, combining fundamental concepts with the most sophisticated data for each scientific subtopic and budding technology. Supplying over 750 figures, and 350 display equations, this impressive achievement in zeolite science observes synthesis through the lens of MFI (ZSM-5 and silicalite). Chapters progress from conceptual building blocks to complex research presentations. www.amazon.com
There are many free ebook versions of this book online but because of its size and some technical issues it is difficult to download. Here it is presented chapter by chapter with a small part of each introduction.
Pramatha Payra and Prabir K. Dutta, The Ohio State University, Columbus, Ohio, U.S.A.
I. INTRODUCTION TO ZEOLITES
Zeolites are microporous crystalline aluminosilicates, composed of TO4 tetrahedra (T = Si, Al) with O atoms connecting neighboring tetrahedra. For a completely siliceous structure, combination of TO4 (T = Si) units in this fashion leads to silica (SiO2), which is an uncharged solid. Upon incorporation of Al into the silica framework, the +3 charge on the Al makes the framework negatively charged, and requires the presence of extra framework cations (inorganic and organic cations can satisfy this requirement) within the structure to keep the overall framework neutral.
2 MFI: A Case Study of Zeolite Synthesis
Ramsharan Singh and Prabir K. Dutta, The Ohio State University, Columbus, Ohio, U.S.A.
Zeolite synthesis occurs by a hydrothermal process with reagents being a silica source, an alumina source, a mineralizing agent such as OH_ or F_, and, for higher Si/Al ratio zeolites, organic molecules as structure-directing agents. The role of inorganic metal cations, such as Na+ or K+, is quite profound. A schematic of the zeolite growth process is shown in Fig. 1.
3 Introduction to the Structural Chemistry of Zeolites
Raul F. Lobo, University of Delaware, Newark, Delaware, U.S.A.
This chapter provides an introduction to the structure of zeolites and related crystalline microporous materials. The structural characteristics of the zeolite family make it unique among inorganic materials. It is difficult to overemphasize that an appreciation of zeolite structure is critical to an understanding of zeolite properties. We urge you to read this chapter carefully before proceeding to the other chapters of this volume.
4 Modeling Nucleation and Growth in Zeolites
C. Richard A. Catlow, David S. Coombes and Ben Slater, The Royal Institution of Great Britain, London, UK; Dewi W. Lewis, University College London, London, UK and J. Carlos G. Pereira, Instituto Superior Tecnico, Lisbon, Portugal
Modeling techniques have been used for many years in investigations of structures, properties, and reactivities of microporous materials (1). Early work focused on modeling of crystal structures (2), but applications quickly developed in the fields of sorption (see Chapter 9 in this volume) and diffusion (see Chapter 10). In recent years, extensive use has been made of highlevel quantum mechanical methods in the study of reaction mechanisms in zeolites (see Chapter 15).
5 Theoretical and Practical Aspects of Zeolite Crystal Growth
Boris Subotic´ and Josip Bronic´, Ruder Boskovic´ Institute, Zagreb, Croatia
Although most of the applications of the zeolites are closely connected with their structural and chemical properties (i.e., type of zeolite, modification by ion exchange and/or isomorphous substitution, etc.), size and morphology of zeolite crystals can play a significant role in the mode and efficiency of their application (1,2). Here are shown some characteristic examples of the influence of size and shape of zeolite crystals in their applications as ion exchangers, catalysts, adsorbents, coatings, and so forth. In order to control particle properties such as size and shape, it is necessary to understand crystal growth, which is the focus of this chapter.
6 Nuclear Magnetic Resonance Studies of Zeolites
Clare P. Grey, State University of New York at Stony Brook, Stony Brook, New York, U.S.A.
Nuclear magnetic resonance (NMR) has been widely used to characterize zeolite structure, acidity, and binding sites, and to study catalytic reactions or sorption processes that occur within the pores of zeolites. NMR is a probe of local structure and often serves as a complementary tool for the probe of long-range order, namely, diffraction. The NMR spectra are sensitive to a range of local interactions, which provide detailed spatial and chemical information. Furthermore, NMR spectroscopy is a quantitative probe of the whole sample and, thus, can be used or to follow the fate of molecules inside the pores of the zeolite, during a catalytic reaction or following gas sorption, or to determine, for example, the extent of aluminum substitution into the zeolite framework.
7 Electron Spin Resonance Characterization of Microporous and Mesoporous Oxide Materials
Larry Kevany, University of Houston, Houston, Texas, U.S.A.
I. ELECTRON SPIN RESONANCE BACKGROUND
Electron spin resonance (ESR) or electron magnetic resonance is a type of magnetic resonance spectroscopy that deals with transitions between magnetic energy levels associated with different orientations of an electron spin in an atom or molecule, generally in an external magnetic field. Measurement of the allowed transitions between the electron magnetic energy levels produces a spectrum of an atomic or molecular system with net electron spin angular momentum. Generally such systems are defined as those having one or more unpaired electrons. Analysis of the ESR spectrum can give information about the identification of the species, the geometrical structure, the electronic structure, and the internal or overall rotational or translational motion of the species. The most common types of systems studied are free radicals, which can be regarded as atoms or molecules containing one unpaired electron, and transition metal ion and rare-earth ions. The specificity of ESR spectroscopy for species containing unpaired electrons is particularly valuable for the study of chemical reaction intermediates.
8 Structural Study of Microporous and Mesoporous Materials by Transmission Electron Microscopy
Osamu Terasaki and Tetsu Ohsuna Tohoku University, Sendai, Japan
Porous materials are classifed in three dierent categories based on the size of pores ....... . Here we confine ourselves in micro-and mesoporous materials. Microporous crystals (hereafter called zeolites) with more than 130 different framework-type structures have been reported. Recently, new ordered mesoporous silicas have also been synthesized in acidic or basic condition by using self-organization of amphiphilic molecules, surfactants, and polymers, and macroporous materials have been synthesized by using a dierent type of bead as a mold. Transmission electron microscopy (TEM) can provide detailed structure of zeolites.
9 Simulating Adsorption of Alkanes in Zeolites
Berend Smit and Rajamani Krishna, University of Amsterdam, Amsterdam, The Netherlands
A proper description of adsorption phenomena is essential in the design of zeolite-based separations and catalysis. Transport and chemical reactions of molecules within zeolites are also significantly influenced by their adsorption characteristics. Though experimental data on adsorption of pure components in various zeolites are available, experimental data on mixture adsorption are scarce (1–3) due to the difficulty of experimentation with mixtures. In order to interpret the experimentally observed product distributions from zeolite-catalyzed processes, we need insights into the energetics and siting of intermediate molecular species formed during the reaction; it is very difficult to obtain such information from experiments.
10 Diffusion in Zeolites
Jorg Karger and Sergey Vasenkov, Leipzig University, Leipzig, Germany and Scott M. Auerbach, University of Massachusetts Amherst, Amherst, Massachusetts, USA
I. GENERAL INTRODUCTION
The dynamic properties of adsorbed molecules play a central role in reactions and separations that take place within the cavities of zeolites and other shape-selective, microporous catalysts. Selectivity may be strongly influenced, e.g., by the diffusivities of reactant and product molecules. However, with this selectivity comes a price: significant transport resistance. Zeolite scientists are thus interested in better understanding diffusion in zeolites to optimize the balance between high flux and high selectivity. These interests have resulted in a burgeoning field of both experimental and theoretical research, which we review in this chapter.
11 Microporous Materials Characterized by Vibrational Spectroscopies
Can Li and Zili Wu, Chinese Academy of Sciences, Dalian, China
The characterization of microporous materials, more popularly called zeolitic materials, began with the discovery and synthesis of zeolites in the 1960s. Various spectroscopic techniques, i.e., X-ray diffraction (XRD), IR, Raman, nuclear magnetic resonance (NMR), electron spin resonance (ESR), and so forth have been used to characterize zeolites and/or zeolite-adsorbate systems. Among these techniques, vibrational spectroscopies, mainly IR spectroscopy and Raman spectroscopy, are most extensively employed for the investigation of zeolites and the interaction between zeolites and adsorbates.
Jayaraman Sivaguru, Jayaramachandran Shailaja, and Vaidhyanathan Ramamurthy, Tulane University, New Orleans, Louisiana, U.S.A.
Being inspired by and having realized the complexity of natural systems, chemists have utilized a number of organized/confined media to study the photochemical and photophysical behavior of guest molecules (1–3). Examples of organized media in which the guest molecules behavior has been investigated include molecular crystals, inclusion
complexes (both in the solid and solution states), liquid crystals, micelles and related assemblies, monolayers, Langmuir-Blodgett films and surfaces, and natural systems such as DNA. In this chapter an overview of the activities in our laboratory, utilizing zeolite as a medium for photo-chemical and photophysical studies, is presented. No attempt is made to provide a comprehensive review of activities in this area.
Kyung Byung Yoon, Sogang University, Seoul, Korea
According to the long-inherited cosmological view of the Orient, the universe consists of yin (-) and yang (+) (1). They refer to entities that are richer in ‘‘negative spirits’’ and their counterparts that are richer in ‘‘positive spirits.’’ The knowledge of chemistry that has been accumulated during the last two centuries has also verified that matter consists of the two: those that are richer in negative-charge density and their counterparts that are richer in positive-charge density. In other words, matter consists of the two that are richer and poorer, respectively, in electron density. Accordingly, matter now can be categorized as electron richer or electron poorer. Consistent with this, in chemistry, compounds have commonly been divided into bases and acids, nucleophiles and electrophiles, and reductants and oxidants (2).
Alain Walcarius, Centre National de la Recherche Scientifique (CNRS)—Universite Henri Poincare (UHP) Nancy I, Villers-les-Nancy, France
The growing interest for zeolite molecular sieves in electro-chemistry arises from the synergistic combination of the attractive properties of these materials with electrochemical
Xavier Rozanska and Rutger A. van Santen, Eindhoven University of Technology, Eindhoven, The Netherlands
A zeolite is a natural or synthetic aluminosilicate crystal of which framework is composed by the assembling of SiO4 and AlO4 tetrahedral units (1–4). The tetravalent Si atoms cannot only be substituted by AlIII, but also by 3- or 5-valent atoms, such as GaIII, FeIII, or PV. If substitutions occur, cations are present to compensate for the framework charge. The materials are acting as solid acids when the compensating cation is a proton. Zeolites have been used for many years in several areas of chemistry because of their interesting
properties: first, they display ion exchange capability; and second, they have good separation property (4,5). The separation of molecules originates from the ordered structure of the zeolite micropores (Fig. 1) (6).
James F. Haw and David M. Marcus, University of Southern California, Los Angeles, California, U.S.A.
Solid (heterogeneous) catalysts (1–4) are favored in industrial processes because they eliminate the need to separate the catalyst from the products. Heterogeneous catalysts can be solid acids, bases, supported metals, mixed metal oxides, or multifunctional materials. Commercial processes based on solid acids outnumber all others, and zeolites (and closely related materials) are usually the solid acids of choice.
Sankar Nair* and Michael Tsapatsis, University of Massachusetts Amherst, Amherst, Massachusetts, U.S.A.
Zeolite-based separations involve pressure swing or temperature swing adsorption. These are unsteady-state processes which rely on cycles of preferential adsorption (of one component over the other) and subsequent desorption. Replacement of a swing adsorptionprocess with a steady-state process is arguably advantageous for several reasons, including
lower operating costs and reduced energy consumption. Over the last decade, much attention has been focused on the development of continuous zeolite-based separations
Katrin Hoffmann, Federal Institute for Materials Research and Testing (BAM), Berlin, Germany
Frank Marlow, Max Planck Institute for Coal Research, Mu¨lheim an der Ruhr, Germany
Communication systems have been dominated by electronic processes, but photonic concepts are increasingly gaining importance in information technology with devices such
as lasers, light-emitting diodes, photodetecting diodes, optical switches, optical amplifiers, optical modulators, and optical fibers. The aim of the efforts is to reduce the size of optical
devices and to integrate them jointly on a single optical circuit.
Masakazu Iwamoto, Tokyo Institute of Technology, Yokohama, Japan and Hidenori Yahiro, Ehime University, Matsuyama, Japan
A. Relevant Reactions in Environmental Catalysis
The use of catalytic processes in pollution abatement and resource recovery is widespread and of significant economic importance for the realization of sustainable chemistry/
industry (1). As has widely been recognized, there are five areas where environmentally benign catalysis would have significant impact:
1. Control of emissions of environmentally unacceptable compounds, especially in flue gases and car exhaust gases
2. Conversion of solid or liquid waste into environmentally acceptable products
3. Selective manufacture of alternative products that can replace environmentally harmful compounds, such as some chlorofluorocarbons (CFCs)
4. Replacement of environmentally hazardous catalysts in existing processes
5. Development of catalysts that enable new technological routes to valuable chemical products without the formation of polluting byproducts
The targets of environmentally benign catalysis lie in air, water, and soil. This chapter will focus primarily on the first topic, that of heterogeneous catalysis for unacceptable materials emitted into the air.
Jun Izumi, Mitsubishi Heavy Industries, Ltd., Nagasaki, Japan
Urgent requirements exist in nuclear related industries for the development of high efficiency processes for waste gas treatment. While mainly distillation and absorption methods have been used in the past, adsorption processes have recently begun to be adopted. A summary of waste gas treatment processes that feature adsorption are shown in Table 1 (with Refs. 1–7).
Howard S. Sherry, University of New Mexico, Albuquerque, New Mexico, U.S.A.
The most important technique used to modify zeolites is ion exchange. This chapter will review the ion-exchange properties of aluminosilicate zeolites with some emphasis on the problems and pitfalls encountered by this author. The techniques used to collect and analyze ion exchange data will be described. The data will be presented in the form of ion exchange isotherms. These isotherms can be used to calculate thermodynamic quantities in the equilibrium case (1), in the design of experiments (2), and in commercial ion-exchange processes (2).
Shivaji Sircar, Lehigh University, Bethlehem, Pennsylvania, U.S.A. and Alan L. Myers, University of Pennsylvania, Philadelphia, Pennsylvania, U.S.A.
Separation and purification of gas mixtures by selective adsorption of one or more of its components on a micro- or mesoporous solid adsorbent is a major unit operation in the
chemical, petrochemical, environmental, medical, and electronic gas industries. Figure 1 demonstrates the phenomenal growth in this technology (1). It shows that the total number of U.S. patents granted between the years of 1980 and 2000 on ‘‘gas separation by adsorption’’ and ‘‘adsorption for air pollution control’’ are more than 3000 and 1000, respectively.
Rajamani Krishna, University of Amsterdam, Amsterdam, The Netherlands
Zeolitic materials are used as sorbents and catalysts in a variety of processes within the chemical, petroleum, petro-chemical, and food industries. Zeolite crystals are incorporated
into binders (such as amorphous aluminosilicate) and perhaps a diluent (typically a clay mineral), and used in the form of powder (in fluidized beds) or pellets (in fixed beds). Alterna-tively, zeolite crystals are coated onto a porous membrane support and used in (catalytic) membrane permeation devices.
Kresimir Pavelic and Mirko Hadzˇija, Ruder Boskovic Institute, Zagreb, Croatia
A particular structural feature of zeolites relative to other aluminosilicate materials, and other crystalline materials in general, is the existence of channels and/or cavities linked by
channels. One of the characteristics that distinguishes zeolites from other porous materials is their variety of pore sizes and shapes. The size and shape of channels/cavities in zeolites
therefore define the structural parameters of a given type of zeolite (1). Properties of zeolites, such as ion exchange, intercrystalline pores that discriminate between molecules
of different dimension, strong acidic sites, and active reservoirs for metal-catalyzed reactions, have earned them extensive industrial uses. Consequently, fundamental zeolite research has become an area of great interest (2). The remarkable applicability of zeolites ranges from uses in biochemistry, the agroindustry, detergents, soil improvements, the nuclear industry, energy storage, and the textile industry (3).