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Enthalpy of Vaporization of Hypersaline Brine from 230 to 280 Bar

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Enthalpy of Vaporization of Hypersaline Brine from 230 to 280 Bar Enthalpy of Vaporization of Hypersaline Brine from 230 to 280 bar A thesis presented to the faculty of the Russ College of Engineering and Technology of Ohio University In partial fulfillment of the requirements for the degree Master of Science David D. Ogden May 2018 © 2018 David D. Ogden. All Rights Reserved. 2 This thesis titled Enthalpy of Vaporization of Hypersaline Brine from 230 to 280 bar by DAVID D. OGDEN has been approved for the Department of Mechanical Engineering and the Russ College of Engineering and Technology by Jason P. Trembly Associate Professor of Mechanical Engineering Dennis Irwin Dean, Russ College of Engineering and Technology 3 ABSTRACT OGDEN, DAVID D., M.S., May 2018, Mechanical Engineering Enthalpy of Vaporization of Hypersaline Brine from 230 to 280 bar Director of Thesis: Jason P. Trembly There is a need for thermodynamic data of mixed brine solutions in order to properly treat brines generated from oil/gas wells and CO2 sequestration. Thermodynamic properties of high concentration, multicomponent brine solutions are unknown, and limited to estimations based on single component solution data. Experimental data for mixed brine solutions at elevated temperatures and pressures does not exist due to the extreme operating conditions above the supercritical point of pure water. This study combines experimental results for mixed brine solutions, with thermodynamic models previously created for single component NaCl solutions to identify deviations resulting from additional dissolved species. Experiments were conducted using a Joule heated desalinator at pressures of 230 to 280 bar and temperatures of 387 to 406 ºC. 4 ACKNOWLEDGMENTS I would like to thank my advisor, Dr. Jason Trembly for his support of my research as well as assisting in the development of this thesis. I would also like to acknowledge the financial support of the National Energy Technology Laboratory (NETL) and the Ohio Water Development Authority. Further, the efforts of Dr. Wen Fan, Mr. Eli Fox, Ms. Rachel Schack and Mr. Dominik Steinberg for assistance in operation of the experimental apparatus and conducting analytical analyses are to be recognized, as well as Mr. Colton Nissen and Mr. Stuart Burkett for assistance in construction of the experimental apparatus. 5 TABLE OF CONTENTS Page Abstract ............................................................................................................................... 3 Acknowledgments............................................................................................................... 4 List of Tables ...................................................................................................................... 6 List of Figures ..................................................................................................................... 7 Chapter 1: Introduction ....................................................................................................... 9 1.1 Background ............................................................................................................... 9 1.2 Objectives ............................................................................................................... 11 Chapter 2: Literature Review ............................................................................................ 13 2.1 Supercritical Water Overview ................................................................................ 13 2.2 Supercritical Brine Thermodynamics ..................................................................... 15 2.3 Solubility of Dissolved Solids in Supercritical Water ............................................ 17 Chapter 3: Methods ........................................................................................................... 24 3.1 Materials ................................................................................................................. 24 3.2 Desalination System ............................................................................................... 26 3.3 Data Acquisition and Controls ................................................................................ 27 3.4 Sample Analysis ..................................................................................................... 29 3.5 Water Recovery ...................................................................................................... 29 3.6 Thermodynamic Modeling ..................................................................................... 30 3.6.1 Specific Heat Capacity ..................................................................................... 30 3.6.2 Enthalpy of Vaporization ................................................................................. 34 Chapter 4: Results ............................................................................................................. 37 4.1 Objective 1 .............................................................................................................. 37 4.2 Objective 2 .............................................................................................................. 43 4.3 Objective 3 .............................................................................................................. 45 4.4 Corrosion ................................................................................................................ 50 Chapter 5: Conclusions ..................................................................................................... 52 Chapter 6: Recommendations ........................................................................................... 53 References ......................................................................................................................... 55 6 LIST OF TABLES Page Table 1. The test brine concentrations were selected based on a review of water produced by oil/gas and CO2 injection wells [32]–[36]. All concentrations are presented in mg∙L-1 or g∙L-1 measured at normal temperature and pressure (293.15 K and 101.3 kPa). ........ 25 Table 2. Summary of experimental results for 50 and 180 g∙L-1 NaCl brines at 250 bar. 40 Table 3. Summary of experimental results for 50 and 180 g∙L-1 multicomponent brines. Data presented are three trial averages with standard deviations. Pseudocritical temperature of pure water is included for reference. ........................................................ 41 Table 4. Vapor product compositions for 50 and 180 g∙L-1 multicomponent brine experimental trials. Concentrations are presented in mg∙L-1, and vapor fractionation is presented as a percentage range from all trials conducted. Note that barium was below the detection limit and is presented as BDL. .......................................................................... 43 7 LIST OF FIGURES Page Figure 1: [A] Specific heat and [B] density of pure water at critical and supercritical pressures [29]. ................................................................................................................... 14 Figure 2: Subcritical and supercritical water divided into 4 distinctions regions with a common intersection at the supercritical point [29]. © 2011 Igor Pioro and Sarah Mokry. Originally published in Heat Transfer - Theoretical Analysis, Experimental Investigations and Industrial Systems under Creative Commons Attribution 3.0 Unported license. Available from: 10.5772/13790 ........................................................................................ 14 Figure 3: Driesner results compared to other state equations. [19] .................................. 17 Figure 4: Phase diagram of NaCl + H2O system at a constant temperature of 375 C.[18] ........................................................................................................................................... 18 Figure 5: Phase diagram for subcritical and supercritical brine at a constant pressure of 250 bar.[9] ......................................................................................................................... 19 Figure 6: P-T-x surface of NaCl-H2O system as described by Benchoff and Pitzer.[25] 20 Figure 7: NaCl concentrations presented against pressure on constant temperature lines from Bischoff and Pitzer results. [25] ............................................................................... 21 Figure 8: Solubility of sodium, potassium and calcium chloride and sulfate species at 250 Bar [30], pseudocritical line presented in green for reference. [29] ................................. 23 Figure 9: Dielectric constant and ion dissociation constant for water at 250 bar. [30] .... 23 Figure 10. (a) Process and instrumentation diagram for the prototype Joule-heating desalination system. (b) Cross section view of the prototype Joule-heating brine desalinator, a close up view of the vapor liquid equilibrium is shown. ............................ 27 Figure 11: Specific heat capacity for water and NaCl aqueous brines at (a) 230 bar, (b) 250 bar and (c) 280 bar. .................................................................................................... 31 Figure 12: Constant concentration lines plotted on the temperature enthalpy diagram at a constant pressure of 230 bar. ............................................................................................ 32 Figure 13. Control volume analysis (a) upper desalinator control volume used to estimate TVLE, (b) lower desalinator control volume used to calculate the enthalpy
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