This book is included in the Self Reliance Primitive Industry section.
PREFACE to Revised Edition.
During the decade since the publication of the first edition of this text, entitled Active Carbon, new vistas have unfolded for the industrial user of activated carbon. There has been a growing awareness of the many diverse forms of carbon usefulness; new processing techniques have been developed; and granular decolorizing carbons are now available commercially.
Such forward steps have increased the spheres of activity in the industrial use of activated carbon. They often introduce problems as to the right path to follow, however, and in many ventures the potential uset is denied the guidance that could be available. To explain, let us review the earlier history of adsorptive carbon in industry. We find that markets were first established in processes already using adsorbents, such as bone char and fullers earth, for the purification of sugar, fats, glycerol, etc. Within those processes there are but few trade secrets, and the success of the operation depends mainly on efficient methods of manufacture and marketing. Consequently the users welcomed any and all aid they could obtain
from suppliers of carbon. In general that attitude still holds in established applications and through such cooperation future growth can be assured in those markets.
Much growth, however, also can develop through participation in new products and in new processes. Unfortunately the opportunities for the supplier to contribute know-how in such ventures are frequently restricted because of the secrecy that so often surrounds the development. The reason for secrecy is understandable: Research and development costs are high, and these costs must be recouped in the relatively brief interval between the date a new product is placed on the market and the time for competition to catch up. Understandably, profit-minded industrialists, aware of ubiquitous competition, are unwilling to make premature disclosures even to those that could provide assistance.
An unfortunate consequence of this situation is that in many ventures that could become more efficient through the use of activated carbon, it may not be used; or it may be used ineffectively because of lack of know-how. In such situations a suitable written text can be useful because it asks no questions and carries away no data. This potential has guided the preparation of this revision. No attempt is made to furnish a definitive treatise; instead, the text is an introduction to basic principles and practices that should be considered in the industrial use of activated carbon. To that end the organization of subject matter has been altered and additional material is included.
Much of the added material is drawn from experiences during nearly fifty years' work with activated carbon. In 1915, I started with the West Virginia Pulp and Paper Company in its endeavor to pioneer the development of decolorizing carbons in this country. That endeavor culminated in the manufacture of Filtchar, the first commercial decolorizing carbon produced in America. From then till 1958, 1 participated in the research, manufacture, and marketing of other activated carbons including Nuchar and Suchar. On reaching retirement, I engaged in free-lance consulting. I am now associated with Barnebey-Cheney, a producer of activated carbon. I am also associated with the AMERICAN SOCIETY FOR TESTING AND MATERIALS in a research study to develop standard testing methods and nomenclature for activated carbon.
The experience of a single individual or group cannot cover an adequate understanding of all aspects of this many-sided subject. Therefore to provide a more comprehensive know-how I have sought the cooperation of others. In this I have had the assistance of sales, service, and research groups who have read sections of the manuscript, and supplied many valued suggestions. For making much of this help available, I am especially indebted to the following:
H. E. Pennington and H. B. Allport, of National Carbon Company; Jonathan C. Cooper, of Pittsburgh Chemical Company; R. W. Behrens, of Atlas Chemical Industries Inc.; Joseph M. Wafer, of West Virginia Pulp and Paper Company; H. L. Barnebey, of
Barnebey-Cheney; W. C. Bokhoven and Chr. van der Meijden, of N.V. Norit-Vereeniging Verkoop Centrale.
I am also grateful to many who have contributed much in varied ways: Some supplied information needed for presenting specialized topics; some assisted in the preparation and editing of the manuscript; some drew attention to important items that otherwise would have been overlooked; still others corrected errors in the presentation. The information has been gathered for a number of years and limitations of space and memory preclude naming all who contributed. A limited list includes:
Ted Barnebey, J. D. Clendenin, Joseph E. Drudy, Marjorie Halstrick, T. J. Hassler, W. F. Heneghan, Donald K. Luke, Jr., F. M. Middleton, John J. Schanz, Jr., F. R. Schwartz, G. H. Scheffler, Evan A. Sigworth, J. H. Steen, Philip L. Walker, Jr., and Frank M. Williams.
I have made extensive use of the Deitz Bibliography of Solid Adsorbents. As it is in the form of a collection of abstracts, this publication offers the reader a better view of the content of each article than does a bare reference to the original source. Similar use has been made of Chemical Abstracts.
A word of explanation is in order for the change in title. The designation Active Carbon, used in the earlier book, is favored in a number of scientific circles, whereas most industrial workers prefer the term Activated Carbon. Inasmuch as this text is focused primarily on industrial aspects, it seems fitting to call this work Activated Carbon.
The preface to the first edition is included to establish continuity, and also to give recognition to the many persons who assisted in the preparation of the original text.
Finally, I am happy to express my perennial gratitude to my wife,
Clara my partner in all undertakings.
JOHN W. HASSLER
June, 1963.
Preface to First Edition
This text has been prepared for operators and research workers in industry. I have attempted to survey principles and practices involved in the use of active carbon with the belief that an insight into the/ underlying features may suggest possible improvements in existing applications and also stimulate a search for new procedures.
The subject matter is grouped into three principal parts. Since many readers will be interested in only certain aspects, each part has been prepared so that it can be read independently of the others. Following an outline of the history and methods of manufacture, the next ten chapters discuss fundamental factors involved in adsorption by active carbon.
Applications are described in Chapters 13-30. A general outline is given of a number of applications, together with the specific objectives that are sought in each case. An operator will often find more helpful information from a description of how things are done in other processes than by copying what is being done elsewhere in his own field. With this in mind, some rather impractical procedures are described because they present novel approaches which could be useful in other applications.
The last four chapters cover experimental methods that have been found helpful in developing industrial applications.
Part of the information in this text has been drawn from personal experiences during thirty-five years' association with the manufacture and marketing of active carbon and this includes information received directly from other workers. To an even larger extent, the discussion is based on information in the literature. Some published data are obscure and other data are in dispute, so that it becomes the responsibility of the author to try and sift the facts. Consequently, the reader should be aware of the fact that the text contains not only facts, but also beliefs and opinions. The inquiring reader may find
statements that he will question. This is as it should be. Questions stimulate independent thinking and this is necessary to integrate new facts with older knowledge. New facts become useful when they enlarge our vision and provide a new approach to problems.
I wish to express appreciation to those authors and publishers who granted permission to reproduce data. 1 have been fortunate in having received suggestions, criticisms, and information from many workers who have specialized knowledge. A number of authors checked references to their work and others reviewed portions of the manuscript. Professors Elroy J. Miller, Harold J. Cassidy, and F. E. Bartell gave helpful suggestions for portions of the text dealing with fundamental aspects of adsorptive behavior. Dr. Homer Adkins reviewed the chapter on catalysis, and Dr. H. L. Riley the section on the structure of carbon. Dr. Arthur Grollman read the chapters dealing with biochemicals; solvent recovery was reviewed by Dr. A. B. Ray, and air purification by Mr. Hugh Porter. The chapters on the removal of toxic gases and that on laboratory methods of gas adsorption were reviewed by personnel of the Chemical Corps Technical Command. Mr. Robert H. Buckie reviewed the entire manuscript and assisted with a number of translations. Much information on industrial applications was furnished by my associates throughout the West Virginia Pulp and Paper Company, and 1 regret that space does not permit detailed mention of the many helpful individual contributions. Finally, I wish to express my deep appreciation to Mr. Joseph Wafer, for without his help and encouragement, the text would never have been started and carried through to completion.
JOHN W. HASSLER
February, 1951
CONTENTS
Chapter 1 - History and Market Review 1 Introduction 2 Early History 3 Recent History 4 Markets Chapter 2 - Elementary Aspects of Adsorption by Activated Carbon 1 Introduction 2 Surfaces and Interfaces 3 Rate of Adsorption 4 Separation by Adsorption 5 Characteristics of Adsorbable Gases and Vapors 6 Characteristics of Adsorbable Solutes 7 Hydrolytic Adsorption 8 Heat of Adsorption Chapter 3 - Gas and Vapor Systems 1 Protection against Toxic Gases 2 Air Purification and Recovery 3 Recovery of Solvent and Other Vapors 4 Separation of Hydrocarbon Gas Mixtures 5 Miscellaneous Applications Chapter 4 - The Survey of a New Venture 1 Introduction 2 Preliminary Survey 3 Decolorization 4 Tastes and Odors 5 Shelf Life; Stability of Product 6 Other Forms of Usefulness 7 Organic Colloids 8 Haze 9 Use of Activated Carbon in Conjunction with other Separations Chapter 5 - Unit Operations in Liquid Systems 1 Introduction 2 Batch-contact Unit Operation 3 Continuous Layer Filtration 4 Continuous Percolation through Granular Carbon 5 Reactivation 6 Storage and Handling Chapter 6 - Unit Processes 1 Introduction 2 Sugar 3 Sugars and Syrups from Conversion of Starch 4 Fats and Oils 5 Alcoholic Beverages 6 Purification of Water 7 Organic Colloids 8 Miscellaneous Foods 9 Organic Chemicals 1 10 Inorganic Chemicals and Metals 11 Dry Cleaning Solvents 12 Industrial and other Wastes 13 Analytical Applications 14 Miscellaneous Applications Chapter 7 - Evaluation of Activated Carbons for Liquid Systems 1 Introduction 2 Selecting an Activated Carbon 3 Quality Control Chapter 8 - Manufacture of Activated Carbon 1 General 2 Theories of Activation Chapter 9 - Nature of Activated Carbon 1 Introduction 2 Surface Tension 3 Capillary Condensation 4 Potential Theory 5 Langmuir Theory 6 Physical and Chemical Adsorption 7 Surface Area 8 Pore Structure 9 Qualitative Characteristics of Surfaces 10 Isotherms and Surface Variables 11 Hydrolytic Adsorption 12 Surface Oxides 13 Adsorption Associated with Chemical Change 14 The Adsorbed Layer 15 Orientation 16 Electrophoresis 17 Heat of Adsorption Chapter 10 - Desorption in Liquid Systems 1 General 2 Industrial Applications Employing Adsorption-Desorption 3 Possible Approaches to Further Study Chapter 11 - Contact Catalysis 1 Theories of Contact Catalysis 2 Applications of Activated Carbon as Catalyst Chapter 12 - Biochemical Aspects of Activated Carbon 1 Biochemistry 2 Pharmacology 3 Influence of Carbon on Biological Processes 4 Biochemicals Chapter 13 - Laboratory Procedures in Gas and Vapor Adsorption 1 Static Adsorption Methods 2 Dynamic Adsorption Methods 3 Miscellaneous Methods Chapter 14 - Laboratory Procedures for Liquid Systems 1 Introduction 2 Measurement Colorless Forms Contamination 3 Decolorization 4 Synthetic Test Solutions 5 Laboratory Procedures for Granular Activated Carbons 6 Specifications 7 Desorption Chapter 15 - Other Properties of Activated Carbon 1 Inorganic Constituents 2 pH of Carbon 3 Structural Characteristics 4 Some Miscellaneous Properties Chapter 16 - Final Gleanings 1 Introduction 2 Measurement of Adsorption 3 Items of Theoretical Interest 4 Surface Oxides 5 Manufacture of a New Carbon 6 Some Aspects of Future Research Appendix: I Glossary Appendix: II Manufacturers and Suppliers Appendix: III Epilogue Index
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