United States Air Pollution Training Institute (APTI) September 20 Environmental Protection MD 17 Agency Environmental Research Center Research Triangle Park, NC Control of Nitrogen Oxides Emissions Student Manual APTI Course 418 Author John R. Richards, Ph.D., P.E. Air Control Techniques, P.C. Editor APPENDIX A Robert M. Schell A-1 ICES Ltd. Control of Nitrogen Oxides Emissions Student Manual APTI Course 418 Author John R. Richards, Ph.D., P.E. Air Control Techniques, P.C. Editor Robert M. Schell ICES Ltd. Developed by ICES Ltd. September 2000 EPA Contract No. 68D99022 APPENDIX A A-2 APPENDIX A A-3 Acknowledgments This text combines original content provided by Dr. John R. Richards, Ph.D., P.E., with the content of EPA Workshop T002-99, Control of Nitrogen Oxides Emissions, which was broadcast in January 1999 to the APTI Distance Learning Network. The author of this student manual, Dr. Richards, and the editor, Robert M. Schell, are hereby acknowledged for their cooperative integration of the original broadcast materials with extended and updated technical content. The T002-99 Workshop presenters who currently appear in the broadcast video are also acknowledged for the original content they contributed. These materials provided a firm foundation and a companion video for this course. The presenters and the chapters of this manual that contain their contributions are given here. Chapter 1 Introduction to Nitrogen Oxides Control Mike Urban Chapter 2 NOX Formation in Combustion Processes Bob Hall Chapter 3 NOX Emission Trends and Sources Douglas Soloman Chapter 4 NOX Regulatory Programs Dave Stonefield, Ravi Srivastava Chapter 5 Combustion Sources John R. Richards Chapter 6 Combustion Modifications Andy Miller Chapter 7 Low NOX Burners Andy Miller Chapter 8 NOX Reburning Bob Hall Chapter 9 Reciprocating Internal Combustion Engines Jack Wasser Chapter 10 Gas Turbines Sims Roy Chapter 11 Selective Catalytic Reduction Anne Johnson Chapter 12 Selective Non-Catalytic Reduction John R. Richards Chapter 13 Continuous Emission Monitoring James A. Jahnke APPENDIX A A-4 APPENDIX A A-5 Disclaimer This document is not an official policy and standards document and does not constitute U.S. Environmental Protection Agency policy. Mention of trade names or commercial products does not constitute endorsement or recommendation for use. APPENDIX A A-6 APPENDIX A A-7 Classroom Agenda Course 418 Control of NOX Emissions DAY 1 Introduction and Organization of the Course Pre-test Chapter 1 Introduction to Nitrogen Oxides Control Regulation of NOX Definition of NOX Origins of NOX 2 NOX Formation in Combustion Processes Introduction NOX formation mechanisms in combustion processes 3 NOX Emission Trends and Sources Anthropogenic sources Natural sources NOX emission trends Ozone season emissions Emissions projections 4 NOX Regulatory Programs Introduction NO2 NAAQS Ozone NAAQS PM10 and PM2.5 NAAQS Visibility impairment Historic review of ozone control strategies Acid rain Other programs 5 Combustion Sources Boilers Stationary internal combustion engines Municipal waste incinerators APPENDIX A A-8 Classroom Agenda Course 418 Control of NOX Emissions DAY 2 Chapter 6 Combustion Modifications Principles of combustion modifications Combustion modification techniques Summary 7 Low NOX Burners LNB operating principles Wall-fired LNBs Tangentially-fired LNBs Operational issues 8 NOX Reburning Introduction Reburning operating principles Wall-fired reburning Cyclone boiler reburning Video Segment Applicability 9 Reciprocating Internal Combustion Engines Pre-combustion control Post-combustion control Case study 10 Gas Turbines Introduction Combustion modification controls Post combustion controls APPENDIX A A-9 Classroom Agenda Course 418 Control of NOX Emissions DAY 3 Chapter 11 Selective Catalytic Reduction Introduction Operating principles SCR configuration Video Segment Reagent (ammonia) injection system Catalyst Video Segment Instrumentation 12 Selective Non-Catalytic Reduction Development Operating principles System components Design and sizing Operation Video Segment 13 Continuous Emission Monitoring CEM regulatory program Measurement techniques CEM systems Quality assurance and quality control Oxygen concentration monitors Emissions calculations Post-test Adjourn APPENDIX A A-10 APPENDIX A A-11 TABLE OF CONTENTS ACRONYMS.................................................................................................. xix LIST OF TABLES .........................................................................................xxiii LIST OF FIGURES ........................................................................................xxv FORWARD...................................................................................................xxix CHAPTER 1 Introduction to Nitrogen Oxides Control.....................................1-1 Student Objectives ....................................................................................1-1 1.1 Regulation of Nitrogen Oxides ..............................................................1-3 1.1.1 Historic Overview.......................................................................1-3 1.1.2 Ozone NAAQS, NOX SIP Call and Section 126 Petitions...............1-4 1.1.3 PM2.5 NAAQS and Regional Haze ................................................1-5 1.1.4 Acid Rain...................................................................................1-5 1.1.5 Stratospheric Ozone ..................................................................1-6 1.2 Definition of Nitrogen Oxides ...............................................................1-6 1.2.1 Nitric Oxide and Nitrogen Dioxide ..............................................1-6 1.2.2 Dinitrogen Tetroxide ..................................................................1-8 1.2.3 Nitrous Oxide ............................................................................1-8 1.2.4 Nitrous Acid and Nitric Acid.......................................................1-9 1.3 Origins of NOX ...................................................................................1-10 Review Exercises ..............................................................................1-11 References........................................................................................1-12 CHAPTER 2 NOX Formation in Combustion Processes...................................2-1 Student Objectives ....................................................................................2-1 2.1 Introduction ........................................................................................2-3 2.2 NOX Formation Mechanisms In Combustion Processes.........................2-4 2.2.1 Thermal NOX .............................................................................2-4 2.2.2 Fuel NOx....................................................................................2-7 2.2.3 Prompt NOx .............................................................................2-10 Review Exercises ..............................................................................2-11 References........................................................................................2-12 CHAPTER 3 NOX Emission Trends and Sources ............................................3-1 Student Objectives ....................................................................................3-1 3.1 Anthropogenic Sources ........................................................................3-4 3.1.1 Electric Generating Units...........................................................3-5 3.1.2 Non-EGU Point Sources.............................................................3-6 3.1.2.1 Industrial Fuel Combustion Sources.............................3-6 3.1.2.2 Industrial Processes .....................................................3-6 3.1.3 Stationary Area Sources ............................................................3-8 3.1.4 Non-Road Mobile Sources ..........................................................3-9 3.1.5 Highway Mobile Sources ..........................................................3-10 3.1.6 Miscellaneous Sources.............................................................3-12 APPENDIX A A-12 3.2 Natural Sources.................................................................................3-12 3.2.1 Biogenic Sources .....................................................................3-12 3.2.2 Geogenic Sources ....................................................................3-15 3.2.2.1 Marine Ecosystems.....................................................3-15 3.2.2.2 Lightning....................................................................3-15 3.2.2.3 Fires...........................................................................3-16 3.2.2.4 Stratospheric Intrusion...............................................3-17 3.2.2.5 Volcanoes and Geysers ...............................................3-17 3.3 NOX Emission Trends ........................................................................3-18 3.4 Ozone Season Emissions ...................................................................3-20 3.5 Emissions Projections........................................................................3-21 Review Exercises ..............................................................................3-23 References........................................................................................3-24 CHAPTER 4 NOX Regulatory Programs ..........................................................4-1 Student