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Book Reviews Developments in Coal-Liquid Mixtures. Edited by Kelly Thambimuthu. IEA Coal Research: London, 1994. IEACW 69, ISBN 92-9029-232-6. 79 pp. E180. This report is a comprehensive review of the technical and economical aspects of coal-water fuel (CWF) preparation and utilization. The author has significant experience in the area of CWF characterization and utilization including an excellent published review of the combustion of coal-liquid mixtures. The author’s familiarity with the subject matter is demonstrated by the range of topics covered in the report. The specific topics addressed include (1) CWF preparation and characteristics, (2) fuel storage, handling, and transportation, (3) atomization, combustion, and product formation, (4) utilization of CWF in boilers and plant conversion, (5) economics and market opportunities, and (6) the status of national activities. The information is presented in such a manner as to be readily understandable t o those not familiar with the production and utilization of coal-water fuels. For those who are currently, or have been, involved in the study of CWFs, the report contains information on past, present, and future CWF production technologies utilized internationally. The section on CWF preparation and characteristics discusses the effect of coal type and properties, specifically, ash content and particle size, on the physical characteristics of the fuel. The importance of viscosity and stability is stressed appropriately so, since these are very important in determining atomization and transportation behavior. The section on atomization, combustion, and product formation discusses the importance of droplet size distribution, as a function of atomization quality, on combustion performance. Of particular importance is the discussion regarding the formation and abatement of gaseous pollutants (NO, and SOz). Given the increasing requirements for the reduction of gaseous pollutants from coal-fired utility boilers, the use of CWFs may become more environmentally attractive. The utilization of CWF in a variety of systems-oil- and coal-designed steam boilers, industrial heating and furnace applications, fluidized bed combustion, gasification, and heat engines-is discussed. This discussion is particularly informative for those who may be familiar with CWFs in specific applications. Included in the report is a discussion of the economics and market opportunities for what might be considered traditional applications of CWF technology. Of particular interest in the future of CWF technology is the utilization of waste fresh and waste coal fines produced during wet coal cleaning for CWF production. The author notes that cost estimates by Science Applications International Corp. indicate that the cost of producing a CWF from fresh waste fines is approximately 2 / 3 that of producing a premium quality CWF. In some cases the quality of waste fines and particle size distribution require relatively little processing depending upon the system in which the fuel will be used. The Pennsylvania Electric Co. (Penelec) has successfully cofired pulverized coal and CWF produced from fresh waste fines. Pulverized coal accounted for 80% of the total thermal input. A stable flame, acceptable burnout, and a reduction in NO, production was observed with no boiler derating. Few, if any, problems with fuel handling and atomization were encountered. An advantage of cofiring CwFs is that lower quality CWFs can be successfully fired without adverse effects to the boiler. This reduces the cost of fuel preparation and expands the coal selection possible for feedstock. In addition, the firing capacity of the facility may be expanded beyond the limits imposed by the facilities’ pulverizers since a portion of the thermal input is derived from CWF. The fact that cofiring CWF results in a reduction in NO, is also attractive. Some discussion of the advantages of cofiring CWFs in this publication would have been appropriate. The success of Penelec’s demonstration adds a new dimension to 0887-0624/95/2509-0566$09.00/0
the possibilities for CWF technology now and in the future and makes the publication of this report timely and informative. Sharon Falcone Miller, The Pennsylvania State University EF950012J
Natural Gas Conversion. 11. Studies in Surface Science and Catalysis. Vol. 81. H. E. Curry-Hyde and R. F. Howe, Editors; Elsevier: New York, 1994. $242.75. 579 pages. Developing the science and technology for economically competitive conversion of natural gas t o liquid fuels and commodity chemicals presents perhaps the most important current energy-related R&D challenge. Recent discoveries of enormous gas deposits now rival or exceed petroleum resources worldwide. Many deposits are in remote locations. This volume, Proceedings of 3rd Natural Gas Conversion Symposium, Sydney, Australia, July 1993, presents a stateof-the-art review by a n international array of experts. Six plenary and three keynote lectures are followed by 86 papers contributed from 18 countries. While there is concern with fundamental identification of catalytically active sites and reaction mechanisms, the main thrust is the search for improved catalysts and for new process engineering (e.g., fluid bed reactors; offshore plants) that will permit gas conversion to compete with petroleum. The anatomy of process economics received special recognition, emphasizing the criticality of production of higher-priced products. Oxidative coupling of methane, OCM, half the book, is approached from the concept of indirect formation of methyl radicals on catalyst surfaces, with further reactions of the radicals in the gas phase. The general objective is to exceed the present limit of 80% selectivity a t 20% conversion to C2products. OCM performances and physicochemical characterizations are reported for catalyst ideas involving combinations of some 30 different elements from every group in the periodic table. Important insight into catalytic functionality is reported, e.g., evidence that peroxide ions may serve as the active form of oxygen on basic oxides. Incremental selectivity improvements is reported by catalyst formulations and by prevention of loss of selectivity in secondary reactions. A new approach to improve economics is based on reaction engineering. Considerable progress is reported in experimental tests using fluid beds, or a stirred jet reactor, or membrane distribution of oxygen, or reactor modeling. The second main topic of this book is production of synthesis gas (CO + HP)and its conversion to oxygenate and hydrocarbon products. Here the search is both for new technology and improvements to present commercial processes. New technology is presented for production of syngas from CH4: by CO2 reforming; by reforming in molten fuel cell; and there is renewed interest in partial oxidation. In regard to methanol synthesis, newly available commercial catalysts were reported t o provide some improvements. Various experimental catalysts provided information on mechanisms and micromorphologxal relationships. Methanol synthesis improvements were sought by ozone sensitization, by variation in reactor packing, and by modeling. Of interest is the description of a test plant, constructed by BHP as part of a strategy to test promptly new technology on a large scale. I t is visualized that it will also provide the basis for possible offshore plant installations. Of importance in production of higher value products, advances were reported in conversion of methanol to Cz + C3 olefins-91% molar selectivity at 100%conversion using molecular sieves SAPO 17 or 34. New information is presented on
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Energy & Fuels 1995, 9, 567 Fischer-Tropsch chemistry for various catalysts based on acidic and molecular sieves supports as well as cobaltcontaining catalysts of interest because of their high activity and low rejection of oxygen as COz. The economics of syncrude production using FT synthesis on a floating platform at a remote offshore field is outlined. Regarded as an important improvement is a new commercial operation of low-temperature slurry-phase FT, reported by SASOL to lower plant investment as well as provide a unique products distribution. Of considerable interest is an up-to-date account provided of the Shell Middle Distillate Synthesis in Malaysia. Thirdly, progress is reported on various topics including direct conversion of methane to organic acids, to acetylene, and other chemicals; use of methane in fuel cells; reduction by CH4 of NO,, new ideas in methane functionalization by homogeneous activation by Pt or Pd complexes. Considerable interest has been expressed in the mercuric ion catalyzed sulfuric acid oxidation of methane to methanol via methyl bisulfate. Plenary Lectures: Recent Advances in Oxidative Coupling of Methane, by Lunsford; The Relevance of Combustion Theory to the Homogeneous Oxidation of Methane, by Gray, Griffiths and Foulds; Aspects of CO2 Reforming of Methane, by RostrupNielsen; Conversion of Natural Gas t o Transportation Fuels via the Shell Middle Distillate Synthesis Process, by Van Wedhem and Senden; New Uses of Methane, by Fujimoto; Current Ideas and Future Prospects in Metal-Catalyzed Methane Conversion, by Crabtree. Keynote Lectures: Natural Gas; Fuel or Feedstock? by Axelrod, Gaffney, Pitchai, and Sofranko; Catalytic Reduction of Nitrogen Oxides with Methane in the Presence of Excess Oxygen, by Armor; Conversion of Natural Gas t o Electricity in Fuel Cells, by Foger. Contributed Papers Topics: Oxidative Coupling; Synthesis Gas Chemistry; Methanol Synthesis and Conversion; FischerTropsch Chemistry: Heterogeneous Methane Activation; Homogeneous Methane Activation; Natural Gas Conversion Related Processes. G. Alex Mills, University of Delaware EF9405768
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equations of state, phase behavior, distillation, critical properties, hydrogen solubility, thermal properties, viscosity, and other properties. It does not go into depth on any of them but does a good job of describing the compromises that sometimes have to be taken t o understand and predict properties of such complex mixtures as petroleum residues and heavy oils. Chapters 3 and 4 cover the chemistry and kinetics of upgrading reactions, including both thermal and catalytic reactions. The coverage is broad, going all the way from individual chemical reaction steps and chemical intermediates, through diffusion in catalyst pores, and on t o heat and mass transfer in plug flow and continuously stirred reactors, with many other relevant subjects also covered. The discussion concentrates on all of the aspects important for heavy oils, something which is lacking in texts which cover the subjects in more depth. The second half of the book, Chapters 5-8, covers the various conversion options. It does not cover other options besides conversion, such as asphalt, fuel oil, or solvent deasphalting. The options are divided into hydroconversion processes, thermal and coking processes, fluid catalytic cracking of residues, and hydrotreating of cracked products. Only processes that are commercially practiced or have been demonstrated on a semicommercial scale are covered. The emphasis in the discussion is on Canadian heavy oil applications. For instance, hydroconversion is said to be favored in process selection. That may be true in Alberta, but the majority of new refinery resid conversion capacity worldwide is in coking and resid cat cracking. Nevertheless, the discussion of the alternatives is good, builds well on the background in the first half of the book, and nicely compares the strengths and weaknesses of the alternatives. Many process flow diagrams are included. The discussion covers product yields, liquid product (and solid product for coking) qualities, reactor hydrodynamics, operability, and environmental impact. Although there are better references on many of the subjects, such as catalysis, chemical composition, and refining, this book pulls together the aspects of all of these and other subjects that are important for upgrading petroleum residues and heavy oils. It has an excellent bibliography that covers the literature through 1993. The book should be useful for everyone interested in the subject. William N. Olmstead, Exxon Research & Engineering Co.
Upgrading Petroleum Residues and Heavy Oils. By Murray R. Gray. Marcel Dekker, Inc.: New York, 1994; 348 pp. $135.
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Heavy oils and distillation residues from either heavy oils or conventional oils are the most difficult petroleum feeds to upgrade to clean, more valuable products. They are also increasing in importance as lighter crude oil resources are preferentially being depleted. This book, which is in the Chemical Industry book series, attempts to cover all of the important aspects of upgrading, from the chemical constituents of the feed to the commercially available processes that are practiced today. It does a good job, and it should be useful for the targeted general technical audience of chemists in refinery laboratories, process and design engineers, and researchers. Although the concepts are relevant to oils worldwide and there are examples of oils from many countries, the author concentrates on the abundant Canadian heavy oils in both the data cited and the discussion. There are practical problems a t the end of each chapter that are good for either advanced engineering students, new practitioners in this or related fields, or those who want t o brush up on the application of important concepts. Chapter 1 describes the properties and chemical composition. It is technically the weakest chapter in the book. The chemical structures are poorly drawn and contain some mistakes. For anyone who is interested in a more in depth analysis on this subject, a previous book in this series, Composition and Analysis of Heavy Petroleum Fractions, by K. H. Altgelt and M. Boduszynski, is superior. The chapter is sufficient for those who need an overview and background for the rest of this book. Chapter 2 describes the thermodynamic and transport properties. It includes discussion of
Petroleum Refining Technology and Economics. By James H. Gary and Glenne E. Handwerk. Marcel Dekker, Inc.: New York, 1994; 463 pages. Third edition. ISBN 0-82479157-6. $59.75.
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This is the third edition of this text which deals with all the major refining operations from refinery products to economic evaluations. The major revisions cover the impact of the Clean Air Acts Regulations and the options that refiners have to meet the regulations. Besides the normal refinery operations, the 18 chapters of the book include those on refinery products, feedstocks, product blending, supporting processes, lube oils, petrochemical feedstocks, additive production, and two important chapters dealing with cost and economics. In addition, there are 5 appendices dealing with definitions of refinery terms, physical properties, routine analysis of selected crude oils, and photos of several major refinery units. The appendices also include a detailed economic evaluation problem which should be very useful to those new to refinery operations. There are sample case study problems which should be useful t o academic as well as industrial readers. After introductory chapters on refinery products and feedstocks, the next two deal with the thermal operations, distillation and coking, and a case study problem on delayed coking. The next 6 chapters cover the catalytic processes of catalytic cracking, hydroprocessing and resid processing, hydrotreating, reforming and isomerization, and alkylation and polymerization. Each of these includes chapter-ending case studies and
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additional problems, all pertinent to the text. There are also suggested additional reading for more detailed information as well as chapter references. Chapter 12 has an interesting gasoline blending problem which should give the reader some feel for the complexity in meeting specifications and environmental issues required by the Clean Air Act, such as balancing octanes, oxygenates, aromatics, and vapor pressure. Chapter 13 deals briefly in part with the environmental issues of waste water, air quality, and noise. Chapter 16 is noteworthy as it covers the production and use of ethers and alcohols, additives for octane control, and for meeting fuel oxygen level regulations for controlling carbon monoxide emissions in some parts of the country. The production of isobutylene from catalytic cracking and commercial dehydrogenation processes is also discussed briefly along with some economics on ether and isobutylene production. The last two chapters dealing with capital cost estimation and economic evaluation are probably one of the unique features of the book. The authors recognize that each refiner has their own system for doing both estimations and evaluations but the definitions and techniques discussed and the
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examples in these two chapters may prove to be most useful for the those being introduced to the subjects for the first time. This book should be useful as a reference for those experienced in refinery operations who wish t o refresh their memories in those areas where they have not been directly involved. It should also be helpful to the uninitiated who are just beginning a career in the field. The case studies and the problems a t the end of most chapters should be useful for classroom instruction. After three editions, the authors have eliminated most typographical errors, although the tables in the text pages 17 and 19 are misnumbered. If there is one disappointment with the book, it would be in the dated references and suggested readings. There have been a number of new publications on specific refinery operations which are more current than many of those cited in the text. The book is well written and easily read and will be valuable reference for any library. Ralph J. Bertolacini, University of Delaware EF940574N
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