Book Reviews
Energy & Fuels, Vol. 3, No. 5, 1989 647 1
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tinguish between models using a single TPR run. However, as shown in the figure, this straight line is not equivalent to the Bhatia-Perlmutter model at a different heat rate of, e.g., 5 K/min. Of course, another straight line could have been devised to represent the 5 K/min curve, but it will not be the line that was successfully used for the Bhatia-Perlmutter model at 1K/min. It is this difference that makes it possible to distinguish between the competing models. It explains why Miura and Silveston needed at least two TPR experiments with different heating rates for model selection. The circumstances just discussed should be similar for distinguishing between the volumetric model and the grain model and between the grain model and the Bhatia-Perlmutter model. We have examined the minimum differences between the heating rates for confident model selection in a more extensive paper to be published el~ewhere.~
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~
1.1
1.5
1.3
1.7
1/Tx IO3 [ K - ' 1 Figure 1. Transformation of the Bhatia-Perlmutter model to the volumetric one by replacing 1 $ 4 4 with
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TPR experiment they conducted. The term In (aeSIRr) gives a straight line as shown in the figure. The straight line on the curve for a = 1 K/min represents the transformation of the Bhatia-Perlmutter model to the volumetric one and will give nearly the same 1 - X vs temperature curve as that of the Bhatia-Perlmutter model. Because this transformation is possible, we may not dis-
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(3) Makino, M.; Silveston, P. L. Determination of Reaction Models and Kinetic Parameters from Experimental Measurement. Submitted for publication in Can. J. Chem. Eng. (4) Visiting Research Professor, also Senior Researcher, Coal and Carbon Department, National Research Institute for Pollution and Resources, Tsukuba, 305, Japan. (5) Visiting Associate Professor, also Associate Professor, Research Laboratory of Carbonaceous Resources Conversion Technology, Kyoto University, Kyoto, 606, Japan.
Mitsunori Makino: Kouichi Miurat P. L. Silveston* Department of Chemical Engineering University of Waterloo Waterloo, Ontario N2L 3G1,Canada Received June 5,1989 Revised Manuscript Received July 26, 1989
Book Reviews Coal Science and Chemistry. Edited by A. Volborth. Coal Science and Technology 10. Elsevier Science Publishers: Amsterdam. 1986. 478 pp.
Coal Science and Chemistry is the 10th and latest volume to the series Coal Science and Technology. The first seven chapters, 206 out of 471 pages, are devoted to review articles. Each one has a different set of authors and a variety of topics. They include ether bond reactions, NMR shift correlations, modeling studies on both devolatilization and combustion, disposable liquefaction catalysts, magnetic susceptibility of coal, oxidation of coal structure, and tandem mass spectrometry of coal-relatedmaterials. With the exception of the first and the sixth articles, the authors attempted to put the literature material into proper perspective, giving their own opinions as to the critical nature of a particular reference. The chapter on disposable liquefaction catalysts, for example, nicely centers the discussion on the key problem in coal liquefaction, that is efficient use of hydrogen. Starting with the historical background, the authors describe the issue from the coal's standpoint, in terms of its physical properties, which lead directly to the engineering concerns. Much research needs to be done in this area, and if this chapter had one drawback, it was that it dealt primarily with higher temperature free-radical approaches to conversion. The second half of the book is devoted to 12 original science articles. Again, each one is on a different subject with topics ranging from environmental aspects of coal, fly ash, geochemistry
of the Mattagami formation lignites, coal slurry electrolysis, depolymerization and coal structure, thermal decomposition of coal (mathematical models), coal maturity, characterization of lignites, adsorption and diffusion, coal-solvent interactions, NAA organic oxygen determination, the hostlguest structure concept and the thermolysis of coal, and finally size exclusion chromatography of coal liquids. In general, these original articles were authoritatively written and well referenced. For example, the chapter of geochemistry and petrography covered some pioneering work using X-ray photoelectron spectroscopy (XPS). This surface-sensitive technique coupled with bulk analysis methods provides detailed structural information rapidly. Recent advances in characterization have led to better understanding of coal chemistry, and each article describes one or more technique in its own specific study. This reference book is a welcome addition to the coal chemist's library and is especially valuable to those who are new to the field or to those interested in the specific areas covered. With the wide variety of specialized topics, many aspects of the book should have broad appeal. Ronald Liotta, Exxon Research & Engineering Company
Coal Classification. By Anne M. Carpenter. London. 1989. 104pp. f60.
IEA Coal Research:
This book presents a broad and balanced view of coal classification and its associated problems. It starts with a brief but
648 Energy & Fuels, Vol. 3, No. 5, 1989
good introduction and then examines the chemical, mechanical and physical, and petrographic properties of coal that are used as a basis for its classification. It also gives a limited but useful review of the potential of four techniques, TGA, NMR, pyrolysis MS, and FTIR, for providing classification parameters. The key section of the book gives a comprehensive review of the various classification systems in use in Western Europe (mainly EEC), North America, and Australia followed by chapters on the significance of the various classification parameters in combustion, liquefaction, and coking. These latter chapters are carefully done and particularly useful. In the introduction, the author makes the true but often unappreciated statement: "The full characterization of coal is a complex, time-consuming and expensive process. Therefore, a great deal of effort over the years has gone into developing systems for classification." She also carefully points out the distinction between scientific and commercial classifications and discusses the common problems of coals that do not fit into a given classification. There are only two areas where the book is weak. One is that references to published American work are very limited and selective compared to European and Commonwealth work. The other and perhaps more serious weakness is that throughout the book there seems to be a lack of appreciation of industrial and commercial practice in using coal. For example, the negative evaluations in the book of the usefulness and reproducibility of both maceral and reflectance analysis are not supported by the fact that these analyses have been standardized, are widely used, and are commercially available in the US.at least. Overall, however, the book is well-done. It is an excellent review of the problems and progress in coal classification and will be of value to coal scientists and engineers. This book will also be very useful in teaching where it should find a place as a supplemental text in a variety of courses dealing with coal. John C. Crelling, Southern Illinois University a t Carbondale
Coal Combustion Chemistry-Correlation Aspects. By E. J. Badin. Coal Science and Technology 6. Elsevier Science Publishers, B. V.: Amsterdam. 1985. 259 pp. $100.00. This book focuses on the chemistry of the mineral matter (termed inorganic impurities) in coal during, and as a result of, the combustion process. Part I, Chemistry and Coal Science Backgrounds, summarizes a substantial part of the literature and introduces some new correlations typically involving ash composition and ash behavior, while Part 11, Correlations, provides previously unpublished correlations based on the concepts described in the initial chapters. The 600 references (many are duplications) indicate the extensive coverage of the literature. Seven appendices and a good author and subject index complete the volume. The author spent much of his career with the TVA after obtaining degrees in chemical engineering and organic chemistry and doing academic teaching. A large part of the book is from a report prepared during his work with the TVA. A major purpose of the book is to provide suggestions for future work to alleviate the problems of fouling, slagging, and incomplete combustion associated with the mineral matter in the coal. An empirical approach is used throughout and seeks some relatively simple relationships to explain the interactions that take place. An introductory 'chapter briefly describes the basic and acidic oxides in mineral matter and some of their reactions. The book is then divided into two parts. Part I, Chemistry and Coal Science Backgrounds, includes Chapters 2-11. Chapter 2, Impurities of Major Abundance Elements in Coal, further describes the eight major acidic and basic oxides and introduces the first of an extended series of correlative plots. Chapter 3, Chemical Equilibrium Considerations, provides many examples from geochemical and other literature to indicate that the fly ash and other ash deposits have been at near-equilibrium conditions. Chapter 4, Basic and Acidic Cations and their Oxides, briefly reviews proton acidity and ionic potential concepts for distinquishing acids and bases and introduces additional correlations with Pauling electronegativities. Chapter 5, Reactions of Impurity Compounds during Coal Combustion, summarizes many references to thermal
Book Reviews reactions of mineral-matter constituents with each other and oxidizable material (pyrite) with oxygen. New correlations involving heat transfer and mineral-matter content are also given. Chapter 6, Catalysis and Inhibition of Coal Combustion by Impurity Compounds, summarizes the literature on acceleration of combustion by basic oxide material and inhibition or deceleration under a wide range of conditions with different materials. A global mechanism of combustion and inhibition is suggested, which involves the formation of peroxides, radical anions, and semiconducting mineral species. Chapter 7, Linear Free Energy Relationships (LFER), summarizes earlier work and introduces a series of new empirical LFERs involving two groups of the major oxides present in mineral matter. Chapter 8, Incomplete Combustion, very briefly refers to some of the work on soot formation and use of chemical additivies to enhance complete combustion. Chapter 9, Deposits of Inorganic Constituents, briefly outlines the deposit types and zones and provides some new correlations between the ash compositions and deposit behavior. Chapter 10, Sticky Alkalinities as Precursors to Deposit Formations, organizes over 40 references in several categories. Chapter 11, Known Empirical Parameters, summarizes about 30 different parameters relating ash composition to some form of ash deposition. Part 11,Correlations, begins with Chapter 12, Correlations of Sagging, High Temperature Fouling, and Combustion. Data for a number of TVA boilers were used to develop new correlations between composition and deposition-related phenomena. Chapter 13, Correlations for Incomplete Combustion, includes a chemical explanation and some additional correlations. The strengths of the book include the compilation of an extensive bibliography in the field that would be useful to anyone doing serious studies in the area. Each chapter has a summary at the end giving the highlights. A number of new correlations that have not appeared in the literature are presented and can make useful departure points for further thoughts on ash problems. On the other hand, the book is largely a noncritical compilation and the reader must do much of the evaluation. Many new correlations are offered in an empirical manner, and the interpretation of these is limited. In other cases, conclusions are made without sufficient supporting arguments to follow the logic. The wealth of information has led to brevity in summarizing much of it, and the book requires a background in the field to appreciate what is presented. An extended "Corrigenda" is included with the book, but does not include many typographical errors that a good spelling checker would have caught. This is only a minor distraction however. The book is recommended for inclusion in libraries where research in the field is being carried out to provide an organized set of references. Karl S. Vorres, Argonne National Laboratory
Catalysts for Fuels from Syngas. By G. Alex Mills. IEA Coal Research: London, Great Britain. 1988. 62 pp. 260. ISBN 92-9029-159-1. The goal of this report is to identify exploratory research results and new catalytic concepts whose development could lead to significant improvements in indirect coal liquefaction. To achieve this, an extensive body of open literature, including technical progress reports, has been reviewed, but the patent literature has not been considered. The report is centered on the second stage of indirect coal liquefaction involving the conversion of hydrogenlcarbon oxides mixtures into liquid fuels. The report opens with a concise, well-written introduction on reaction pathways (and associated thermodynamics) for forming chemicals and fuels from synthesis gas. The rest of the report consists of 37 pages of text divided into two main chapters on Oxygenate Fuels from Syngasand Hydrocarbon Fuels from Syngas and three short chapters on Scientific Design of Catalysts (1 page), Economic Considerations (3 pages), and Assessment and Recommendations (3 pages), followed by the extensive reference list (11pages). The reference list, principally citations from the last 5 years, is not intended to be, nor should it be considered to be, comprehensive in scope since it omits many primary references. However, it does quote most key research papers and reviews on the topics covered in this report.
Book Reviews The chapter discussing catalysts for synthesizing oxygenate fuels and chemicals considers both heterogeneous, both gas/solid and the newer liquid-phase dispersed gas/solid systems, and homogeneous catalysts, and a section on the application of biocatalysis to produce oxygenates is even included. The oxygenates that are emphasized include methanol, the higher linear alcohols, 2-methyl-1-propanol, MTBE, methyl formate, and acetic acid. The mechanistic perspectives that are given throughout the discussion are insightful. The discussion is generally balanced, and the tables and figures derived from the literature are informative and useful. However, the briefness of the discussion is annoying at times, e.g. in the catalyst preparation and reaction chemistry determination sections. In the presentation of a series of questions and answers presented by Chinchen et al. (1984) in regard to the structure of the active Cu/ZnO methanol synthesis catalyst, it is stated that the “critical oxidation state of copper in the catalyst is copper metal.” However, Chinchen et al. published two papers in 1986 where they indicated that these catalysts must contain oxidized copper species, likely on the metallic copper, in order to exhibit high methanol synthesis activity, which was supported by Denise et al. in 1987. This is alluded to in the following paragraph in the report, but the 1986 and 1987 references are not given. The discussion of hydrocarbon synthesis from H2/C0 is a concise, informative introduction and overview of Fischer-Tropsch (FT) catalysts and technology. A wide range of catalysts and processes are considered, but an emphasis is placed on iron catalysts, the ZSM-5 catalyst, and the Mobil methanol to gasoline (MTG) process. Also discussed are approaches to reaction enT process 80 that the selectivityis shifted toward gineering of the E waxes, isoparaffins, or low molecular weight olefins. Selectivity-controlling concepts considered include partial poisoning, use of slurry-phase FT reactors, and catalyst dispersion. As pointed out, driving forces are the desires to produce hydrocarbon fuels in a particular limited carbon number range in high yields and to reduce the methane yield below that predicted by the Anderson-Schulz-Flory distribution. In the final chapter, a list of catalytic improvements that could significantly contribute to more economical manufacture of synthetic liquid fuels from synthesis gas is given. Approximately 30 specific recommendationsfor new or current research directions are described in the categories of near-term, mid-term, and long-range applications, with an emphasis on opportunities for advancing catalytic technologies that improve the economics of indirect coal liquefaction. The report ends with a reference list that includes the titles of the quoted papers and reports, and this is very informative and useful €or a concise report such as this. This very readable report will be very useful as an introduction for researchers new to the general area of catalytic syntheses of liquid fuels from synthesis gas, as well as providing a valuable scientific and engineering overview of both hydrocarbon synthesis and the production of oxygenates for the established scientist. This report is recommended reading for everyone seeking potentially rewarding fields of research and insight into the scientific design of new and improved catalysts that can be coupled with improved process engineering. Richard G. Herman, Lehigh University
NMR Techniques and Applications in Geochemistry and Soil Chemistry. By M. A. Wilson. Pergamon Press: New York. 1989. 353 pp. $63.00. The stated purpose of this 353-page book is to attempt to remove, or at least reduce, the communication barriers between NMR spectroscopists and geochemists. This goal is substantially achieved, more 80 with respect to the spectroscopists,and the book is highly recommended as a useful reference for those wishing to pursue research of this type. The first four chapters serve as an introduction to the theory and practice of NMR spectroscopy. Elementary NMR Theory Applicable to Geochemistry (Chapter 1)dwells on such topics as the rotating frame, the Bloch equations, spin-spin and spin-lattice relaxation, and the chemical shift. Elementary NMR Practice Applicable to Geochemistry (Chapter 2) discusses the magnet, sample preparation, probes, and choice of experimental conditions in general terms. Solution NMR (Chapter 3) and Solid State
Energy & Fuels, Vol. 3, No. 5, 1989 649 NMR (Chapter 4) specifically discuss the essential aspects of data acquisition from the theoretical point of view. Thus, the solution N M R chapter involves summaries of proton decoupling, relaxation measurements/mechanisms, NOE, and polarization-transfer experiments, while the solid-state NMR chapter introduces the concepts of dipolar interactions, chemical shift anisotropy, cross polarization, dipolar dephasing, and the most common relaxation time measurements relevant to solids research. The remaining chapters dwell specifically on topics of geochemical interest. Minerals and Their Structure (Chapter 5) mainly involves %i and nAl NMR. Lignins, polysaccharidesand lipids are introduced in Precursors To Organic Matter in the Geosphere (Chapter 6). Whole Soil NMR (Chapter 7) treats the subject of soil organic matter as well as giving a brief overview of 31P, 16N, ?3i, and 27Al NMR of soils. Humic Substances (Chapter 8) goes into some detail on solution and solid-state NMR chemical shift analysis and the origins of structural variations in these materials. Oil Shale is discussed in Chapter 9. Its precursors and pyrolysis studies are discussed. Peat chemical shift assignments and relaxation data are covered in Chapter 10 (Peat). Chapter 11 (Coal) gives an overview of lignites, aromaticity trends, coalifcation processes, macerals, molecular motion, and difficulties in quantifying the solid-state NMR of these materials. Coal Derivatives (Chapter 12) discusses oxidation, functional group analysis by ‘H and 13CNMR, 0-alkylation, silylation, and related topics. Coal Conversion (Chapter 13) centers on the major topic of pyrolysis, including the fate of aromatic and aliphatic carbons during conversion and hydrogen transfer observed by using 2H NMR. The analysis of crude and refinery oils has been deliberately omitted by the author. Chapters range from 6 to 37 pages in length and, of necessity, are confined to the essentials of the topics under review. Within each chapter the references are generally comprehensive and as current as 1986. The monograph is not without its share of errors, omissions, and oversights, however, including typographical errors. The symbol H (instead of B ) is used to symbolize the magnetic field. In Chapter 1,the wrong coordinate system is shown in a figure describing the rotating frame coordinate system, the proper coordinates appearing later in Chapter 3. The explanation of the origin of the line-narrowing effects of MAS is inaccurate in parts of Chapter 4. The worst problems arise in references to spindiffusion processes, where poor wording and mistakes may take their toll on unsuspecting readers. The discussion is ambiguously and/or erroneously couched in terms of “polarization diffusing” between proton types instead of spin temperature arguments. The author also wrongly states the spin diffusion requires mutual bonds between nuclei to be operative. Discussion of the line widths in quadrupolar nuclei as a function of the asymmetry parameter is misleading. The index is somewhat incomplete. While a large number of terms are listed, some often-discussed subjects appear to be indexed only once, leaving many valuable references to be found by the reader. However, the organization of the chapters obviates this latter problem to some degree. As the author anticipated, in an attempt to cover such a broad spectrum of experimental and theoretical topics, the book has suffered from oversimplificationto some degree. Some topics are still probably beyond relevance to nonspectroscopists (detailed spinning sideband analysis and multiple pulse proton NMR) and some topics are inevitably dated in light of recent developments (e.g., rotor materials suitable for geochemical studies, rotor and probe designs, advances in heteronuclear NMR of minerals and coals, advances in determining correlations between Si and A1 chemical shifts and bond lengths/angles in minerals, etc). The greatest strengths of this book relate to its discussions of the applications of solid-state NMR and its extensive bibliographies at the end of each chapter. The applications chapters are succinct and well organized. Although there are many solution NMR discussions, solid-state NMR dominates the book. The liberal use of figures, tables, and spectra greatly adds to the book’s usefulness. Although those with geochemistry backgrounds only may have difficulty with the theoretical and/or experimental considerations, they will most certainly greatly benefit from the excellent discussionsof the applications. In this sense, the author has managed to substantially bridge the communications gap between the disciplines. David E. Axelson, NMR Technologies Inc.
650 Energy & Fuels, Vol. 3, No. 5, 1989 Natural Gas Substitutes from Coal and Oil. By Shaik A. Qadar. Coal Science and Technology No. 8. Elsevier: Amsterdam, The Netherlands. 1985. xvi + 413 pp. This book has the objective, in the author’s words, “to provide state-of-the-art knowledge on chemistry and technology-on producing natural gas substitutes” in a text to “servicethe needs of professionals in industry, R&D organizations and academic institutions”. In this reviewer’s opinion, this book fails to reach this objective due to faults in two areas: (1)Although written in 1985, the book does not reflect the basic fact that natural gas is now, and has been, in abundance-and the conversion of coal and oil to natural gas is of little interest, though synthesis gas manufacture is still useful. (2) The combination of a multitude of simple errors, major mistakes, lack of critical distinctions among processes, and outmoded examples of technology makes the work cumbersome to use and unreliable. The book covers a wide scope and includes a broad survey of the literature, covering the properties of coal and oil, the chemistry of coal and oil gasification, including catalysis, the technologies for gasifying coal and oil, and the processes for methanation to make a methane-rich product gas. With the possible exception of the first chapter (Properties of Coal), the book fails in many aspects: Some minor points first: The appearance of the text is annoying. There are many typographical errors, many drawings are not aligned properly on the pages, and the nonjustification on the right seems odd (I have never seen this in a book). A table (or tables) of nomenclature is missing-and is sorely needed. In some reaction rate equations, the text “C(0)” is unfamiliar, at least to me, and no units are given for the various , , ,C (H20),C, and expressions pertaining to concentrations,e.g. PCO.The use of both “p” and “P“in the same table, presumably to indicate partial pressure, is also puzzling. This type of presentation makes the use of the equations essentially impossible. The text offers no help on how the equations can be used. Much of the text (for example, the illustrations of oil refining) seems both nongermane to the subject and so old and out of date as to be completely useless or misleading. Some examples are given later. In the description of the various coal gasification processes, much of the information is simply wrong, even to disagreeing with some of the information given in the tables from the literature (which are correct). Greater care should have been exercised in editing the text. Certain major technologies are not even mentioned that were certainly well-known in 1984-1985. (The book‘s date is 1985.)
Book Reviews These include the Dow gasification process (the world’s largest commercial coal gasification plant) and the Union Carbide and Dow special amine processes for C02and Ha removal from gases. No mention is made of the split of the Shell-Koppers process in 1982 into the Shell process (Shell hterpational) and the Prenflo process (Krupp-Koppers). Each process is being developed separately. A few examples of the various technical errors will suffice (there are many more): A table shows correctly that the Stretford process removes H& (although without mentioning H2S is converted to sulfur) while the text lumps the Stretford process with the Benfield and Catacarb processes as containing KzCO3 and as a C02 and H2S removal process. (Why was not the Lo-Cat process-now more prevalent-mentioned?) The section on oil refining is really not germane to oil gasification. Processes such as gas oil hydrocracking make products best suited to making gasoline-not methane. In addition, for catalytic cracking, to say that “most of the cracking of the feed takes place in the cracker” is at best pedantic. The illustration of a “typical“ FCC process, which shows slurry decant oil in the recycle, is vintage early 1950s, hardly the “state of the art”. While the use of transfer line reactors is mentioned, there is no indication that they are the most useful form in which the synthetic zeolite-based catalysta (which are described briefly) are mainly used. Exxon’s catalytic gasification description is incorrect in at least three instances: (1) the company’s name is wrongly stated; (2) external heat is required (most ER&E papers shows a furnace on the recycle gas-the book does not); (3) there was never a pilot plant of 80 ton/day considered,much less ”operated successfully“, as is stated. For several processes (BGC-L, Texaco, Shell-Koppers, hightemperature Winkler, Westinghouse),the oxygen (and/or steam) consumptions given in the text are too high and the indicated ranges do not include the correct values given in the flow charta, which were derived from SFA Pacific’s report to EPRI. The name of the compound used in the Purisol process, denoted as NMP, is never correctly given: N-methyl-2-pyrrolidone. A small “n”is used once, replaced by “normal”,and one or two “r’s” are used. (“N” simply refers to the fact that the methyl group is connected to the nitrogen atom in the ring compound.) So much caution is required in using this text that I simply cannot recommend it-rather, it is a classic case of “let the reader beware”. Bernard Schulman, SFA Pacific Inc.
