Phsicochemical Treatment of Hazardous Wastes - Chapter 1 potx

CRC PRESS Boca Raton London New York Washington, D.C. Physicochemical Treatment of Hazardous Wastes WALTER Z. TANG This book contains information obtained from authentic and highly regarded sources. Reprinted material is quoted with permission, and sources are indicated. A wide variety of references are listed. Reasonable efforts have been made to publish reliable data and information, but the author and the publisher cannot assume responsibility for the validity of all materials or for the consequences of their use. Neither this book nor any part may be reproduced or transmitted in any form or by any means, electronic or mechanical, including photocopying, microfilming, and recording, or by any information storage or retrieval system, without prior permission in writing from the publisher. The consent of CRC Press LLC does not extend to copying for general distribution, for promotion, for creating new works, or for resale. Specific permission must be obtained in writing from CRC Press LLC for such copying. Direct all inquiries to CRC Press LLC, 2000 N.W. Corporate Blvd., Boca Raton, Florida 33431. Trademark Notice: Product or corporate names may be trademarks or registered trademarks, and are used only for identification and explanation, without intent to infringe. Visit the CRC Press Web site at www.crcpress.com © 2004 by CRC Press LLC Lewis Publishers is an imprint of CRC Press LLC No claim to original U.S. Government works International Standard Book Number 1-56676-927-2 Library of Congress Card Number 2003055435 Printed in the United States of America 1 2 3 4 5 6 7 8 9 0 Printed on acid-free paper Library of Congress Cataloging-in-Publication Data Tang, Walter Z. Physicochemical treatment of hazardous wastes / Walter Z. Tang p. cm. Includes bibliographical references and index. ISBN 1-56676-927-2 (alk. paper) 1. Hazardous wastes—Purification. I. Title. TD1060.T35 2003 628.4 ′ 2—dc21 2003055435 TX69272_C00.fm Page 2 Wednesday, November 19, 2003 1:21 PM © 2004 by CRC Press LLC Dedication In memory of my father, Yuxiang Tang To my mother, Yongcui Hu, and To my children, William and Elizabeth, with love. TX69272_C00.fm Page 3 Wednesday, November 19, 2003 1:21 PM © 2004 by CRC Press LLC Preface On average, one ton of hazardous waste per person is generated annually by industries in the United States. Before the Resource Conservation and Recovery Act of 1984, hazardous wastes were improperly disposed of into the environment without any regulation. As a result, remediation of these contaminated sites and management of the ongoing hazardous waste sources are two major tasks to be achieved by treatment technologies. Due to the complex nature of the contaminated media and of the pollutants, environ- mental professionals are facing a host of questions, such as: What are the contaminated media? What is the nature of the pollutants? What are the concentrations of each pollutant? Among biological, physicochemical, or thermal technologies, if physicochemical processes are to be the solution, the treatability of various pollutants must be assessed before a process can be properly designed. This book systematically examines the treatability of hazardous wastes by various physicochemical treatment processes according to the Quantitative Structure–Activity Relationships (QSARs) between kinetic rate constants and molecular descriptors. I have attempted to achieve five major goals in this book: (1) fundamental theories of thermokinetics such as the transition state theory are used to integrate research findings in Advanced Oxidation Process (AOP) research; (2) reaction kinetics and mechanisms for each AOP are explained in terms of elementary reactions and the reactive center; (3) QSARs are introduced as methodologies to assess the treatability of organic compounds; (4) com- putational molecular descriptors such as the E HOMO and E LUMO are used extensively in the QSAR analysis; (5) the kinetics of various AOPs are com- pared so that the most effective process can be selected for a given class of organic pollutants. This book is divided into five parts. Chapter 1 to Chapter 4 define the hazardous waste problems and physicochemical approaches to solve these problems. Chapter 5 explains QSAR theory and its application to predicting molecular descriptors and hydroxyl radical reactions. Chapter 6 to Chapter 12 focus on each of the eight most important AOPs. Chapter 13 presents a major reductive treatment technology, zero-valence iron, and Chapter 14 compares each AOP according to its oxidation kinetics for specific classes of organic compounds. Each chapter begins with an introduction of the process and its historical development. The intention is to demonstrate how funda- mental sciences guide the search for these innovative technologies. Also, such introductions provide the information necessary for readers to delve into the literature for current research topics. Then, the principles of the process and the degradation kinetics, along with mechanisms of organic TX69272_C00.fm Page 5 Wednesday, November 19, 2003 1:21 PM © 2004 by CRC Press LLC pollutants are explained in terms of elementary reactions. These elementary reactions not only are important in assessing the treatability of organic pol- lutants using QSAR but are also critical in properly designing AOP processes. Finally, QSAR models are discussed to demonstrate the effect of molecular structure on their degradation kinetics and to rank the treatability of each organic compound. This book is intended for graduates, engineers, and scientists affiliated with universities, consulting firms, or national laboratories and who are dealing with the remediation of hazardous wastes in water, groundwater, and industrial wastewater. Due to the in-depth discussion of organic chem- istry, graduate students in environmental engineering and upper-level undergraduates in chemistry, chemical engineering, or environmental sci- ences who intend to enter environmental engineering should find it useful in their professional development. Students will learn a systematic approach to applying various sciences to the search for effective treatment technologies in terms of thermokinetic principles. Engineers will find the QSAR models extremely useful in selecting treatment processes for hazardous wastes according to the molecular structures of organic pollutants. Scientists in industrial and governmental laboratories, as well as designers and reviewers in remediation projects, will also find the book helpful in their efforts to restore our environment and keep it clean. During the 1970s, the U.S. Environmental Protection Agency designated phase-transfer technologies such as air stripping and activated carbon adsorption as the best available technologies. The search for mineralizing organic pollutants shifted the focus from phase-transfer technologies to oxi- dative technologies after the Hazardous Waste Amendment in 1984. As a result, AOPs were developed in laboratories, extended to pilot sites, and finally applied in the field from the 1980s to the present. The concept of an AOP includes any process that uses hydroxyl radicals as the predominant species; however, the concept failed to provide fundamental theories such as transition state theory to guide research communities in their search for the most effective oxidation processes. In a strict sense, then, AOP should be defined as a Catalytic Oxidation Process (COP), which would provide sound scientific footing for the search for innovative technologies. It is well documented that oxidants such as oxygen, ozone, and hydrogen peroxide oxidize organic pollutants slowly. It is only when they are catalytically decomposed into other active species such as hydroxyl radicals that the activation barrier of the activated complex can be significantly lowered. The catalysts normally used are ultraviolet photons, transition metals or their ions, ultrasound, and electrons. Increasing temperature and pressure can further enhance the catalytic effect. My research on AOPs began over 12 years ago at the University of Dela- ware. When I worked on the degradation of phenols by a visible photon/ CdS system, I had to wake up at midnight in order to take samples from a photocatalytic reactor because the reaction half time in degrading 0.001- M phenol is about 1 day. After I found that Fenton’s reagent was an extremely TX69272_C00.fm Page 6 Wednesday, November 19, 2003 1:21 PM © 2004 by CRC Press LLC fast process, I added hydrogen peroxide and ferrous ion separately to the reactor. The reaction half time reduced from one day to a few hours. When I added hydrogen peroxide first and then the ferrous sulfate, the reaction half time was reduced to a few minutes. It became clear to me during my investigation of the oxidation kinetics and mechanisms of chlorinated phe- nols by Fenton’s reagent that the efficiency of AOPs depends upon both the rate and the amount of hydroxyl radical generated and the molecular struc- ture of organic compounds. It has long been recognized that the treatability of different classes of organic compounds differs significantly. Furthermore, the treatability of chlorinated compounds within a given class of organic pollutants decreases as the chlorine content in a molecule increases. Indeed, the carbon in tetra- chloride has been oxidized by chlorine so much that it is even insensitive to hydroxyl radical attack. Therefore, elementary iron may be a more econom- ical way to reduce these pollutants rather than to oxidize them. To quantify the effect of chlorine, QSAR models are used to assess the effect of chlorine on molecular descriptors such as E HOMO and E LUMO . The treatability of organic compounds by each AOP, then, can be evaluated using QSAR models of the oxidation kinetic rate constants and molecular descriptors. Thermokinetics, group theory, and computational QSARs should find broad application in future research effort on AOPs for several reasons: (1) thermokinetics bridges thermodynamics and kinetics, which serve as the foundation for QSAR analysis; (2) group theory may offer kinetic calculations of activated complex for a given class of compounds, and the resulting degradation rate constants can be more accurately estimated; and (3) as more data regarding operational costs become available for each technology, QSARs may be incorporated into the calculations to estimate the operational cost of a specific compound. In addition, nanotechnology will become another research focus in the next decade to develop nanoparticles such as elementary iron, TiO 2 , nanofiltration, and electromembranes in the physico- chemical treatment of hazardous wastes. TX69272_C00.fm Page 7 Wednesday, November 19, 2003 1:21 PM © 2004 by CRC Press LLC About the Author Walter Z. Tang (B.S., Sanitary Engineering, Chongqing University, Chongqing, China, 1983; M.S., Environmental Engineering, Tsinghua Uni- versity, Beijing, China, 1986; M.S., Environmental Engineering, University of Missouri-Rolla, 1988; Ph.D., Environmental Engineering, University of Delaware, 1993) is an Associate Professor and Graduate Director for Environmental Engineering in the Department of Civil and Environmental Engineering at Florida International University (FIU), Miami, FL. He has been a registered Profes- sional Engineer in Florida since 1993. Dr. Tang has had extensive research experience over the past 14 years in the area of physicochemical treatment processes; environmental applications of aquatic, organic, catalytic, and col- loidal chemistry; advanced oxidation processes; environmental molecular structure–activity relationships (QSARs); and methodology in environmen- tal impact assessment. Dr. Tang is the principal investigator for 14 research projects supported by the U.S. Environmental Protection Agency, the National Institutes of Health, and the National Science Foundation. He has published 24 peer-reviewed papers and 41 conference papers, co-authored one book, and contributed one chapter to a book. Also, he has written graduate teaching manuals for three different graduate courses. He has been a referee for 12 journals and has served as a proposal reviewer for the NSF and the National Research Council. Dr. Tang has organized and presided over 11 sessions at various national and international conferences on advanced oxidation processes (AOPs) and was the invited speaker at Florida Atlantic University in 2001. Dr. Tang has supervised three post doctors, three visiting professors, and 35 graduate students in environmental engineering, and he has taught six undergraduate courses and nine graduate courses in the Department of Civil and Environmental Engineering at FIU. Dr. Tang received FIU’s Faculty Research Award in 1997, Faculty Teaching Award in 1998, and Departmental Teacher of the Year Award in 1998. He is a member of Chi Epsilon and is listed in Who’s Who in the World , Who’s Who in America , Who’s Who in Science and Engineering , and Who’s Who Among America’s Teacher s. Since 1994, Dr. Tang has been a co-principal investigator in joint research projects on AOPs with professors at Tsinghua University, Chongqing Uni- versity, and the Third Medical University of Chinese Military in Chongqing, China. As a research fellow in the China–Cornell Fellowship Program TX69272_C00.fm Page 9 Wednesday, November 19, 2003 1:21 PM © 2004 by CRC Press LLC supported by the Rockefeller Foundation, Dr. Tang offered six seminars at Tsinghua University. As a co-principal investigator from 1998 to 2002 of the Two-Bases Program sponsored by the China National Science Foundation, he advised a Ph.D. student at Tsinghua University on his dissertation: QSARs in the Anaerobic Degradability of Organic Pollutants. Chongqing University and Chongqing Jianzhu University granted the visiting professorship to Dr. Tang in 1999. He won six joint research projects sponsored by the Chinese Ministry of Education for Chongqing University. He was the invited speaker at Nankai University and Gansu Industry University in 2002 and at Wuhan University in 2003. He was named the Outstanding Chinese Scholar in the southern region of the United States and served as a Foreign Expert in the State Sunshine Program of China. The Chinese Ministry of Education invited Dr. Tang to Beijing as a state guest for the 50th anniversary of China National Day in 1999. TX69272_C00.fm Page 10 Wednesday, November 19, 2003 1:21 PM © 2004 by CRC Press LLC Acknowledgments I would like to acknowledge the contributions to this book made by my former graduate students: Tzai-Shian Jung, Angela Pierotti, Sangeeta Dulashia, Todd Hendrix, Ricardo Martinez, Lucero Vaca, Stephanie Tassos, Rena Chen, Taweeporn Fongtong, Jiun-Jia Hsu, Kenneth Morris, Jose Polar, Carlos Hernandez, and Jeffrey Czajkowski. I thank Jiashun Huang, Dennis Maddox, and Pia Hansson Nunoo for their many hours devoted to typing and drawing of the figures. I would like to thank all the students since 1991 at Florida International University (FIU) who took the graduate course, Advanced Treatment System, upon which the book is based. Students who assisted in this book include Bernine Khan, Lillian Costa-Mayoral, Christo- pher Wilson, and Oscar Carmona. A special acknowledgment goes to Geor- gio Tachiev of the Hemisphere Center for Environmental Technology at FIU for his constructive proofreading. I am grateful to Dr. C.P. Huang at the University of Delaware for intro- ducing me to the research of AOPs. Many QSAR models were developed through financial support from the U.S. Environmental Protection Agency, National Science Foundation, and National Institutes of Health, and their support is greatly appreciated. Thanks go to Mrs. Virginia Broadway at the USEPA for supporting and administrating five EPA fellowships to my stu- dents over the last decade. Dr. William Cooper and his colleagues are acknowledged for their work on high-energy electron beams. I would like to thank Dean Vish Prasad and Associate Dean David Shen of the College of Engineering at FIU for allowing me to complete the book. I am in debt to Gail Renard and Sara Kreisman, my book editors at CRC Press LLC, who provided excellent professional guidance and spent numerous days editing and proofreading the manuscript. TX69272_C00.fm Page 11 Wednesday, November 19, 2003 1:21 PM © 2004 by CRC Press LLC Table of Contents Chapter 1 Environmental Laws 1.1 Introduction 1.2 Environmental Laws 1.2.1 National Environmental Policy Act (NEPA) 1.2.2 Occupational Safety and Health Act (OSHA) 1.2.3 Clean Water Act (CWA) 1.2.4 Safe Drinking Water Act (SDWA) 1.2.5 Toxic Substances Control Act (TSCA) 1.2.6 Resource Conservation and Recovery Act (RCRA) 1.2.7 Hazardous and Solid Waste Amendments (HSWA) 1.2.7.1 Comprehensive Environmental Response, Compensation and Liability Act (CERCLA) 1.2.7.2 Superfund Amendments Reauthorization Act (SARA) 1.2.7.3 Clean Air Act (CAA) 1.3 Summary References Chapter 2 Environmental Hazardous Wastes 2.1 Introduction 2.2 Classification of Hazardous Pollutants 2.3 Sources of Hazardous Waste 2.4 Contaminated Media of Hazardous Wastes 2.4.1 Groundwater 2.4.2 Soil 2.4.3 Air 2.4.4 Sludge and Sediments 2.5 Distribution of Hazardous Pollutants in Contaminated Sites 2.5.1 National Priorities List Sites 2.5.1.1 Contaminants 2.5.2 Resource Conservation and Recovery Act 2.5.2.1 Contaminated Media 2.5.2.2 Contaminants 2.5.3 Underground Storage Tanks Sites 2.5.3.1 Contaminated Media 2.5.3.2 Contaminants 2.5.4 Department of Defense 2.5.4.1 Contaminated Media TX69272_bookTOC.fm Page 13 Thursday, November 20, 2003 10:55 AM © 2004 by CRC Press LLC [...]... 20, 2003 10 :55 AM 11 .3.4 Chlorinated C1 and C2 Volatile Organic Compounds 11 .3.5 Pentachlorophenate 11 .3.6 para-Nitrophenol 11 .3.7 para-Nitrophenyl Acetate 11 .3.8 Nitrobenzene 11 .3.9 Hydroxybenzoic Acid 11 .3 .10 Chlorinated Hydrocarbons 11 .3 .11 Chloroform 11 .3 .12 CFC 11 and CFC 11 3 11 .3 .13 Parathion 11 .3 .14 Hydantoin Chemicals 11 .3 .15 Methanol 11 .3 .16 Polymer and Iodide 11 .3 .17 Hydrogen Sulfide 11 .4 Engineering... Physical Processes 11 .2 .1. 1 Compression and Rarefaction 11 .2 .1. 2 Cavitation 11 .2 .1. 3 Microstreaming 11 .2 .1. 4 Cavitation Temperatures Probed by EPR 11 .2.2 Chemical Processes 11 .2.2 .1 H2–O2 Combustion in Cavitation Bubbles 11 .3 Degradation of Organic Pollutants in Aqueous Solutions 11 .3 .1 Phenol 11 .3.2 Monochlorophenols 11 .3.3 2-Chlorophenol © 2004 by CRC Press LLC TX69272_bookTOC.fm Page 21 Thursday, November... TX69272_C 01. fm Page 2 Tuesday, November 11 , 2003 11 :33 AM 2 Physicochemical Treatment of Hazardous Wastes CRAA 12 0 PPA Number of Laws 10 0 HWSA CERCLA CAAA 80 SARA SDWAA 60 RCRA CAA FWPCA 40 TSCA NEPA OSHA 20 0 18 70 18 80 18 90 19 00 19 10 19 20 19 30 19 40 19 50 19 60 19 70 19 80 19 90 2000 Years FIGURE 1. 1 Cumulative growth in federal environmental laws and amendments in the United States 1. 2 1. 2 .1 Environmental Laws National... 10 :55 AM 13 .2.2 Kinetics 13 .2.3 Adsorption 13 .2.4 Halogenated Hydrocarbons 13 .3 Degradation of Hazardous Wastes 13 .3 .1 Organic Pollutants 13 .3 .1. 1 Unsaturated Halogenated Compounds 13 .3 .1. 2 Saturated Halogenated Compounds 13 .3 .1. 3 Polychlorobiphenyls 13 .3 .1. 4 Nitroaromatic Compounds 13 .3 .1. 5 Nitrates and Nitrites 13 .3.2 Reduction of Heavy Metals 13 .3.2 .1 Chromium 13 .3.2.2 Arsenic 13 .3.2.3 Uranium 13 .3.2.4... References Chapter 10 Supercritical Water Oxidation 379 10 .1 Introduction 10 .2 Fundamental Theory 10 .2 .1 Characteristics of Supercritical Water 10 .3 SCWO Processes 10 .3 .1 Process Description of SCWO 10 .3.2 Effects of Operating Parameters of SCWO 10 .3.2 .1 Reaction Time 10 .3.2.2 Oxidants 10 .3.2.3 Temperature 10 .3.2.4 Pressure 10 .3.2.5 Catalysts 10 .4 Degradation of Hazardous Wastes in SCWO 10 .4 .1 Carbon... Improvement 13 .6 Summary References Chapter 14 Combinations of Advanced Oxidation 14 .1 14.2 14 .3 14 .4 Processes Introduction Fundamental Theory Process Description Degradation of Organic Pollutants 14 .4 .1 Phenol 14 .4 .1. 1 Comparison of Pseudo First-Order Kinetic Constant 14 .4 .1. 2 Cost Estimation 14 .4.2 para-Hydroxybenzoic Acid 14 .4.2 .1 Oxidation Processes Using UV Radiation 14 .4.2.2 AOPs Using Ozone 14 .4.2.3... Monoxide 10 .4.2 Aliphatic Organic Compounds 10 .4.3 Methane and Methanol 10 .4.4 Cresol 10 .4.5 Hydroxybenzaldehydes 10 .4.6 Phenol 10 .4.7 Substituted Phenols 10 .4.8 Mixture of Organic Pollutants 10 .4.9 Sludge 10 .5 QSAR Models 10 .5 .1 Aliphatic Compounds 10 .5.2 Aromatic Compounds 10 .6 Summary References Chapter 11 Sonolysis 423 11 .1 Introduction 11 .2 Fundamental Processes in Sonochemistry 11 .2 .1 Physical... 13 .3.2.4 Mercury 13 .3.3 Reduction of Inorganic Pollutants 13 .3.3 .1 Chlorine 13 .4 QSAR Models 13 .5 Engineering Applications 13 .5 .1 Continuous and Funnel-and-Gate PRBs 13 .5 .1. 1 Characteristics of Reactive Media 13 .5 .1. 2 Types of Reactive Media 13 .5.2 Monitoring 13 .5.2 .1 Planning the Monitoring Effort 13 .5.2.2 Compliance Monitoring 13 .5.2.3 Performance Monitoring 13 .5.2.4 Microbial Characterization 13 .5.3 Engineering... 10 :55 AM 14 .4.3 Chlorophenols 14 .4.3 .1 Comparison of Various AOPs 14 .4.3.2 UV/H2O2 System 14 .4.3.3 Photo–Fenton’s Reagent System 14 .4.3.4 UV/O3 System 14 .4.3.5 pH Effect on the Ozone Oxidation of Chlorophenols 14 .4.4 Reactive Dyes 14 .4.4 .1 Ozone Treatment 14 .4.4.2 UV/TiO2 14 .4.5 1, 3,5-Trichlorobenzene (TCB) and Pentanoic Acid (PA) 14 .4.6 Polycyclic Aromatic Hydrocarbons (PAHs) 14 .4.6 .1 Anthracene 14 .4.6.2... References Chapter 12 High-Energy Electron Beam 4 61 12 .1 Introduction 12 .2 Chemistry of Aqueous Electrons 12 .2 .1 Formation of Radical Species 12 .2.2 Hydroxyl Radical 12 .2.3 Hydrogen Peroxide 12 .2.4 Aqueous Electron 12 .2.5 Hydrogen Radical 12 .3 Irradiation of Toxic Organic Chemicals in Aqueous Solutions 12 .3 .1 Saturated Halogenated Methanes 12 .3.2 Unsaturated Halogenated Ethenes 12 .3.3 Substituted Benzenes 12 .3.4 . Hydroxybenzoic Acid 11 .3 .10 Chlorinated Hydrocarbons 11 .3 .11 Chloroform 11 .3 .12 CFC 11 and CFC 11 3 11 .3 .13 Parathion 11 .3 .14 Hydantoin Chemicals 11 .3 .15 Methanol 11 .3 .16 Polymer and Iodide 11 .3 .17 Hydrogen. 11 .2 .1 Physical Processes 11 .2 .1. 1 Compression and Rarefaction 11 .2 .1. 2 Cavitation 11 .2 .1. 3 Microstreaming 11 .2 .1. 4 Cavitation Temperatures Probed by EPR 11 .2.2 Chemical Processes 11 .2.2 .1. LLC 11 .3.4 Chlorinated C 1 and C 2 Volatile Organic Compounds 11 .3.5 Pentachlorophenate 11 .3.6 para -Nitrophenol 11 .3.7 para -Nitrophenyl Acetate 11 .3.8 Nitrobenzene 11 .3.9