The Removal of Barium, Strontium, Calcium and Magnesium from Hydraulic Fracturing
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The Removal of Barium, Strontium, Calcium and Magnesium from Hydraulic Fracturing Produced Water Using Precipitation with Traditional and Alternative Reactant Feedstocks A thesis presented to the faculty of the Voinovich School of Leadership & Public Affairs In partial fulfillment of the requirements for the degree Master of Science Jess D. Cogan April 2016 © 2016 Jess D. Cogan. All Rights Reserved. 2 This thesis titled The Removal of Barium, Strontium, Calcium and Magnesium from Hydraulic Fracturing Produced Water Using Precipitation with Traditional and Alternative Reactant Feedstocks by JESS D. COGAN has been approved for the Program of Environmental Studies and the Voinovich School of Leadership & Public Affairs by Natalie A. Kruse Daniels Associate Professor of Environmental Studies Mark Weinberg Director, Voinovich School of Leadership & Public Affairs 3 ABSTRACT COGAN, JESS D., M.S., April 2016, Environmental Studies The Removal of Barium, Strontium, Calcium and Magnesium from Hydraulic Fracturing Produced Water Using Precipitation with Traditional and Alternative Reactant Feedstocks Director of Thesis: Natalie A. Kruse Daniels Marcellus and Utica shale gas exploration is an industry that expands from southeastern New York, West Virginia, Pennsylvania and Ohio. The recovery of natural gas from the Marcellus and Utica shale beds is done through hydraulic fracturing. Hydraulic fracturing is a process that pumps large amounts of water into the shale formation causing fractures, allowing the gas to flow to the surface. As the water returns to the surface it is contaminated with inorganic compound found within the shale formation. This water is characterized as produced and flowback water. This study tested the removal rates of Ba+2, Sr+2, Ca+2 and Mg+2 from four synthetic produced water solutions undergoing treatment. The treatments were sulfation to remove Ba+2, softening to remove Ca+2, and hydrolysis to remove Mg+2. Sr+2 was also removed from the synthetic produced water solutions, but was not treated for specifically. Strontium removal occurred through co-precipitation during barium, calcium and magnesium treatments. The treatment order was found to impact the removal efficiency of these constituents. The optimized treatment of sulfation - hydrolysis- softening resulted in a 97-100% removal of barium, 97-100% removal of magnesium, 84-100% removal of calcium, and 64-100% removal of strontium. Acid mine drainage treatment showed 4 efficient removal of barium from all four synthetic solutions ranging from 63-99% removal, but strontium removals were low ranging from 1-16% removal. 5 DEDICATION This thesis is dedicated to my family, who instilled and supported my love for the outdoors and the beauty it provides. 6 ACKNOWLEDGMENTS A big thank you goes out to my advisor, Dr. Natalie Kruse for her utmost support and help through the research, writing, and completion of this project. I would like to thank my committee members Dr. Dina Lopez and Dr. Jason Trembly for their support and advisement. I would also like to thank the staff at the Institute for Sustainable Energy and the Environment, Shyler Switzer, David Ogden, Mira Cooper and Dr. Wen Fan for their cooperativeness and troubleshooting of the project hurdles, I would also like to thank Dr. Ben Stuart and Dr. Anirudh Ruhil for their help and advisement. I would like to thank my family for their support and the opportunity for this project provided to me by Voinovich School of Leadership and Public Affairs. 7 TABLE OF CONTENTS Page Abstract ............................................................................................................................... 3 Dedication ........................................................................................................................... 5 Acknowledgments............................................................................................................... 6 List of Tables ...................................................................................................................... 9 List of Figures ................................................................................................................... 10 Chapter 1: Introduction ..................................................................................................... 12 1.1 Objectives, Deliverables, Hypothesis ..................................................................... 14 Chapter 2: Literature Synthesis ......................................................................................... 16 2.1 Produced Water Composition ................................................................................. 16 2.2 Environmental Health and Effects .......................................................................... 18 2.3 Naturally Occurring Radioactive material (NORM) .............................................. 20 2.4 Treatment and Disposal Methods ........................................................................... 21 2.5 Precipitation Treatment ........................................................................................... 24 2.6 Acid Mine Drainage as a Possible Treatment Strategy .......................................... 24 Chapter 3: Methods ........................................................................................................... 27 3.1 Stock Solution Composition ................................................................................... 27 3.2 Equilibrium Studies ................................................................................................ 28 3.2.1 Sulfation ........................................................................................................... 28 3.2.3 Hydrolysis ........................................................................................................ 30 3.2.3 Softening .......................................................................................................... 33 3.3 Kinetics ................................................................................................................... 35 3.4 Acid Mine Drainage Treatment .............................................................................. 36 Chapter 4: Results and Discussion .................................................................................... 39 4.1 Batch Experiments .................................................................................................. 39 4.2 Kinetics ................................................................................................................... 49 4.3 Acid Mine Drainage Treatment .............................................................................. 60 Chapter 5: Conclusions ..................................................................................................... 68 5.1 Batch Experiments .................................................................................................. 68 5.2 Kinetics ................................................................................................................... 69 8 5.3 Acid Mine Drainage Treatment .............................................................................. 69 References ......................................................................................................................... 71 Appendix 1 – Batch Experiment Results and Summary Statistics ................................... 76 Appendix 2 – Kinetics Results and Summary Statistics ................................................... 79 Appendix 3 – Acid Mine Drainage Treatment Results and Summary Statistics .............. 83 9 LIST OF TABLES Page Table 1: Produced Water Quality for Pennsylvania, Ohio and West Virginia ................. 17 Table 2: Alternative Treatment Method Costs . ................................................................ 23 Table 3: Targeted mg/L of Constituents In Stock Solutions............................................. 28 Table 4: Amount of Constituents Added to Stock Solutions. ........................................... 28 Table 5: Solution pH During Precipitation Treatments .................................................... 49 Table 6: Solution pH During AMD Treatments ............................................................... 65 10 LIST OF FIGURES Page Figure 1. Flow Chart Followed for Sulfation Testing....................................................... 30 Figure 2. Flow Chart Followed for Hydrolysis Testing. ................................................... 32 Figure 3. Flow Chart Followed for Softening Testing. ..................................................... 35 Figure 4. Flow Chart Followed for Acid Mine Drainage Testing. ................................... 38 Figure 5a and 5b. Low IC (0.5) Removal Results with Hydrolysis Stage 3 and Softening Stage 3.. ............................................................................................................................. 41 Figure 6a and 6b. Medium IC (0.5) Removal Results with Hydrolysis Stage 3 and Softening Stage 3.. ............................................................................................................ 43 Figure 7a and 7b. High IC (2) Removal Results with Hydrolysis Stage 3 and Softening Stage 3.. ............................................................................................................................. 45 Figure 8a and 8b. High IC (4) Removal Results with Hydrolysis Stage 3 and Softening Stage 3.. ............................................................................................................................