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An Experimental Test Plan for the Characterization of Molten Salt Thermochemical Properties in Heat Transport Systems

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An Experimental Test Plan for the Characterization of Molten Salt Thermochemical Properties in Heat Transport Systems INL/EXT-10-19921 An Experimental Test Plan for the Characterization of Molten Salt Thermochemical Properties in Heat Transport Systems Pattrick Calderoni September 2010 DISCLAIMER This information was prepared as an account of work sponsored by an agency of the U.S. Government. Neither the U.S. Government nor any agency thereof, nor any of their employees, makes any warranty, expressed or implied, or assumes any legal liability or responsibility for the accuracy, completeness, or usefulness, of any information, apparatus, product, or process disclosed, or represents that its use would not infringe privately owned rights. References herein to any specific commercial product, process, or service by trade name, trade mark, manufacturer, or otherwise, does not necessarily constitute or imply its endorsement, recommendation, or favoring by the U.S. Government or any agency thereof. The views and opinions of authors expressed herein do not necessarily state or reflect those of the U.S. Government or any agency thereof. INL/EXT-10-19921 An Experimental Test Plan for the Characterization of Molten Salt Thermochemical Properties in Heat Transport Systems Pattrick Calderoni September 2010 Idaho National Laboratory Idaho Falls, Idaho 83415 http://www.inl.gov Prepared for the U.S. Department of Energy Office of Nuclear Energy Under DOE Idaho Operations Office Contract DE-AC07-05ID14517 ABSTRACT Molten salts are considered within the Very High Temperature Reactor program as heat transfer media because of their intrinsically favorable thermophysical properties at temperatures starting from 300°C and extending up to 1200°C. In this context, two main applications of molten salt are considered, both involving fluoride-based materials: as primary coolants for a heterogeneous fuel reactor core and as secondary heat transport medium to a helium power cycle for electricity generation or other processing plants, such as hydrogen production. The reference design concept here considered is the Advanced High Temperature Reactor (AHTR), which is a large passively safe reactor that uses solid graphite-matrix coated-particle fuel (similar to that used in gas-cooled reactors) and a molten salt primary and secondary coolant with peak temperatures between 700 and 1000°C, depending upon the application. However, the considerations included in this report apply to any high temperature system employing fluoride salts as heat transfer fluid, including intermediate heat exchangers for gas-cooled reactor concepts and homogenous molten salt concepts, and extending also to fast reactors, accelerator-driven systems, and fusion energy systems. The purpose of this report is to identify the technical issues related to the thermophysical and thermochemical properties of the molten salts that would require experimental characterization in order to proceed with a credible design of heat transfer systems and their subsequent safety evaluation and licensing. In particular, the report outlines an experimental research and development test plan that would have to be incorporated as part of the design and operation of an engineering-scaled facility aimed at validating molten salt heat transfer components, such as intermediate heat exchangers. This report builds on a previous review of thermophysical properties and thermochemical characteristics of candidate molten salt coolants generated as part of the same project. However, this work focuses on two materials: the LiF- BeF2 eutectic (67 and 33 mol%, respectively, also known as flibe) as primary coolant and the LiF-NaF-KF eutectic (46.5, 11.5, and 52 mol%, respectively, also known as flinak) as secondary heat transport fluid. Common issues are identified involving the preparation and purification of the materials as well as the development of suitable diagnostics. Issues specific to each material and its application are then considered, focusing on the compatibility with structural materials and the extension of the existing properties database. v vi CONTENTS ABSTRACT .................................................................................................................................................. v ACRONYMS ............................................................................................................................................... ix 1. INTRODUCTION .............................................................................................................................. 1 1.1 Molten Salt Composition ......................................................................................................... 2 1.2 The Advanced High Temperature Reactor as Reference Design Concept .............................. 3 2. EXTENSION OF DATABASE OF PHYSICAL PROPERTIES RELEVANT TO HEAT TRANSFER APPLICATIONS .......................................................................................................... 6 3. DETECTION AND CONTROL OF MELT CHEMICAL COMPOSITION IN A HEAT TRANSFER TEST FACILITY ........................................................................................................ 11 3.1 Purification ............................................................................................................................. 11 3.1.1 Purification by Chemical Processing ........................................................................ 11 3.1.2 Purification by Electrochemical Methods ................................................................. 11 3.2 Electrochemical Analytical Methods ..................................................................................... 12 3.2.1 Electrical Conductivity ............................................................................................. 12 3.2.2 Potentiometry-EMF Measurement ............................................................................ 13 3.2.3 Various Methods of Voltammetry ............................................................................ 13 3.2.4 Chronopotentiometry ................................................................................................ 16 3.2.5 Reference Electrodes for Electrochemical Analysis ................................................. 16 3.3 Sampling and chemical analysis ............................................................................................ 17 4. MATERIAL COMPATIBILITY ISSUES RELEVANT TO A HEAT TRANSFER TEST FACILITY ........................................................................................................................................ 19 4.1 Definition of Corrosion in Fluoride Molten Salts .................................................................. 19 4.2 Limitations in Available Database of Structural Materials Corrosion in Molten Salt ........... 21 5. CONCLUSION ................................................................................................................................ 22 6. REFERENCES ................................................................................................................................. 23 FIGURES ,21 Figure 1. Lithium fluoride (LiF) and beryllium di-fluoride (BeF2) eutectic phase diagram. ..................... 2 Figure 2. Flibe handling during MSRE related experiments at ORNL. ........................................................ 3 Figure 3. AHTR system schematic.20 ............................................................................................................ 4 Figure 4. Flibe density and viscosity. ........................................................................................................... 7 Figure 5. Flibe surface tension and specific heat capacity. ........................................................................... 8 Figure 6. Flibe thermal conductivity and Nusselt number according to Dittus Boelter correlation. ............ 8 Figure 7. Flinak density and viscosity. ......................................................................................................... 9 Figure 8. Flinak surface tension and specific heat capacity. ......................................................................... 9 vii Figure 9. Flinak thermal conductivity and Nusselt number according to Dittus Boelter correlation. ........ 10 Figure 10. Plateaus shown for 0.2 nM Pb2+, Cd2+, and Zn2+ in 0.05 M KCl solution. ................................ 14 Figure 11. Current-potential curves from various scan rates and peak current versus square root scan rate plot for iron impurity in flinak. .................................................................................... 15 Figure 12. (a) Schematic illustration of anodic chronopotentiograms at different current densities and (b) corresponding plot of i1/2 vs. concentration to determine solubility. .......................... 16 Figure 13. Comparison of the stability of structural alloy elements with respect to fluoride corrosion [laurant thesis]. ........................................................................................................... 20 TABLES Table 1. AHTR main operating parameters.20 .............................................................................................. 5 viii ACRONYMS AHTR Advanced High Temperature Reactor ARE Aircraft Reactor Experiment BeF2 beryllium di-fluoride ICP-AES inductively coupled plasma atomic emission spectroscopy ICP-MS inductively coupled plasma mass spectroscopy LiF lithium fluoride Lif-NaF-KF lithium, sodium and potassium fluoride MSRE Molten Salt Reactor Experiment ORNL Oak Ridge National Laboratory R&D research and
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