Mercury Control E-Book
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- Herausgeber: Wiley-VCH
- Kategorie: Wissenschaft und neue Technologien
- Sprache: Englisch
This essential handbook and ready reference offers a detailed overview of the existing and currently researched technologies available for the control of mercury in coal-derived gas streams and that are viable for meeting the strict standards set by environmental protection agencies.
Written by an internationally acclaimed author team from government agencies, academia and industry, it details US, EU, Asia-Pacific and other international perspectives, regulations and guidelines.
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Veröffentlichungsjahr: 2014
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Table of Contents
Cover
Related Titles
Title Page
Copyright
List of Contributors
Mercury R&D Book Foreword
Preface
List of Abbreviations
Part I: Mercury in the Environment: Origin, Fate, and Regulation
Chapter 1: Mercury in the Environment
1.1 Introduction
1.2 Mercury as a Chemical Element
1.3 Direct Uses of Mercury
1.4 Atmospheric Transport and Deposition
1.5 Atmospheric Reactions and Lifetime
1.6 Mercury Biogeochemical Cycling
References
Chapter 2: Mercury and Halogens in Coal
2.1 Introduction
2.2 Mercury in U.S. Coals
2.3 Mercury in International Coals
2.4 Halogens in Coal
2.5 Summary
Acknowledgments
References
Chapter 3: Regulations
3.1 U.S. Regulations
References
Chapter 4: International Legislation and Trends
4.1 Introduction
4.2 International Legislation
4.3 Regional and National Legislation
4.4 Summary
References
Part II: Mercury Measurement in Coal Gas
Chapter 5: Continuous Mercury Monitors for Fossil Fuel-Fired Utilities
5.1 Introduction
5.2 Components of a CMM
5.3 Installation and Verification Requirements
5.4 Major CMM Tests
5.5 CMM Vendors
References
Chapter 6: Batch Methods for Mercury Monitoring
6.1 Introduction
6.2 Wet Chemistry Batch Methods
6.3 Dry Batch Methods
6.4 Recommendations
References
Part III: Mercury Chemistry in Coal Utilization Systems and Air Pollution Control Devices
Chapter 7: Mercury Behavior in Coal Combustion Systems
7.1 Introduction
7.2 Coal Combustion Boilers
7.3 Mercury Chemistry in Combustion Systems
7.4 Air Pollution Control Devices on Utility and Industrial Boilers
7.5 Mercury Behavior in Coal-Fired Boilers
7.6 Summary
References
Chapter 8: Gasification Systems
8.1 Principles of Coal Gasification
8.2 Gasification Technologies Overview and Gasifier Descriptions
8.3 Gasification Applications and Downstream Gas Cleanup and Processing
8.4 Mercury Transformations and Fate
8.5 Hg Measurement in a Reducing Environment
8.6 Hg Control Technologies for Gasification
8.7 Hg and the MATS Rule for Gasifiers
References
Chapter 9: Mercury Emissions Control for the Cement Manufacturing Industry
9.1 Introduction
9.2 Cement Manufacturing Process Description
9.3 State of Knowledge on the Source and Behavior of Mercury in the Cement Kiln System
9.4 Mercury Emissions Control Solutions in the Cement Industry
9.5 Conclusions
References
Part IV: Mercury Research Programs in the United States
Chapter 10: DOE's Mercury Control Technology Research, Development, and Demonstration Program
10.1 Introduction
10.2 Background
10.3 Summary
Disclaimer
References
Chapter 11: U.S. EPA Research Program
11.1 Introduction
11.2 Congressionally Mandated Studies
11.3 Control Technology from Work on Municipal Waste Combustors (MWCs)
11.4 Mercury Chemistry, Adsorption, and Sorbent Development
11.5 Coal Combustion Residues and By-Products
11.6 EPA SBIR Program
References
Chapter 12: The Electric Power Research Institute's Program to Control Mercury Emissions from Coal-Fired Power Plants
12.1 Introduction
12.2 Co-Benefits of Installed Controls
12.3 Sorbent Injection
12.4 Boiler Chemical Addition
12.5 Novel Concepts for Mercury Control
12.6 Integration of Controls for Mercury with Controls for Other Air Pollutants
12.7 Summary
References
Part V: Mercury Control Processes
Chapter 13: Mercury Control Using Combustion Modification
13.1 Mercury Speciation in Coal-Fired Power Plants without Added Catalysts
13.2 Role of Unburned Carbon in Mercury Oxidation and Adsorption
13.3 Synergistic Relationship between UBC and Calcium in Flyash
13.4 Potential Combustion Modification Strategies to Mitigate Mercury Emissions
13.5 Effects of Combustion Modifications on Mercury Oxidation across SCR Catalysts
References
Chapter 14: Fuel and Flue-Gas Additives
14.1 Background
14.2 Summary
References
Chapter 15: Catalysts for the Oxidation of Mercury
15.1 Introduction
15.2 Hg Oxidation and Affecting Parameters
15.3 Conclusions and Future Research
References
Chapter 16: Mercury Capture in Wet Flue Gas Desulfurization Systems
16.1 Introduction
16.2 Fate of Net Mercury Removed by Wet FGD Systems
16.3 Mercury Reemissions
16.4 Effects of Flue Gas Mercury Oxidation Technologies on FGD Capture of Mercury
References
Chapter 17: Introduction to Carbon Sorbents for Pollution Control
17.1 Carbon Materials
17.2 Carbon Activation
17.3 Carbon Particle Shapes and Forms
17.4 Activated Carbon Applications
17.5 Activated Carbon Properties in Emission Systems
17.6 Summary
References
Chapter 18: Activated Carbon Injection
18.1 Introduction
18.2 The Activated Carbon Injection System
18.3 Factors Influencing the Effectiveness of Activated Carbon
18.4 Balance-of-Plant Impacts
18.5 Future Considerations
References
Chapter 19: Halogenated Carbon Sorbents
19.1 Introduction
19.2 Application of Activated Carbon for Mercury Control
19.3 Development of Halogenated Activated Carbon
References
Chapter 20: Concrete-Compatible Activated Carbon
20.1 Introduction
20.2 Concrete-Compatibility Metrics
20.3 Production of Concrete-Compatible Products Including C-PAC™
20.4 C-PAC™ Specification
20.5 Concrete Compatibility Test – Field Fly Ash/C-PAC™ Mixture
References
Chapter 21: Novel Capture Technologies: Non-carbon Sorbents and Photochemical Oxidations
21.1 Introduction
21.2 Non-carbon Sorbents
21.3 Photochemical Removal of Mercury from Flue Gas
Disclaimer
References
Chapter 22: Sorbents for Gasification Processes
22.1 Introduction
22.2 Background
22.3 Warm/Humid Gas Temperature Mercury Sorbent Capture Techniques
22.4 Cold Gas Cleanup of Mercury
22.5 Summary
Disclaimer
References
Part VI: Modeling of Mercury Chemistry in Air Pollution Control Devices
Chapter 23: Mercury-Carbon Surface Chemistry
23.1 Nature of the Bonding of Mercury to the Carbon Surface
23.2 Effects of Acid Gases on Mercury Capacities on Carbon
23.3 Kinetic HCl Effect
23.4 Summary
References
Chapter 24: Atomistic-Level Models
24.1 Introduction
24.2 Homogeneous Mercury Oxidation Kinetics
24.3 Heterogeneous Chemistry
24.4 Conclusions and Future Work
References
Chapter 25: Predicting Hg Emissions Rates with Device-Level Models and Reaction Mechanisms
25.1 Introduction and Scope
25.2 The Reaction System
25.3 Hg Transformations
25.4 Summary
References
Index
Disclaimer
End User License Agreement
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Guide
Cover
Table of Contents
Mercury R&D Book Foreword
Preface
Part I: Mercury in the Environment: Origin, Fate, and Regulation
Chapter 1: Mercury in the Environment
List of Illustrations
Figure 1.1
Figure 2.1
Figure 2.2
Figure 2.3
Figure 2.4
Figure 2.5
Figure 2.6
Figure 4.1
Figure 4.2
Figure 4.3
Figure 5.1
Figure 5.2
Figure 5.3
Figure 5.4
Figure 5.5
Figure 5.6
Figure 5.7
Figure 5.8
Figure 5.9
Figure 5.10
Figure 5.11
Figure 5.12
Figure 6.1
Figure 6.2
Figure 6.3
Figure 6.4
Figure 6.5
Figure 7.1
Figure 7.2
Figure 7.3
Figure 7.4
Figure 7.5
Figure 7.6
Figure 7.7
Figure 7.8
Figure 7.9
Figure 7.10
Figure 8.1
Figure 9.1
Figure 9.2
Figure 9.3
Figure 9.4
Figure 9.5
Figure 9.6
Figure 9.7
Figure 10.1
Figure 10.2
Figure 10.3
Figure 10.4
Figure 10.5
Figure 10.6
Figure 12.1
Figure 12.2
Figure 12.3
Figure 12.4
Figure 12.5
Figure 12.6
Figure 12.7
Figure 12.8
Figure 12.9
Figure 12.10
Figure 12.11
Figure 12.12
Figure 12.13
Figure 12.14
Figure 12.15
Figure 12.16
Figure 12.17
Figure 13.1
Figure 13.2
Figure 13.3
Figure 13.5
Figure 14.1
Figure 14.2
Figure 14.3
Figure 14.4
Figure 15.1
Figure 16.1
Figure 16.2
Figure 16.3
Figure 16.4
Figure 16.5
Figure 16.6
Figure 17.1
Figure 17.2
Figure 17.3
Figure 17.4
Figure 17.5
Figure 17.6
Figure 17.7
Figure 17.8
Figure 17.9
Figure 17.10
Figure 17.11
Figure 18.1
Figure 18.2
Figure 18.3
Figure 18.4
Figure 18.5
Figure 18.6
Figure 18.7
Figure 18.8
Figure 18.9
Figure 19.1
Figure 19.2
Figure 20.1
Figure 20.2
Figure 20.3
Figure 20.4
Figure 20.5
Figure 20.6
Figure 20.7
Figure 20.8
Figure 20.9
Figure 20.10
Figure 20.11
Figure 20.12
Figure 20.13
Figure 22.1
Figure 22.2
Figure 22.3
Figure 22.4
Figure 23.1
Figure 23.2
Figure 23.3
Figure 24.1
Figure 24.2
Figure 24.3
Figure 24.4
Figure 24.5
Figure 24.6
Figure 25.1
Figure 25.2
Figure 25.3
Figure 25.4
Figure 25.5
Figure 25.6
Figure 25.7
Figure 25.8
List of Tables
Table 1.1
Table 1.2
Table 2.1
Table 2.2
Table 2.3
Table 2.4
Table 3.1
Table 3.2
Table 4.1
Table 5.1
Table 6.1
Table 6.2
Table 6.3
Table 7.1
Table 7.2
Table 7.3
Table 7.4
Table 8.1
Table 8.2
Table 9.1
Table 16.1
Table 17.1
Table 17.2
Table 18.1
Table 19.1
Table 20.1
Table 20.2
Table 24.1
Table 24.2
Table 24.3
Table 24.4
Table 25.1
Related Titles
Cai, Y., Liu, G., O'Driscoll, N. (eds.)
Environmental Chemistry and Toxicology of Mercury
2012
ISBN: 978-0-470-57872-8 (Also available in a variety of electronic formats)
Garland, J.J. (ed.)
Mercury Cadmium Telluride - Growth, Properties and Applications
2011
ISBN: 978-0-470-69706-1 (Also available in a variety of electronic formats)
Colbeck, I., Lazaridis, M. (eds.)
Aerosol Science - Technology and Applications
2014
ISBN: 978-1-119-97792-6(Also available in a variety of electronic formats)
Agranovski, I. (ed.)
Aerosols - Science and Technology
2010
ISBN: 978-3-527-32660-0
Edited by Evan J. Granite, Henry W. Pennline, and Constance Senior
Mercury Control
for Coal-Derived Gas Streams
The Editors
Dr. Evan J. Granite
US Department of Energy
National Energy Technology Laboratory
PO Box 10940
Pittsburgh, PA 15236
USA
Henry W. Pennline
US Department of Energy
National Energy Technology Laboratory
PO Box 10940
Pittsburgh, PA 15236
USA
Constance Senior
ADA Environmental Solutions
9135 S. Ridgeline Blvd, Suite 200
Highlands Ranch, CO 80129
USA
All books published by Wiley-VCH are carefully produced. Nevertheless, authors, editors, and publisher do not warrant the information contained in these books, including this book, to be free of errors. Readers are advised to keep in mind that statements, data, illustrations, procedural details or other items may inadvertently be inaccurate.
Library of Congress Card No.: applied for
British Library Cataloguing-in-Publication Data
A catalogue record for this book is available from the British Library.
Bibliographic information published by the Deutsche Nationalbibliothek
The Deutsche Nationalbibliothek lists this publication in the Deutsche Nationalbibliografie; detailed bibliographic data are available on the Internet at <http://dnb.d-nb.de>.
© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Boschstr. 12, 69469 Weinheim, Germany
All rights reserved (including those of translation into other languages). No part of this book may be reproduced in any form – by photoprinting, microfilm, or any other means – nor transmitted or translated into a machine language without written permission from the publishers. Registered names, trademarks, etc. used in this book, even when not specifically marked as such, are not to be considered unprotected by law.
Print ISBN: 978-3-527-32949-6
ePDF ISBN: 978-3-527-65881-7
ePub ISBN: 978-3-527-65880-0
Mobi ISBN: 978-3-527-65879-4
oBook ISBN: 978-3-527-65878-7
List of Contributors
Gary Blythe
URS Corporation
Process Technology Office
Amberglen Blvd.
Austin, TX 78729
USA
Ramsay Chang
Electric Power Research Institute
Hillview Ave
Palo Alto, CA 94304-1338
USA
Jared P. Ciferno
U.S Department of Energy
National Energy Technology Laboratory
Pittsburgh, PA 15236-0940
USA
Thomas J. Feeley III
U.S Department of Energy
National Energy Technology Laboratory
Pittsburgh, PA 15236-0940
USA
Thomas K. Gale
Novinda Corp.
18th Street
Suite 1755
North Tower
Denver, CO 80202
USA
S. Behrooz Ghorishi
CoaLogix – SCR Tech
Steele Creek Road
Charlotte, NC 28273
USA
Evan J. Granite
US Department of Energy
National Energy Technology Laboratory
PO Box 10940
Pittsburgh, PA 15236
USA
Shameem Hasan
Schreiber
Yonley & Associates
Westwoods Business Park Drive
Ellisville, MO 63021
USA
Brian S. Higgins
EnviroCare International
Green Island Road
American Canyon, CA 94503
USA
Nick Hutson
U.S Environmental Protection Agency
Energy Strategies Group
Office of Air Quality Planning and Standards
T. W. Alexander Drive (D243-01)
Research Triangle Park
NC 27711
USA
Andrew P. Jones
U.S Department of Energy
National Energy Technology Laboratory
Pittsburgh, PA 15236-0940
USA
Bruce Keiser
Nalco, An Ecolab Company
West Diehl Road
Naperville, IL 60563-1198
USA
Charles D. Kellett
Schreiber
Yonley & Associates
Westwoods Business Park Drive
Ellisville, MO 63021
USA
Allan Kolker
U.S Geological Survey
Sunrise Valley Drive
Mail Stop 956
Reston, Virginia 20192-0002
USA
Balaji Krishnakumar
Niksa Energy Associates LLC
Terrace Drive
Belmont, CA 94002
USA
Dennis L. Laudal
University of North Dakota
Energy & Environmental Research Center (EERC)
North 23rd Street
Stop 9018
Grand Forks, ND 58202-9018
USA
Nicholas Lentz
University of North Dakota
Institute for Energy Studies
Centennial Drive Stop 8153
Upson II Room 366L
Grand Forks, ND 58202-8153
USA
Leonard Levin
Electric Power Research Institute
Hillview Ave.
Palo Alto, CA 94304
USA
John Meier
Nalco, An Ecolab Company
West Diehl Road
Naperville, IL 60563-1198
USA
Larry S. Monroe
Southern Company
Birmingham, AL
USA
Ronald K. Munson
Leonardo Technologies, Inc.
Bannock, OH 43972
USA
James T. Murphy
Leonardo Technologies, Inc.
Bannock, OH 43972
USA
Robert Nebergall
Cabot Norit Activated Carbon
University Avenue
Marshall, TX 75670
USA
Stephen Niksa
Niksa Energy Associates LLC
Terrace Drive
Belmont, CA 94002
USA
Edwin S. Olson
University of North Dakota
Energy & Environmental Research Center (EERC)
North 23rd Street
Stop 9018
Grand Forks, ND 58202-9018
USA
Henry W. Pennline
US Department of Energy
National Energy Technology Laboratory
P.O Box 10940
Pittsburgh, PA 15236
USA
Jeffrey C. Quick
Utah Geological Survey
West North Temple
Suite 3110
Salt Lake City, UT 84114-6100
USA
Robert Schreiber Jr.
Schreiber Yonley & Associates
Westwoods Business Park Drive
Ellisville, MO 63021
USA
Constance Senior
ADA Environmental Solutions
S. Ridgeline Boulevard
Suite 200
Highlands Ranch, CO 80129
USA
April Freeman Sibley
Southern Company Services
Birmingham, AL 35242
USA
Sharon M. Sjostrom
ADA Environment Solutions
S. Ridgeline Boulevard
Suite 200
Highlands Ranch, CO 80129
USA
Lesley L. Sloss
IEA Clean Coal Centre
Park House
Northfields
London SW18 6DD
UK
Karen J. Uffalussy
US Department of Energy
National Energy Technology Lab
Cochrans Mill Road
Pittsburgh, PA 15236-0940
USA
Jennifer Wilcox
Stanford University
Department of Energy Resources Engineering
Panama Street
Green Earth Sciences 092A
Stanford, CA 94305-2220
USA
Joe Wong
ADA Carbon Solutions LLC
W. Canal Court
Littleton, CO 80120-5632
USA
Carrie Yonley
Schreiber
Yonley & Associates
Westwoods Business Park Drive
Ellisville, MO 63021
USA
Mercury R&D Book Foreword
This book is very timely and important, because as I write this foreword, the U.S. Environmental Protection Agency (EPA) is finalizing the first mercury emission limitations on coal-fired power plants, known as the Mercury and Air Toxics Standards (MATS) rule. This regulation will require significant reductions of the amount of mercury (and other chemicals) contained in the coal fuel before the flue gas is released into the atmosphere.
The information in this volume has mostly been developed over the past decade, where I was engaged as a front line research manager for one of the largest power companies in the United States, Southern Company, which has many coal-fired power plants in its fleet. I have testified before the U.S. Senate on mercury chemistry and behavior in coal-fired boilers (http://epw.senate.gov/108th/Monroe_060503.htm), and have been in a leadership position for the utility industry in several organizations, namely, the Electric Power Research Institute (EPRI), the Coal Utilization Research Council (CURC), and the Utility Air Regulatory Group (UARG). I was the project manager for one of the first full-scale power plant tests of dedicated mercury control, at Alabama Power's Plant Gaston – which won an R&D Magazine “R&D 100” award in 2003. The Gaston project involved many of the authors included in this volume, especially Tom Feeley, Ramsay Chang, and Sharon Sjostrom. This is a subject that I know well.
In addition, several authors and I have collaborated on other related mercury studies. One of the most intriguing was the innovative research of the fate of mercury in coal power plant plumes, using first a fixed wing airplane and then an airship for plume sampling. This effort was led by Leonard Levin of EPRI, and included Dennis Laudal (University of North Dakota) and Jeff Ryan (U.S. EPA). Another cooperative effort through EPRI has been the computer modeling of mercury in power plants in two different efforts, led by Constance Senior and Steve Niksa.
The utility industry was taken by surprise with the announcement by the outgoing Clinton administration that it would be subject to a Maximum Achievable Control Technology (MACT) rule for mercury on 14 December 2000. That action kicked the industry into a frantic search for any data or information that could help us develop reliable control technology choices. Notably, EPRI, through the efforts of Ramsay Chang, and the U.S. Department of Energy (DOE)'s National Energy Technology Laboratory (NETL), had already started working on mercury chemistry and control for coal-fired power plants. The subsequent efforts have largely been successful as an example of a public–private R&D partnership; where the utility industry and the suppliers of technology and materials to the industry worked with the DOE NETL to quickly advance the state of knowledge.
As the R&D progressed, an informal steering group of utility researchers, vendors of hardware and materials, and the U.S. DOE NETL was able to leverage the NETL funding to explore different options for controlling mercury from almost all power plant and coal-type combinations. In the early years of R&D, we found that we knew less and less about mercury chemistry with every new test and discovery, as contradictory results were more the rule.
The editors have assembled an experienced group of authors to make this volume, a “Who's Who's” of mercury research from the United States over the past decade. I feel lucky to have worked with virtually every one of the assembled group, and call most of them close friends. There is no better group of technical professionals to guide you in understanding the issues of mercury in coal-derived gas streams.
The volume is arranged in a logical sequence, beginning with the fate of mercury in the environment, written by Leonard Levin of EPRI. The applicable regulations, both for the United States and the international context, follow along with descriptions of trace elements in coal and the means to measure mercury in gas streams. The heart of the work is presented in the following sections on mercury chemistry, research programs, and the different technology systems that can be used and adapted for mercury control. The important topic of the stability of mercury in the solid coal combustion residues is also addressed next. Finally, the state-of-the-art in mercury modeling, both at the fundamental and process levels, is presented.
This is the manuscript that I – and the whole industry – needed back in 2000, as we contemplated what we would have do to reduce mercury emissions to meet upcoming regulations. It will serve as both a reference for those already engaged in the research and control efforts, and as an invaluable introduction for those just now becoming interested in the subject. I highly recommend it to the technical reader.
October 2014
Larry S. Monroe
Georgia Power Company
Atlanta, GA, USA
Preface
This book has its genesis in a Department of Energy (DOE) Topical Report on “Sorbents for Mercury Removal from Flue Gas” that Henry Pennline asked me to write in 1996. As a new post-doc hired to study sorbents for the capture of mercury, Henry suggested that a thorough literature review and survey would be an excellent way to start. As the topical report progressed and was nearly complete in 1997, I suggested to Henry that we write a book about mercury in flue gas. Henry shot this idea down at the time, correctly stating that we had much more to learn. Henry Pennline has turned out to be the best supervisor, researcher, colleague, and friend I could ever have. He was a little skeptical of my abilities at first, having observed my unusual photographic memory for foods; my suit and tie attire in the laboratory (unusual at DOE); and my dropping a large $25 quartz tube for the micro-balance on my first day on the job. I hope I end up doing something good in my research career to justify Henry's faith in me.
Mercury is a semi-noble metal, with both a fascinating chemistry and numerous applications throughout human history. Coal-derived flue gas and coal-derived syngas are both complex stews containing numerous species and exist over a wide temperature range at pulverized combustion and integrated gasification combined cycle (IGCC) plants, respectively. Having completed a MS thesis on coal gasification, I already knew going into the DOE that one could happily study coal flue gas and syngas for many lifetimes. Being introduced to mercury at DOE, I quickly found a terrific subject, with many wonderful colleagues.
In 1998 I met Dr Constance Senior at DOE in Pittsburgh. Constance was leading a large DOE-funded study on the behavior of the trace elements in coal-fired power plants. She impressed me immediately as a tenacious leader and terrific researcher. Constance exhibited extraordinary leadership – her efforts in corralling a large and diverse group of researchers from industry, academia, and the government resulted in a nearly 800-page report for DOE; a special issue of Fuel Processing Technology on the trace elements in coal-fired power plants in 2000; and a great expansion of our understanding of mercury in flue gas. I had the pleasure of meeting Constance again at the Workshop on Source Emission and Ambient Air Monitoring in Minneapolis in 1999. Despite the fact that I was an unknown post-doc at DOE, she introduced me to many of the researchers at dinner (a large pot of minestrone soup and a gigantic pizza that covered the entire table) in the Mall of America. I learned a lesson that day from Constance; always be nice to your colleagues. Hopefully I have done this. Dr Senior made Herculean efforts to help this book get completed; she is one-in-a-million.
Our work at DOE has allowed us to meet many wonderful colleagues at venues such as the Annual Mercury Control Technology Meetings that were held in Pittsburgh; the AIChE and ACS National Meetings; the Air Quality Conferences, and the Mega Symposiums. At the joint ACS-AIChE National Meeting held in the spring of 2008 in New Orleans, I recruited Tom Feeley, Ramsay Chang, and Constance Senior to be my keynote speakers on mercury. They did an outstanding job, highlighting a program that had 29 speakers on the various aspects of mercury in coal-derived gases. The idea for the book on mercury, having never left my mind, was revived. In 2009 I came up with a draft outline for this book, and happily in 2010, Dr Julia Stuthe from John Wiley recruited me to organize a book on mercury in coal-derived gases. Having already planned a book, I bent her ears with a 40-page PowerPoint presentation, abstract, and outline over a burrito and spicy chicken tortilla soup dinner in San Antonio during the 2010 AIChE National Meeting. Julia – forgive me. Dr Stuthe has recently left John Wiley, and I wish her great success. Lesley Belfit from John Wiley has done an outstanding job in helping us complete this book.
Coal contains a trace level of mercury of approximately 0.1 ppm. Mercury is a neurotoxin, and can travel long distances once emitted through the stacks of coal-burning power plants. Approximately 30–40% of the electricity in the United States is generated through the combustion of coal. Coal is an abundant resource in the United States – the country has a supply for at least 200 years. The challenge is to utilize the abundant domestic coal for energy independence in environmentally friendly ways.
With the US EPA issuing a national regulation on 21 December, 2011, requiring 91% removal of mercury, and many states already with their own regulations, the need exists for low-cost mercury removal techniques that can be applied to coal-burning power plants. The injection of powdered activated carbon into the ductwork upstream of the particulate control device is the most developed technology for mercury capture. Alternative techniques for mercury capture will also play a role in the near future because of the numerous configurations of air pollution control devices present within the power plants, as well as the many different coals being burned. These methods employ sorbents, catalysts, scrubber liquors, flue gas or coal additives, combustion modification, flue gas cooling, barrier discharges, and ultraviolet radiation for the removal of mercury from flue gas streams. The DOE Mercury Program has been a huge success, spurring development, demonstration, and commercialization of many technologies for the capture of mercury.
The future research needs for mercury control include improved sorbent-flue gas contact, development of poison-resistant sorbents and catalysts, new scrubber additives for retention of mercury within wet flue gas desulfurization (WFGD) systems, concrete-friendly activated carbons, new continuous measurement methods, by-products research, and development of an ASTM standard laboratory test for sorbent activity for mercury capture.
This book aims to cover the technologies for mercury capture and measurement from coal-derived flue gas. The fate of mercury in the environment, a great motivation for the regulations, research, development, and commercialization of capture and measurement methods, is covered in Chapter 1. The trace elements in coal are detailed in Chapter 2. In addition, the regulatory issues, both in the United States and internationally, are discussed in Chapters 3 and 4. Methods for the detection of mercury in flue gas are covered in Chapters 5 and 6. Later chapters discuss the many methods for mercury control, the various research programs, activated carbon technologies, the cement industry, gasification, mercury carbon surface chemistry, and modeling.
I thank Constance and Henry for their outstanding efforts in making this book become a reality. Constance and Henry took my crude initial outline for the book and greatly improved it. Tom Feeley deserves many thanks for the great success of the DOE Mercury Program, and for supporting our in-house research on flue gas. Gary Stiegel and Jenny Tennant from DOE have been terrific in supporting our efforts in understanding the trace elements in gasification systems. Our authors and colleagues Constance Senior, Henry Pennline, Larry Monroe, Leonard Levin, Allan Kolker, Jeff Quick, Leslie Sloss, Nick Hutson, Denny Laudal, Carrie Yonley, Tom Feeley, Ramsay Chang, Tom Gale, Brian Higgins, April Sibley, Gary Blythe, Joe Wong, Nick Lentz, Sharon Sjostrom, Rob Nebergall, Behrooz Ghorshi, Ed Olson, Karen Uffalussy, Jennifer Wilcox, and Steve Niksa did an outstanding job. They are the leading figures in the mercury capture research, development, demonstration-commercialization communities; and are also terrific colleagues and friends. Some of our authors have been working on the mercury issue for over 20 years.
Finally, I thank Phil and Rita Granite, for interest in mercury, suggestions over the years for techniques for mercury control, and for being terrific parents. The same thanks also go to my brother Larry Granite at Environmental Protection Agency (EPA). Linda Granite has humored me, feigning interest in mercury while we were dating (I bent her ears with papers on sorbents and photochemical removal of mercury on our first date – a steak dinner; despite this she went out with me again!), and has been an angel through the years as my mind is sometimes elsewhere on the topic of mercury. Linda and our daughters Ana and Marissa Granite always provide inspiration.
October 2014
Evan Granite
Pittsburgh, PA
List of Abbreviations
ACI
Activated carbon injection
APCD
Air pollution control device
APH
Air preheater
BAT
Best available technique or technology
BEP
Best environmental practice
CAMR
Clean air mercury rule
CEMS
Continuous emission monitoring system
CFBC
Circulating fluidized bed combustor
CSAPR
Cross-states air pollution rule
CS-ESP
Cold-side ESP
DOE
Department of Energy
DSI
Dry sorbent injection
EC
European Commission
ECN
Economizer
EGU
Electricity generating unit
ELV
Emission limit value
EPA
Environmental Protection Agency
EPRI
Electric Power Research Institute
ESP
Electrostatic precipitator
ESPc
Cold-side electrostatic precipitator
ESPh
Hot-side electrostatic precipitator
EU
European Union
FBC
Fluidized bed combustor
FF
Fabric (or baghouse) filter
FGD
Flue gas desulfurization
GHSV
Gas hourly space velocity
HAP
Hazardous air pollutant
HELCOM
Helsinki Commission
ICI
Industrial, commercial, and institutional
ICR
Information collection request
IED
Industrial Emissions Directive
IPPC
Integrated pollution prevention and control
L/G
Ratio of volumetric flowrates of liquid to gas in WFGD
LCPD
Large Combustion Plant Directive
LNB
Low NOx burner
LOI
Loss on ignition
LRTAP
Long-range transboundary air pollution
MATS
Mercury and air toxics standards
MEPOP
Mercury and persistent organic pollutants
MW
Megawatt
NARAP
North American regional action plan
NEPM
National Environmental Protection Measures (Australia)
NERP
National Emission Reduction Plan
NETL
National Energy Technology Laboratory
NHMRC
National Health and Medical Research Council (Australia)
NPI
National Pollutants Inventory
OFA
Overfire air
OSPAR
Oslo and Paris Commission
PAC
Powdered activated carbon
PCD
Particulate control device
PM
Particulate matter
SCEM
Semi-continuous emissions monitor
SCR
Selective catalytic reduction
SDA
Spray dry absorber for flue gas desulfurization
SED
Solvent Emissions Directive
SNCR
Selective non-catalytic reduction
SO
2
Sulfur dioxide
TOXECON
Advanced sorbent injection configuration licensed by EPRI
UBC
Unburned carbon
UNECE
United Nations Economic Commission for Europe
UNEP
United Nations Environment Programme
WFGD
Wet flue gas desulfurization
WID
Waste Incineration Directive
XAFS
X-ray absorption fine structure
XPS
X-ray photoemission spectroscopy
Part IMercury in the Environment: Origin, Fate, and Regulation
1Mercury in the Environment
Leonard Levin
1.1 Introduction
Mercury is a naturally occurring chemical element found ubiquitously throughout both the natural and human environments. Mercury occurs throughout the earth's crust and is most commonly found in its geological occurrence as the mineral cinnabar (mercuric sulfide, HgS2). Elemental mercury, the uncombined form, occurs at room temperature and sea level pressure as a liquid, the only chemical element so occurring. Due to its relatively high vapor pressure, liquid mercury will evaporate readily into the atmosphere.
Elemental mercury can be oxidized to the mercurous (Hg1+) or mercuric (Hg2+) inorganic form in the presence of hydroxyl radicals, ozone, or a number of other oxidizing agents. The more commonly occurring mercuric form readily recombines into either water-soluble forms, such as with halogens (e.g., HgCl2), or insoluble salts (HgS2).
Surface exposure of geological mercury minerals or elemental mercury concentrations led to the presence of both elemental and inorganic mercury in the global atmosphere, even prior to its enhanced release due to human activity after the onset of the Industrial Revolution (mid-eighteenth century). Indeed, this ubiquity of mercury, and its uptake by fauna via leaf stomata and root systems, leads to its association with fossil fuels such as oil and coal. These fuels derive from burial and metamorphosis of plant matter under anoxic conditions via stages starting with peat formation. Core sampling of peat formations in Arctic Canada by Givelet et al. [1] has shown transitory excursions of mercury deposition dating from before 1700 CE attributed to wildfires set by First Nations for land clearing.
One feature of interest to investigators is the relative increase in abundance of mercury in the environment from the pre-Columbian era to the present day, due to human mobilization of the substance. This mobilization has occurred in several ways, but primarily through either direct use of mercury in products or via combustion-related emissions of fuel-associated mercury. The use of elemental mercury in medical and consumer products has occurred over hundreds of years, in such instances as the forming of pelts and felts into chapeaux and its use in electric switches. Fuel-associated mercury continues to be released globally in the production of power, space and process heat, process steam, and other uses.
This relative increase in global mercury cycling in the modern era can be determined by comparing mercury concentrations at both deep and shallow depths in cores of glacial ice or lake sediments, or by comparing global source inventories of mercury. In the case of inventory comparisons, the modern: preindustrial ratios are derived from separately calculating emission rates from undisturbed natural background sources (exposed mercuriferous deposits, surface, and undersea volcanism) with the total of those sources and human sources (atmospheric evasion from inactive mining sites, mineral recovery sites, point and area fuel combustion sources, and waste sites).
Each such method has both advantages and disadvantages. Core samples can represent localized conditions (e.g., lensing of lake sediments), while global inventories are subject to large uncertainties due to spatial scaling of local measurements, inaccurate extrapolation to unmeasured sources, and so on. Generally, results indicate that, globally, there is roughly three to four times as much mercury cycling through the biogeochemical and human environment currently as there was in pre-Columbian times (see Figure 1.1) [2]. This modern: preindustrial ratio, however, is a global average. There are many individual experimental samples in ice cores, peat bogs, lake-bottom sediments, and other environments globally exhibiting much higher ratios. For example, Schuster et al. [3] found a 20-fold enhancement ratio in ice core data from the Lower Fremont Glacier, Wind River Mountains, Wyoming, USA.
Figure 1.1 Global biogeochemical cycle for mercury. Natural (preindustrial) fluxes (megagrams (Mg) per year) and inventories, in megagrams, are noted in black. Anthropogenic contributions are in gray. Natural fluxes augmented by anthropogenic activities are noted by gray-and-black dashed lines. (Modified from Selin et al. [4].) A mean enrichment factor of 3 between the preindustrial and present-day mercury deposition, based on remote sediment cores, is used as a constraint. (Figure from Selin [2] © 2009 by Annual Review.)
The atmospheric lifetime of vapor-phase elemental mercury is believed to be roughly 7–12 months, in bulk, although the mean lifetime of reactive oxidized mercury is more likely measured in days to weeks. Atmospheric oxidized mercury may undergo chemical reduction to the insoluble gaseous elemental form, or may be removed from the atmosphere by solution in precipitation or by dry deposition to the earth's surface.
Mercury concentrations in the planetary boundary layer appear to react to changes in global input within months to years (see, for example, [5]). There is a much longer period for aquatic systems to fully react to changes in mercury input via deposition and runoff, but this is somewhat dependent on the trophic depth of the ecosystem involved. Large piscivorous fish represent multiyear mercury reservoirs whose body burden of mercury (primarily as methylmercury) acts as multiyear transfers of an integrated record of mercury exposure from their feeding patterns.
1.2 Mercury as a Chemical Element
Mercury is a chemical element (atomic number 80, isotope-weighted atomic mass 200.59 amu) known as a distinct substance since the earliest days of civilization. The Greek word for mercury, Yδραργυρος, means “water + silver.” This was adapted into the Latin hydrargyros, for “water–silver.” Both terms refer to the morphology of pure elemental mercury at room temperature, a silvery liquid, and the only chemical element occurring in pure form as a liquid at ambient temperatures.
The abundance of naturally occurring stable isotopes of mercury is shown in Table 1.1 [6]. In addition, several unstable isotopes of mercury are known. One of these, 203Hg, is commonly used as a spiked tracer in, for example, experiments on mercury methylation in aquatic systems [7].
Table 1.1 Background natural abundance of stable mercury isotopes
Isotope
198
Hg
199
Hg
200
Hg
201
Hg
202
Hg
204
Hg
Abundance (%)
10
17
23
13
30
7
1.2.1 Physical and Chemical Properties of the Forms of Mercury
A key variable of mercury and its chemically combined forms is its vapor pressure. The vapor pressure is of interest because one form of transference of mercury from the earth's surface to the overlying atmosphere is evasion, or net positive flux into the atmosphere [8].
1.2.2 Associations with Minerals and Fuels
Mercury is typically found in association with fossil fuels: coal, petroleum, and natural gas. Mercury associated with coal deposits ranges globally from 0.02 to 1.0 ppmw [9]. This range is similar to that found for the occurrence of mercury in background topsoil samples (<0.01–4.6 ppmw, [10]). Mercury association with coal is thought to be via diagenesis in coalbeds [11, 12]: during metamorphic processes, inclusions of pyritic minerals into coalbed fracture zones have brought with them mercury inclusions. This is in opposition to the obvious association of naturally occurring atmospheric mercury in surface vegetation later incorporated into sedimentary precursors to coalbed seams. The pyritic association of mercury in coal is primarily evident in bituminous and anthracite seams, while subbituminous and lignite coals tend to have mercury associated with organic constituents, perhaps the remnant of mercury ligands in surface vegetal deposits. The pyrite association is borne out by concentration enrichments of ∼×100 in analyses of pyrites from coal versus the concentrations in whole coal samples.
1.3 Direct Uses of Mercury
Mercury in medical treatment: Mercury in various chemical forms has long served as an artisanal medical treatment. Although liquid mercury is still used in scattered applications in the United States, it was more widely used in the early twentieth century for treatment of venereal disease; one documented example is the syphilis treatment of Karen Blixen (“Isaac Dinesen,” Out of Africa) in Kenya by prescription of mercury pills [13]. Chinese herbal balls, with recommended doses of two balls swallowed per day, have been found to have mercuric sulfide added to their composition [14]. The daily dose of mercury can amount to 1200 mg. For a 70 kg consumer, this dose is equivalent to nearly 200 000 times the Environmental Protection Agency (EPA) mercury Reference Dose of 0.1 µg kg−1 day−1. More common uses of mercury have been in medical devices such as thermometers and sphygmomanometers; in the latter case, replacement of these devices where mercury is employed by aneroid or digital versions has produced problematic intercomparisons of readings [15].
Mercury in products: Mercury, particularly elemental mercury in liquid form, has often been directly used in consumer and industrial products and processes. In the United States, this was particularly the case for its use in batteries and switches [16]. Another common use was as a conductor in quiet mercury switches, which were commonly used in natural gas and petroleum distribution lines [17]. These uses have dropped significantly in recent years (Table 1.2). One of the last remaining large consumer uses for mercury is in fluorescent lamps, including compact fluorescent lamps (CFLs), each of which typically contains several milligrams of mercury [18].
Table 1.2 Total mercury sold in pumps in the United States (pounds)
2001 Total mercury
2004 Total mercury
2007 Total mercury
12 745 (6.4 ton)
13 911 (7.0 ton)
10 383 (5.2 ton)
a
ahttp://www.newmoa.org/prevention/mercury/imerc/factsheets/pumps.cfm#4
Source: NEWMOA [19].
1.4 Atmospheric Transport and Deposition
The concentration of mercury in ambient air is on the order of 1–5 ppt. Most of this occurs as gaseous elemental mercury (GEM), especially above the atmospheric boundary layer, although trace levels of the divalent form and even methylmercury have been measured [20]. A recurring public fallacy is that, as mercury is classified as a “heavy metal,” [21, 22], the substance “falls out of the sky” quickly upon being emitted to the atmosphere. Because the mercury from heated elevated sources disperses in the atmosphere, gravitational settling at the atomic or molecular level does not play a role in mercury dynamics – except for particulate-bound mercury (Hgp, primarily HgII bound to crustal and combustion particles), where particle deposition velocities do play a role. The high vapor pressure of elemental mercury serves to disperse it widely so that atmospheric turbulence keeps GEM in the atmosphere for a lifetime of 7–16 months (e-folding time). This long lifetime in the free troposphere classifies mercury, particularly elemental mercury, as a global pollutant [23].
1.5 Atmospheric Reactions and Lifetime
Mercury released to the atmosphere from natural sources, such as volcanoes or mercuriferous crustal deposits, is generally in the form of elemental mercury (Hg0), commonly termed gaseous elemental mercury in its atmospheric occurrence. Anthropogenic emissions are, in general, a mix of GEM and divalent mercury (HgII), referred to as reactive gaseous mercury or RGM in its atmospheric occurrence. The lifetime of mercury species in the atmosphere is bounded by the reaction and removal rates of the two primary species, GEM and RGM. The oxidation of GEM to RGM by ozone, O3, has been studied by many investigators. An important removal mechanism for RGM is due to its relatively high solubility in precipitable water. Calvert and Lindberg [24] concluded that the single-stage reaction Hg + O3 → HgO + O2 was less likely to occur than an intermediary unstable molecule HgO3, decaying to OHgOO, and then decomposing into HgO + O2. Further removal reactions have been investigated; one such process, the oxidation of Hg0 by hydroxyl radical, OH, was found by Goodsite et al. [25] to be a relatively unimportant step.
The atmospheric lifetime (average residence time) of GEM is normally assumed to be 7–15 months. Work by Selin et al. [4] tried to refine these numbers into the contributing factors: removal by dry deposition; oxidation to RGM by homogeneous- and heterogeneous-phase reactions in the atmosphere; additions by reduction reactions of RGM in the upper troposphere/lower stratosphere (UTLS); and evasion of GEM from surface reservoirs. Each of these processes is still poorly understood, particularly the subsidence and transport of UTLS mercury forms. The reservoir of RGM just above the tropopause plays an important role in nighttime subsidence peaks of RGM in the lower troposphere [26] and in Arctic mercury depletion events (AMDEs) [27].
1.6 Mercury Biogeochemical Cycling
Once deposited to the earth's surface, mercury may undergo a complex series of reactions that may result in one or more steps in its biogeochemical cycling: being re-evaded to the atmosphere, bound to organic compounds in the terrestrial understory; dissolved in seawater and removed by binding to marine “snow” [28].
One important study of mercury dynamics in an aquatic watershed was the Mercury Experiment to Assess Atmospheric Loading in Canada and the United States (METAALICUS) experiment [29]. During the METAALICUS experiment, solutions of mercuric chloride, each “tagged” with elevated concentrations of a different naturally occurring stable isotope of mercury, were deposited in segments of a test watershed in Ontario, Canada. This isotope spiking allowed tracing of the rate and partitioning of mercury introduced into each watershed compartment to be traced over both time and space. The isotope spikes were introduced into the upland and wetland compartments as simulated precipitation: using fixed-wing aircraft, solutions of isotope-spiked HgNO3 were distributed over each compartment just prior to or during periods of rainfall in the area. The wetland and upland spikes were added yearly for 3 years. The waterbody spike was applied by a small boat cruising a crisscross pattern on the lake itself; the water surface applications occurred every 2 weeks during the open-water seasons.
METAALICUS results from the first 3 years of the study showed that mercury movement from the application compartments (surfaces of wetlands, uplands, and waterbody) to sequestration in soils and sediments, respectively, was still underway at the end of the application period. Upland spike mercury was, by that time, preferentially found (areal mass distribution) in the underlying soil, but still progressing from the surface vegetation exposed to the original spike application. Wetland spike mercury exhibited the opposite distribution: that addition was still predominantly in the lowlands vegetation than in the underlying peat. Overall, there was a 2–5% increase in peat, soil, and sediment mercury concentrations from the 3 years' additions.
Lake water column mercury showed an overall 53% increase in concentration due to the introduction of the lake spike itself, while the upper layer of lake-bottom sediments revealed a 5% concentration increase. Since Lake 658 communicates with an adjacent shield lake via a narrow weird outflow, a 5% portion of the spike was itself lost through the outflow. The researchers estimated that 25–30% of the wetland and upland spikes, and 45% of the lake spike, were lost to the atmosphere via evasion over the 3-year period.
The METAALICUS findings are significant in several regards. As the only whole-ecosystem mercury study to date, the experiment demonstrates once more the relatively slow response of lake bodies to changes in atmospheric deposition. The authors conclude that lakes receiving all of their new mercury via deposition, such as perched seepage lakes, might respond to step changes in deposition (such as were simulated by the spike additions) over about a decade; that is, a proportional change in water column mercury to the deposition step would require that period of time to be reached. For drainage lakes, a longer adjustment period can be expected.
Additionally, the findings concerning evasion losses are a critical experimental check on assumptions used in mercury modeling. Generally, regional and global models of mercury assume a prompt re-emission of 50% of deposited mercury (see, e.g., [30]). This re-emitted or evaded mercury is the primary contributor to what is generally termed the grasshopper effect [31]: successive deposition and re-emission of mercury from lower to higher latitudes (down-gradient transport), leading to a successive and relatively high build-up rate of mercury (and other pollutants) in high temperate and boreal regions. The experiment at Lake 658 reveals that this effect is probably dominated by evasion from oceans and water bodies rather than terrestrial environments, and so is limited by the sum of deposition to and native mercury emissions from those marine and aquatic environments.
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2Mercury and Halogens in Coal
Allan Kolker and Jeffrey C. Quick
2.1 Introduction
2.1.1 Mode of Occurrence of Mercury (Hg) in Coal
In bituminous coals, the iron disulfide, pyrite and its FeS2 polymorph, marcasite, typically host the greatest fraction of Hg present [1–8], with lesser fractions of Hg associated with organic matter and with non-FeS2 mineral hosts. Evidence for the occurrence of Hg and other trace metals in Fe disulfides in coal is reviewed by Kolker [9], including crystal chemistry and controls on element substitution in Fe disulfides and available data on Hg concentrations from direct determinations by microanalysis. In cases where individual Fe disulfide grains in coal have been analyzed, Hg contents are in the tens to hundreds of times those in the whole coal. But assuming that pyrite-rich coals are necessarily Hg-rich coals is an oversimplification. A good example to the contrary is the U.S. bituminous Illinois #6 coal. This commercially important coal has relatively high contents of total and pyritic sulfur widely attributed to marine influence, but low to moderate Hg (and As) contents [10–12], as the extent of substitution in Illinois #6 pyrite by impurities is relatively small [7, 12–14].
In low-rank coals, including lignite and subbituminous coals, Hg and S contents are generally lower overall than in bituminous coals, and the proportion of Hg occurring in association with organic material is greater [2, 15]. From the standpoint of Hg capture, compared to bituminous coals, the lower overall Hg content of low-rank coals is offset by the tendency of these coals to also have lower halogen contents, and, because of their lower calorific value, the requirement that greater amounts of low-rank coal are needed to achieve an equivalent energy output.
As shown elsewhere in this volume, the form of Hg in feed coal does not impact Hg speciation at boiler temperatures. In the furnace, Hg is present in the elemental form but it can combine to form compounds as the flue gas cools. Knowledge of the mode of occurrence of Hg in coal has important implications for the extent to which pre-combustion Hg control might be possible (following section), whereas the halogen species present influence post-combustion Hg capture.
