THERMAL DECOMPOSITION STUDY OF HYDROXYLAMINE NITRATE DURING STORAGE AND HANDLING A Thesis by CHUANJI ZHANG Submitted to the Office of Graduate Studies of Texas A&M University in partial fulfillment of the requirements for the degree of MASTER OF SCIENCE May 2006 Major Subject: Chemical EngineeringTHERMAL DECOMPOSITION STUDY OF HYDROXYLAMINE NITRATE DURING STORAGE AND HANDLING A Thesis by CHUANJI ZHANG Submitted to the Office of Graduate Studies of Texas A&M University in partial fulfillment of the requirements for the degree of MASTER OF SCIENCE Approved by: Chair of Committee, M. Sam Mannan Committee Members, Kenneth R. Hall Debjyoti Banerjee Head of Department, Kenneth R. Hall May 2006 Major Subject: Chemical EngineeringiiiABSTRACT Thermal Decomposition Study of Hydroxylamine Nitrate During Storage and Handling. (May 2006) Chuanji Zhang, B.S., Anhui Normal University, China Chair of Advisory Committee: Dr. M. Sam Mannan Hydroxylamine nitrate (HAN), an important agent for the nuclear industry and the U.S. Army, has been involved in several costly incidents. To prevent similar incidents, the study of HAN safe storage and handling boundary has become extremely important for industries. However, HAN decomposition involves complicated reaction pathways due to its autocatalytic behavior and therefore presents a challenge for definition of safe boundaries of HAN storage and handling. This research focused on HAN decomposition behavior under various conditions and proposed isothermal aging testing and kinetic-based simulation to determine safety boundaries for HAN storage and handling. Specifically, HAN decomposition in the presence of glass, titanium, stainless steel with titanium, or stainless steel was examined in an Automatic Pressure Tracking Adiabatic Calorimeter (APTAC). n-th order kinetics was used for initial reaction rate estimation. Because stainless steel is a commonly used material for HAN containers, isothermal aging tests were conducted in a stainless steel cell toivdetermine the maximum safe storage time of HAN. Moreover, by changing thermal inertia, data for HAN decomposition in the stainless steel cell were examined and the experimental results were simulated by the Thermal Safety Software package. This work offers useful guidance for industries that manufacture, handle, and store HAN. The experimental data acquired not only can help with aspects of process safety design, including emergency relief systems, process control, and process equipment selection, but also is a useful reference for the associated theoretical study of autocatalytic decomposition behavior.vDEDICATION To my husband Huachun Xu and all my family members in ChinaviACKNOWLEDGMENTS I would like to express my appreciation to my advisor, Dr. M. Sam Mannan, for the opportunity of working in the Reactive Chemicals Research Laboratory and working on this industrial project. Over the past two years of my master’s study, his guidance and encouragement have supported me in completing this work. I would like to thank Dr. Kenneth R. Hall and Dr. Debjyoti Banerjee for their dedication to serving as my committee members. I also thank Dr. William J. Rogers for his communications with the industrial company that provided HAN samples for testing and for his advice on laboratory techniques. I am full of gratitude to Dr. Arcady Kossoy for his instructions in kinetics modeling with CISP software. Many thanks go to my colleagues for their assistance in learning and maintaining the APTAC and for their friendly help during graduate study and life, especially to Peter Ralbovsky for his technical advice on the troubleshooting of the APTAC, to Chunyang Wei for the APTAC training and helpful discussion, and to Susan Mitchell for English correction of the entire thesis. I also express my gratitude to Towanna Hubacek for help with graduating document work, and to all the staff at the Mary Kay O’Connor Process Safety Center for help with literature searches and workshop training during my master’s program. Last but not least, I am deeply grateful to my husband, Huachun Xu, for his understanding of my study and career. Without his total and unwavering support, Iviiwould not be able to study chemical engineering and to pursue this master’s degree.viiiTABLE OF CONTENTS Page ABSTRACT ................................................................................................................. iii DEDICATION............................................................................................................... v ACKNOWLEDGMENTS............................................................................................ vi TABLE OF CONTENTS ........................................................................................... viii LIST OF TABLES........................................................................................................ xi LIST OF FIGURES..................................................................................................... xii CHAPTER I INTRODUCTION.......................................................................................... 1 II CALORIMETRY APPROACH FOR THE STUDY OF THERMAL HAZARDS ..................................................................................................... 6 2.1. Introduction ........................................................................................... 6 2.2. Screening Level Calorimetry................................................................. 7 2.2.1.Differential Thermal Analysis (DTA) .......................................... 8 2.2.2.Differential Scanning Calorimetry (DSC).................................... 9 2.2.3.Reactive System Screening Tool (RSST)................................... 10 2.2.4.Thermogravimetric Analysis (TGA) ...........................................11 2.2.5.Isoperibolic Calorimetry ............................................................ 12 2.3. Advanced Calorimetry ........................................................................ 13 2.3.1.Accelerating Rate Calorimeter (ARC) ....................................... 14 2.3.2.Automatic Pressure Tracking Adiabatic Calorimeter (APTAC) 16 2.4. Comparison of Calorimeters ............................................................... 19 2.5. Miniature Calorimetry......................................................................... 23 2.6. APTAC