Professional Documents
Culture Documents
by
Keigo Karakama
in
(Mechanical Engineering)
(Vancouver)
December 2011
light water coolant at high temperature and pressure beyond the critical point of water (374⁰C
and 22.1 MPa). The dramatic decrease in the solubility of magnetite in supercritical water
suggests that the precipitation of magnetite particles will occur in the reactor core which can
A once-through flow system was modified to develop experimental techniques for studying
the deposition and transport of magnetite particles in supercritical water onto stainless steel
316L. Experiments were run with temperatures ranging from 200°C to 400°C and a pressure
of 23.7 MPa. A hydrothermal method for synthesizing magnetite particles was adapted for
producing simulated corrosion products in which a typical run had an iron concentration of
An online monitoring technique using thermal resistance to infer deposit loadings showed
deposition and removal cycles of the corrosion product on the tube wall. Scanning electron
microscope images of particles on the tube inner wall and those collected by the high
temperature, high pressure filters revealed magnetite particles which were several hundred
nanometers to several microns in diameter depending on the precursor and condition of the
system. Ultrasound and acid wash cleaning methods were used to remove deposits from the
test section for determining deposit thickness and adhesive strength. The strength of deposit
adhesion was observed to increase along the tube, particularly under supercritical conditions
suggesting precipitation of dissolved species may enhance the strength of the deposit. By
ii
comparing the results, a comprehensive approach was developed to study magnetite fouling
Finally, comparison between a simulation model based on mass transport equations and
experimental deposition suggests that mass transport alone can overestimate the deposition
thickness when surface attachment and removal are significant as they were for many
experiments in this study. The simulation predicted as an upper limit scenario that fouling in
a CANDU SCWR could increase the fuel cladding temperature at certain locations by up to
iii
Preface
its analysis were done by the author. All Atomic absorption spectroscopy analysis, scanning
electron microscopy images and energy dispersive x-ray analysis was completed by the
author at the Materials Engineering Laboratories. X-ray diffraction data and analysis in
iv
Table of Contents
Abstract ..................................................................................................................................... ii
Preface...................................................................................................................................... iv
Table of Contents ...................................................................................................................... v
List of Tables ......................................................................................................................... viii
List of Figures .......................................................................................................................... ix
List of Symbols and Abbreviations......................................................................................... xv
Acknowledgements ............................................................................................................... xvii
1 Introduction ....................................................................................................................... 1
1.1 Supercritical Water ..................................................................................................... 1
1.2 Systems using Supercritical Water Medium .............................................................. 3
1.3 Scope and Objectives ................................................................................................. 3
2 Literature Review.............................................................................................................. 6
2.1 Applications of Supercritical Water ........................................................................... 6
2.1.1 Supercritical Fossil-fueled Power Plants ............................................................ 6
2.1.2 Supercritical Water Oxidation ............................................................................ 8
2.1.3 Nuclear Energy and the Generation IV Nuclear Reactors .................................. 8
2.1.4 CANDU Supercritical Water Reactors ............................................................. 10
2.2 Materials for SCWR ................................................................................................. 11
2.3 Corrosion and Fouling in Subcritical and Supercritical Water ................................ 13
2.3.1 Properties of Magnetite ..................................................................................... 13
2.3.2 Magnetite and its Solubility in High Temperature and Pressure Water ........... 15
2.3.3 Corrosion........................................................................................................... 17
2.3.4 Fouling .............................................................................................................. 18
2.3.5 Corrosion Product Removal and Transport ...................................................... 22
3 Heat Transfer and Deposition Modeling......................................................................... 25
3.1 Overview .................................................................................................................. 25
3.2 Heat Transfer Calculations of Water........................................................................ 25
3.2.1 Enthalpy of Fluid in the Test Section ............................................................... 25
3.2.2 Heat Transfer Coefficient in Supercritical Water ............................................. 26
v
3.2.3 Temperature of the Oxide Layer ....................................................................... 28
3.2.4 Temperature of the Outside Wall Temperature ................................................ 28
3.2.5 Buoyancy Calculations ..................................................................................... 29
3.3 Deposition Calculations ........................................................................................... 31
3.4 CANDU Supercritical Water Reactor Simulation ................................................... 38
4 Experiments .................................................................................................................... 41
4.1 Supercritical Water Once-through Flow Apparatus ................................................. 41
4.2 Flow and Temperature Control ................................................................................ 44
4.2.1 Safety ................................................................................................................ 44
4.2.2 Pressure Measurements ..................................................................................... 45
4.2.3 Flow Rate Measurements .................................................................................. 45
4.2.4 Fluid Conductivity Measurements .................................................................... 46
4.2.5 Dissolved Oxygen Concentration Measurements ............................................. 46
4.3 Particle Synthesis for Modeling Power Plant Fouling ............................................. 46
4.4 Experimental Procedure ........................................................................................... 48
4.4.1 Experiments with Precursor .............................................................................. 48
4.4.2 Experiments with Magnetite Particles .............................................................. 50
4.4.3 Post Experiment Cleaning................................................................................. 51
4.5 Analytical Methods .................................................................................................. 51
4.5.1 Online Thermal Resistance Monitoring ............................................................ 51
4.5.2 SEM Imaging for Filters and Tube Deposits .................................................... 59
4.5.3 Particulate Filtering System .............................................................................. 60
4.5.4 Deposit Thickness and Strength of Oxide Adhesion ........................................ 67
5 Results and Discussion of Experiments .......................................................................... 69
5.1 Reference Condition ................................................................................................. 70
5.1.1 Temperature Analysis ....................................................................................... 70
5.1.2 Filter Analysis ................................................................................................... 72
5.1.3 Deposit Analysis ............................................................................................... 73
5.2 Effect of Heat Flux ................................................................................................... 80
5.2.1 Temperature Analysis ....................................................................................... 80
5.2.2 Filter Analysis ................................................................................................... 80
vi
5.2.3 Deposit Analysis ............................................................................................... 84
5.3 High pH Conditions ................................................................................................. 87
5.3.1 Temperature Analysis ....................................................................................... 89
5.3.2 Filter Analysis ................................................................................................... 91
5.3.3 Deposit Analysis ............................................................................................... 93
5.4 Low Concentration and Blank Experiment .............................................................. 95
5.5 Overall Summary and Mass Balance ....................................................................... 95
6 Results and Discussion of Simulations ......................................................................... 100
6.1 Comparison between Simulation and Experimental .............................................. 100
6.2 Simulation for CANDU SCWR ............................................................................. 103
6.3 Limitations of the Simulation................................................................................. 107
7 Conclusion .................................................................................................................... 109
8 Recommendations ......................................................................................................... 112
References ............................................................................................................................. 113
Appendix A: MATLAB Code .............................................................................................. 120
Appendix B: Filter Parts Drawings ....................................................................................... 131
Appendix C: Results of Experiments.................................................................................... 133
C. 1. Reference Condition, Ferrous Chloride .............................................................. 133
C. 2. Reference Condition, Ferrous Sulfate ................................................................ 138
C. 3. Low Heat Flux, Ferrous Chloride ....................................................................... 143
C. 4. Low Heat Flux, Ferrous Sulfate ......................................................................... 148
C. 5. No Heat Flux, Ferrous Sulfate ............................................................................ 153
C. 6. High pH, Ferrous Sulfate .................................................................................... 158
C. 7. High pH & Subcritical, Ferrous Sulfate ............................................................. 163
C. 8. Low Concentration, Ferrous Chloride ................................................................ 166
C. 9. Blank Run ........................................................................................................... 169
Appendix D: Filter Flow Rates ............................................................................................. 172
Appendix E: Atomic Absorption Spectroscopy.................................................................... 173
vii
List of Tables
viii
List of Figures
Figure 1-1: Pressure - temperature diagram for water, grey region indicating supercritical
conditions............................................................................................................. 1
Figure 1-2: Density of water vs. temperature at various pressures, showing the effects of
pressure on the pseudocritical temperature ......................................................... 2
Figure 2-1: Simplified drawing of a direct cycle coolant for Generation IV CANDU SCWR
........................................................................................................................... 11
Figure 2-2: Pourbaix diagram (a) Fe – H2O at 25ºC and 1 atm, (b) Fe – H2O at 374°C and
220 atm (c) Fe/Cr – H2O at 25°C and 1 atm, (d) Fe/Cr – H2O at 374ºC and 220
atm. Based on SUPCRT92 (Propp et al., 1996) ............................................... 14
Figure 2-3: Magnetite solubility adapted from Cook and Fatoux (2009) for neutral pH water
at 25 MPa, Guzonas et al. (2009) for pH = 9.3 at 30 MPa, Burrill (2000) for
neutral pH at 25 MPa, and Sweeton and Baes Jr. (1970) experimental results. 16
Figure 3-1: Calculation of Grq/Grth for determination of the effects of buoyancy along the
test section using Bazargan et al. (2005) ........................................................... 31
Figure 3-2: Effect of particle diameter and fluid temperature on deposition velocity for
experimental apparatus ...................................................................................... 38
Figure 3-3: Cross-sectional view of CANFLEX 43 rod fuel bundle and drawing of
equivalent tube for simulation calculations (not to scale) ................................. 40
Figure 4-1: SCW system used in all experiments located in the Mechanical Engineering
laboratories. ....................................................................................................... 41
Figure 4-2: Schematic of supercritical once-through flow apparatus................................... 42
Figure 4-3: Mounting block and test section inlet ................................................................ 54
Figure 4-4: Electrical wiring, heater controls and location of surface welded thermocouples
and bulk fluid thermocouples ............................................................................ 57
Figure 4-5: Saturation temperature of 231.51ºC at 417psi, calibration for Experiment #1 . 58
Figure 4-6: Temperature of test section, calculated vs. calibrated thermocouples............... 58
Figure 4-7: Test section sample for SEM analysis ............................................................... 60
Figure 4-8: SS316L LTHP filter installed after the heat exchanger ..................................... 61
Figure 4-9: HTHP filter with silver membrane and SS304 back support ............................ 62
Figure 4-10: Glass fiber membrane and Swin-Lok LTLP filter holder .................................. 63
Figure 4-11: SEM photograph of clean silver membrane, 0.2µm pore size, using a Hitachi
S3000N SEM ..................................................................................................... 65
Figure 4-12: EDX of silver membrane to determine elemental composition of background 65
Figure 4-13: SEM photograph of clean glass fiber filter, 0.7µm pore size, a Hitachi S2300
SEM ................................................................................................................... 66
Figure 4-14: EDX of glass fiber filter to determine elemental composition of background .. 66
Figure 5-1: Temperature measurements of test section vs. time for reference condition with
ferrous chloride precursor (Experiment #1) ...................................................... 71
ix
Figure 5-2: SEM photograph of magnetite deposit on test section tube surface, 0.15 m
location. Reference condition with ferrous chloride precursor (Experiment #1)
........................................................................................................................... 73
Figure 5-3: SEM photograph of magnetite deposit on test section tube surface, 0.60 m
location. Reference condition with ferrous chloride precursor (Experiment #1)
........................................................................................................................... 74
Figure 5-4: SEM photograph of magnetite deposit on test section tube surface, 1.20 m
location. Reference condition with ferrous chloride precursor (Experiment #1)
........................................................................................................................... 74
Figure 5-5: SEM photograph of magnetite deposit on test section tube surface, 1.65 m
location. Reference condition with ferrous chloride precursor (Experiment #1)
........................................................................................................................... 75
Figure 5-6: XRD of tube deposits of test section, reference condition ferrous chloride
precursor (Experment #1) .................................................................................. 76
Figure 5-7: XRD of tube deposit of test section, reference condition ferrous sulfate
precursor (Experiment #2) ................................................................................. 76
Figure 5-8: Deposit thickness on test section for reference condition with ferrous chloride
precursor (Experiment #1) ................................................................................. 79
Figure 5-9: Deposit thickness on test section for reference condition with ferrous sulfate
precursor (Experiment #2) ................................................................................. 79
Figure 5-10: SEM photograph of particles collected on HTHP filter, 5.0k magnification, for
low heat flux with ferrous chloride precursor (Experiment #3) ........................ 81
Figure 5-11: EDX of HTHP filter for low heat flux with ferrous chloride precursor ............ 81
Figure 5-12: SEM photograph of particles collected on HTHP filter, 5.0k magnification, for
low heat flux with ferrous sulfate precursor (Experiment #4)........................... 82
Figure 5-13: SEM photograph of particles collected on HTHP filter, 5.0k magnification, for
no heat flux with ferrous chloride (Experiment #5) .......................................... 82
Figure 5-14: XRD of deposit on HTHP filter for low heat flux with ferrous chloride
precursor (Experiment #3) ................................................................................. 83
Figure 5-15: Deposit thickness on test section, low heat flux with ferrous sulfate precursor
(Experiment #4) ................................................................................................. 84
Figure 5-16: Calibration of the conductivity meter for determining NaOH concentration in
primary tank ....................................................................................................... 88
Figure 5-17: Predicted pH of the system using data from Arden (1950).............................. 89
Figure 5-18: Temperature measurements of test section vs. time for high pH with ferrous
sulfate precursor (Experiment #6). Power turned off briefly at t = 48 minutes. 90
Figure 5-19: SEM photograph of particles collected on HTHP filter, 10.0k magnification, for
high pH, ferrous sulfate (Experiment #6) .......................................................... 91
Figure 5-20: SEM photograph of particles collected on LTHP filter, 2.0k magnification, for
high pH, ferrous sulfate (Experiment #6) .......................................................... 92
x
Figure 5-21: SEM photograph of particles collected on HTHP filter, 5.0k magnification, for
high pH, subcritical, ferrous sulfate (Experiment #7) ....................................... 92
Figure 5-22: SEM photograph of particles collected on LTHP filter, 2.0k magnification, for
high pH, subcritical, ferrous sulfate (Experiment #7) ....................................... 93
Figure 5-23: Deposit thickness on test section (Experiment #6) ............................................ 94
Figure 6-1: Comparison between simulation and experimental for reference conditions (a)
Experiment #1, ferrous chloride with average particle size = 4 µm, magnetite
concentration = 200 mg/L (b) Experiment #2, ferrous sulfate with average
particle size = 1 µm, magnetite concentration = 299 mg/L. ............................ 100
Figure 6-2: Comparison between simulation and experimental for ferrous sulfate
experiments with (a) Experiment #4, low heat flux with average particle size =
1 µm, magnetite concentration = 108 mg/L and (b) Experiment #5, no heat flux
with average particle size = 2 µm, magnetite concentration = 89 mg/L. ........ 101
Figure 6-3: Comparison between simulation and experimental for Experiment #6, high pH,
ferrous sulfate. Simulation was run with an average particle size = 0.15µm,
magnetite concentration = 321 mg/L. .............................................................. 102
Figure 6-4: Bulk fluid and fuel cladding-surface temperature without particle deposition 104
Figure 6-5: Bulk fluid and fuel cladding-surface temperature after 1 year of operation with
magnetite particles of 150 nm diameter .......................................................... 104
Figure 6-6: Magnetite deposition thickness on fuel cladding after 1 year of operation for
150 nm and 1 µm average particle diameters .................................................. 105
Figure C-1: Temperature measurements of test section vs. time for reference condition with
ferrous chloride precursor. (Experiment #1) ................................................... 134
Figure C-2: SEM photograph of particles collected on HTHP filter, 2.0k magnification, for
reference condition with ferrous chloride precursor. Low flow rate in secondary
line resulting in very few particles collected. (Experiment #1) ....................... 134
Figure C-3: SEM photograph of particles collected on LTHP filter, 1.8k magnification, for
reference condition with ferrous chloride precursor. (Experiment #1) ........... 135
Figure C-4: SEM photograph of particles collected on LTLP filter, 2.0k magnification, for
reference condition with ferrous chloride precursor. Low flow rate in secondary
line resulting in very few particles collected. (Experiment #1) ....................... 135
Figure C-5: SEM photograph of magnetite deposit on test section tube surface, (a) 0.15 m,
(b) 0.60 m, (c) 1.20 m, and (d) 1.65 m location. (Experiment #1) .................. 136
Figure C-6: Deposit thickness on test section for reference condition with ferrous chloride
precursor. (Experiment #1) .............................................................................. 137
Figure C-7: Comparison between simulation and experimental for reference condition
ferrous chloride. Simulation was run with an average particle size = 4 µm,
magnetite concentration = 200 mg/L. .............................................................. 137
xi
Figure C-8: Temperature measurements of test section vs. time, temperature fluctuations
were found in both the inlet and outlet bulk temperatures which may be
attributed to the inconsistent flow. (Experiment #2) ....................................... 139
Figure C-9: SEM photograph of particles collected on HTHP filter, 2.0k magnification, for
reference condition with ferrous sulfate. (Experiment #2) .............................. 139
Figure C-10: SEM photograph of particles collected on LTHP filter, 2.0k magnification, for
reference condition with ferrous sulfate. (Experiment #2) .............................. 140
Figure C-11: SEM photograph of particles collected on LTLP filter, 2.0k magnification, for
reference condition with ferrous sulfate. (Experiment #2) .............................. 140
Figure C-12: SEM photograph of magnetite deposit on test section tube surface, (a) 0.15 m,
(b) 0.60 m, (c) 1.20 m, and (d) 1.65 m location. (Experiment #2) .................. 141
Figure C-13: Deposit thickness on test section for reference condition with ferrous sulfate
precursor. (Experiment #2) .............................................................................. 142
Figure C-14: Comparison between simulation and experimental for reference condition
ferrous sulfate. Simulation was run with an average particle size = 1 µm,
magnetite concentration = 190 mg/L. .............................................................. 142
Figure C-15: Temperature measurements of test section vs. time for low heat flux ferrous
chloride precursor. (Experiment #3) ................................................................ 144
Figure C-16: SEM photograph of particles collected on HTHP filter, 2.0k magnification, for
low heat flux with ferrous chloride precursor. (Experiment #3) ..................... 144
Figure C-17: SEM photograph of particles collected on LTHP filter, 2.0k magnification, for
low heat flux with ferrous chloride precursor. (Experiment #3) ..................... 145
Figure C-18: SEM photograph of particles collected on LTLP filter, - magnification, for low
heat flux with ferrous chloride precursor. (Experiment #3) ............................ 145
Figure C-19: SEM photograph of magnetite deposit on test section tube surface, (a) 0.10 m,
(b) 0.30 m, and (c) 0.90 m location. (Experiment #3) ..................................... 146
Figure C-20: Deposit thickness on test section for low heat flux ferrous chloride precursor.
(Experiment #3) ............................................................................................... 147
Figure C-21: Temperature measurements of test section vs. time for low heat flux with
ferrous sulfate precursor. (Experiment #4) ...................................................... 149
Figure C-22: SEM photograph of particles collected on HTHP filter, 2.0k magnification, for
low heat flux ferrous sulfate precursor (Experiment #4) ................................. 149
Figure C-23: SEM photograph of particles collected on LTHP filter, 2.0k magnification, for
low heat flux ferrous sulfate precursor. (Experiment #4) ................................ 150
Figure C-24: SEM photograph of particles collected on LTLP filter, 2.0k magnification, for
low heat flux ferrous sulfate precursor. (Experiment #4) ................................ 150
Figure C-25: SEM photograph of magnetite deposit on test section tube surface, (a) 0.15 m,
(b) 0.60 m, (c) 1.20 m, and (d) 1.65 m location. (Experiment #4) .................. 151
Figure C-26: Deposit thickness on test section for low heat flux ferrous sulfate precursor.
(Experiment #4) ............................................................................................... 152
xii
Figure C-27: Comparison between simulation and experimental for low heat flux, ferrous
sulfate. Simulation was run with an average particle size = 1 µm, magnetite
concentration = 108 mg/L................................................................................ 152
Figure C-28: Temperature measurements of test section vs. time for no heat flux with ferrous
sulfate precursor. (Experiment #5) .................................................................. 154
Figure C-29: SEM photograph of particles collected on HTHP filter, 2.0k magnification, for
no heat flux with ferrous sulfate precursor. (Experiment #5).......................... 154
Figure C-30: SEM photograph of particles collected on LTHP filter, 2.0k magnification, for
no heat flux with ferrous sulfate precursor. (Experiment #5).......................... 155
Figure C-31: SEM photograph of particles collected on LTLP filter, 2.0k magnification, for
no heat flux with ferrous sulfate precursor. (Experiment #5).......................... 155
Figure C-32: SEM photograph of magnetite deposit on test section tube surface, (a) 0.15 m,
(b) 0.60 m, (c) 1.20 m, and (d) 1.65 m location. (Experiment #5) .................. 156
Figure C-33: Deposit thickness on test section for no heat flux with ferrous sulfate precursor.
(Experiment #5) ............................................................................................... 157
Figure C-34: Comparison between simulation and experimental for no heat flux with ferrous
sulfate precursor. Simulation was run with an average particle size = 2 µm,
magnetite concentration = 89 mg/L. ................................................................ 157
Figure C-35: Temperature measurements of test section vs. time for high pH with ferrous
sulfate precursor. (Experiment #6) .................................................................. 159
Figure C-36: SEM photograph of particles collected on HTHP filter, 2.0k magnification, for
high pH with ferrous sulfate precursor. (Experiment #6) ................................ 159
Figure C-37: SEM photograph of particles collected on LTHP filter, 2.0k magnification, for
high pH with ferrous sulfate precursor. (Experiment #6) ................................ 160
Figure C-38: SEM photograph of particles collected on LTLP filter, 2.0k magnification, for
high pH with ferrous sulfate precursor. (Experiment #6) ................................ 160
Figure C-39: SEM photograph of magnetite deposit on test section tube surface, (a) 0.15 m,
(b) 0.60 m, (c) 1.20 m, and (d) 1.65 m location. (Experiment #6) .................. 161
Figure C-40:Deposit thickness on test section for high pH with ferrous sulfate precursor.
(Experiment #6) ............................................................................................... 162
Figure C-41: Comparison between simulation and experimental for high pH, ferrous sulfate.
Simulation was run with an average particle size 0.15 µm, magnetite
concentration = 321 mg/L................................................................................ 162
Figure C-42: Temperature measurements of test section vs. time for high pH & subcritical
with ferrous sulfate precursor. (Experiment #7) .............................................. 164
Figure C-43: SEM photograph of particles collected on HTHP filter, 2.0k magnification, for
high pH & subcritical with ferrous sulfate precursor. (Experiment #7) .......... 164
Figure C-44: SEM photograph of particles collected on LTHP filter, 2.0k magnification, for
high pH & subcritical with ferrous sulfate precursor. (Experiment #7) .......... 165
xiii
Figure C-45: SEM photograph of particles collected on LTLP filter, 2.0k magnification, for
high pH & subcritical with ferrous sulfate precursor. (Experiment #7) .......... 165
Figure C-46: Temperature measurements of test section vs. time for low concentration with
ferrous chloride precursor. (Experiment #8) ................................................... 167
Figure C-47: SEM photograph of particles collected on HTHP filter, 2.0k magnification, for
low concentration with ferrous chloride precursor. (Experiment #8).............. 167
Figure C-48: SEM photograph of particles collected on LTHP filter, 2.0k magnification, for
low concentration with ferrous chloride precursor. (Experiment #8).............. 168
Figure C-49: SEM photograph of particles collected on LTLP filter, 2.0k magnification, for
low concentration with ferrous chloride precursor. (Experiment #8).............. 168
Figure C-50: Temperature measurements of test section vs. time for high pH & subcritical
with ferrous sulfate precursor. (Experiment #9) .............................................. 170
Figure C-51: SEM photograph of particles collected on HTHP filter, 2.0k magnification,
blank run. (Experiment #9) .............................................................................. 170
Figure C-52: SEM photograph of particles collected on LTHP filter, 5.0k magnification,
blank run. (Experiment #9) .............................................................................. 171
Figure C-53: SEM photograph of particles collected on LTLP filter, 2.0k magnification,
blank run. (Experiment #9) .............................................................................. 171
Figure E-1: Calibration curve for iron concentration using AAS, nitric acid matrix ......... 173
Figure E-2: Calibration curve for iron concentration using AAS, nitric acid and copper
sulfate matrix ................................................................................................... 174
xiv
List of Symbols and Abbreviations
f Friction factor
Gr Grashoff number
H1 Enthalpy [kJ/kg]
H2 Enthalpy [kJ/kg]
HKF Helgeson-Kirkham-Flowers
Nu Nusselt number
Pr Prandtl number
Re Reynolds number
Sc Schmidt number
xv
SCWO Supercritical Water Oxidation
U* Frictional velocity
ε Tube roughness
xvi
Acknowledgements
First and foremost I would like to thank my supervisors, Dr. Steven Rogak and Dr. Akram
Alfantazi for their invaluable insight and guidance into making this thesis possible. I would
also like to express my gratitude to Dr. Edouard Asselin whose advice gave further direction
to this thesis. Furthermore, I would like to thank NSERC and AECL for their financial
I would like to thank Andrej Boskovics for his help on the construction of the electrical
heaters and flow loop. Additionally, I would like to thank my lab colleagues, Tirdad Nickchi,
Hamid Zebardast, Hugo Tjong, Arka Soewono, Mohammad Taghavi, and Kamran Alba for
Also, many thanks to the technicians who were incredibly helpful and patient in teaching me
the operation and analysis of the equipment: Dr. Berend Wassink on atomic absorption
spectroscopy, Jacob Kabel on the scanning electron microscope, Anita Lam for X-ray
diffraction analysis, the mechanical machine shop for their assistance in machining
components, the electronics shop for their advice on the electrical heater and controls, and
Perry Yabuno for always making sure that parts were ordered and received as soon as
possible.
Finally, I would like to thank all my friends and family who provided moral support
xvii
1 Introduction
Supercritical water (SCW) refers to water above the critical point of 374⁰C and 22.1 MPa.
Above this temperature and pressure, water exists only as a single phase fluid with very
Supercritical
water
Liquid
Pressure
374ºC
22.1MPa
Solid
Vapor
Temperature
Figure 1-1: Pressure - temperature diagram for water, grey region indicating supercritical
conditions.
Viscosity, density, and dissolution of non-polar and polar species can change dramatically
and is an excellent solvent for other polar substances such as inorganic salts. On the other
hand, organic species are generally non-polar and therefore are usually not soluble in
subcritical water. In supercritical conditions, the characteristics described above are reversed
1
and non-polar organic species and gases become significantly soluble, while ionic species
While the critical temperature gives the threshold temperature for achieving supercritical
often times more useful to describe the transition using the “pseudocritical” temperature. The
maximum for any given supercritical pressure. This temperature increases as the pressure
increases as shown in Figure 1-2. Other parameters such as heat capacity and ionic product of
water are also affected by pressure and its transition also shifts to higher temperature as
Figure 1-2: Density of water vs. temperature at various pressures, showing the effects of
pressure on the pseudocritical temperature
2
1.2 Systems using Supercritical Water Medium
Supercritical water has been a crucial medium in numerous industrial and research
applications for its interesting properties. Large variations in fluid and thermal properties
near the critical point offers an opportunity to fine tune fast chemical reactions with only
small adjustments in pressure and temperature (Kritzer, 2004). The special properties of
supercritical water as an excellent solvent for organic material have led to the technology of
supercritical water oxidation systems (Shaw et al., 1991) while the excellent heat transport
characteristics have led to power plants operating at higher temperature and pressure.
Material degradation has been a major limiting factor, however, new technology in materials
in the last few decades have allowed coal-fired power plants to operate in supercritical
conditions (Viswanathan et al., 2005). Finally, the need for cleaner and more efficient energy
has recently prompted research into supercritical water reactors (SCWR) for nuclear power
plants. Despite the operational experience with supercritical water in various applications,
Both the UBC Mechanical and Materials Engineering departments are collaborating with
AECL in the development of monitoring techniques for corrosion and fouling in supercritical
water. The primary application for the technology is for the CANDU supercritical water
reactors, however, the scope of this research can be applied for many similar systems such as
supercritical fossil-fueled and supercritical light water reactors. The purpose of this particular
3
Experimental investigations were conducted to examine four techniques for measuring and
monitoring fouling and transport of magnetite in supercritical water. These experiments were
focused on determining the effects of heat flux, temperature and pH on the particle size,
deposition rate, and adhesive strength of particle to the wall. A once-through flow loop was
replicate SCWR conditions. A hydrothermal method for synthesizing iron oxide particles in
supercritical water was adapted for producing simulated magnetite corrosion particles.
temperature measurements was constructed by the author for this study to measure fouling
and removal rates. High and low temperature filters were also fabricated and installed after
the test section to collect particles in each experiment. These filters were analyzed using
Scanning Electron Microscopy (SEM) to provide insight into the effects of pH on the
magnetite particle size and structure produced in supercritical water. In addition, deposition
morphology and thickness was determined using SEM and Atomic Absorption Spectroscopy
(AAS). A novel, two-step cleaning procedure was developed for qualitatively determining
A heat and mass transfer model was created to compare simulations with experimental
deposition thicknesses to determine if a mass transport limited model can accurately predict
deposition of magnetite particles in supercritical water. Due to the lack of experimental data
4
assumed to be mass transport limited. Simulations were also run to quantify the deposition of
magnetite onto a CANDU nuclear reactor for one year. The results and its implications on a
SCWR are presented in Chapter 6. Finally the conclusions and recommendations for future
5
2 Literature Review
The thermal efficiency of fossil-fueled power plants has increased over the past century by
operating steam at higher pressure and temperature, and thereby increasing the
thermodynamic efficiency (Masuyama, 2001). In the 1920’s, the pressure and temperature
was limited to 4 MPa and 370°C due to the mechanical properties of carbon steel. However,
high temperature resistant steels have allowed coal-fired power plants to operate as high as
24 MPa and 600°C. With nearly two dozen power plants worldwide currently operating at
580 – 600°C and 24 – 25 MPa, there is considerable operational experience with supercritical
water in power generation (Viswanathan et al., 2005). These experiences with supercritical
fossil-fueled power plants can provide invaluable insight into possible operational issues for
a nuclear SCWR.
Studies on the scaling of austenitic steels in supercritical fossil-fueled power plants show a
duplex oxide structure in which the outer layer is likely to exfoliate compared to an inner
layer of chromium and nickel oxide which almost never exfoliates. Once the scale thickness
reaches approximately 100 – 200 µm, oxides on austenitic steel begin to exfoliate due to the
differences in thermal expansion between the tube surface and the outer oxide layer,
especially during startup and stop time of the boiler (Masuyama, 2001). It was also found
that fine-grained steels and high-Cr steels had very slow oxide growth with very little
6
exfoliation. In general, chromium content above 20% was effective at preventing steam oxide
buildup. Tube plugging due to exfoliated material buildup can cause overheating in the
portion of the tube, resulting in creep rupture of the piping when the pressure due to the
fouling buildup exceeds the creep strength of the tubing (Masuyama, 2001). In addition,
exfoliated material has also been found to erode turbine components in a supercritical fossil-
fueled power plant if solid particles are found in the fluid stream. Therefore, scale build-up
and its resistance to exfoliation is a major concern for any system running SCW.
There are several key differences between a supercritical fossil-fueled power plant and
nuclear SCWR design requirements which make it particularly challenging for SCWR (Was
et al., 2007). First, compared to supercritical fossil-fueled power plants which usually can
have fire tubes with wall thickness of up to 10 mm, the fuel cladding in a nuclear reactor core
is restricted to 0.5 - 0.6 mm due to thermal and neutron efficiency (Zhang et al., 2009).
Larger amount of corrosion product deposits are often found on superheater tubes operating
above the critical point in a supercritical fossil-fueled power plant and it is not unusual to
find oxide films of several hundred micrometer thickness on these tubes (Cook & Fatoux,
2009). Such high fouling rates and deposit thickness would be unacceptable for a fuel
cladding in a SCWR. Second, the cooling water in the boiler tubes sees a geometrically
smooth surface along the boiler while the core of a SCWR will have a fuel assembly of
7
2.1.2 Supercritical Water Oxidation
The high solubility of organic species in supercritical water has led to the research in
“supercritical water oxidation” (SCWO), technology which was developed for destroying
hazardous organic waste (Helling & Tester, 1988). Despite its initial success, problems with
fouling and corrosion resulted in high operating costs which has forced the majority of
commercial SCWO plants constructed and operated in the late 90’s and early 2000’s to
permanently shut down (Marrone et al., 2005). There was extensive experimental work
however, the environment is often highly oxidizing and in some cases highly acidic which
are significantly different from the water chemistry which will likely be used for a CANDU
SCWR (Kritzer, 2004). It has been well observed from SCWO research that acidic water
chemistry promotes rapid corrosion, especially slightly below the pseudocritical temperature.
With inorganic salts in supercritical conditions, very high fouling rates are observed and the
deposit can completely plug flow of a system resulting in increased system pressure and the
As energy demand continues to increase and the effects of energy production on the global
environment escalates, the need for cleaner and more efficient technology grows ever more
important. Nuclear energy provides approximately 13.8% of the world’s energy demand and
its fuel provides energy with low greenhouse gas emissions making it an ideal candidate for
future energy production (International Atomic Energy Agency, 2010). These facilities
require some of the most advanced technology available and the Generation III++ is the most
8
recent design incorporating the technology developed for the industry over the last half
century. Generation IV nuclear technology is to succeed the current Generation III++ nuclear
reactors with state-of-the-art technology to improve on safety, lower byproduct waste, and
higher efficiency (Cook & Fatoux, 2009; Khartabil, 2009). There are currently six emerging
technologies for Generation IV nuclear reactors, one of these systems being SCWR in which
the coolant will operate above the critical point of water. The first of the Generation IV
nuclear reactors utilizing SCWR technology are expected to go online in 2025 as presented in
The higher operating temperature and pressure of a SCWR is expected to increase the
35% for conventional nuclear power plants (Naidin et al., 2009). This is due to the single
phase coolant which improves heat transfer and simplifies the overall design by reducing the
number of equipment and flow loops. In addition, the higher enthalpy of the coolant at higher
temperatures especially near the critical point offers an opportunity to decrease the mass flow
of the coolant for the same thermal output, resulting in smaller pumps, piping and housing
9
2.1.4 CANDU Supercritical Water Reactors
reactor developed by Atomic Energy of Canada Limited (AECL). The CANDU nuclear
design is unique in that it uses heavy water as a moderator versus light water, which allows
the reactors to use non-enriched uranium as fuel. In addition, the CANDU reactors use
pressure tubes rather than a pressure vessel in the reactor core, simplifying high pressure
designs and making the movement towards a supercritical coolant the next logical step
The coolant would enter the reactor core at 350⁰C and leave the core at above 600⁰C and
25MPa, finally leading to a high pressure turbine in the case of a direct cycle system (Naidin
et al., 2009). A simplified drawing of the proposed CANDU SCWR is provided in Figure
2-1.
The low solubility of inorganic salts in supercritical water suggest that there is greater
possibility for higher fouling rates of metal oxides in a SCWR core than previously seen in a
subcritical CANDU reactor. Metal oxides may nucleate from solution to form nano to
micrometer sized particles which may foul onto various heat transfer surfaces, leading to
higher than expected temperatures and accelerating material degradation. Particles which do
not deposit may be carried in the bulk fluid to the steam turbines which can lead to solid
10
Turbine Generator
Reactor Core
Condenser
Preheater
Pump
Figure 2-1: Simplified drawing of a direct cycle coolant for Generation IV CANDU SCWR
There are currently five materials that are under evaluation as potential materials to be used
in SCWR for various components such as the fuel cladding, pressure tubes, etc. (Zhang et al.,
2009).
Modified zircaloys
11
Experiments presented in this study are constructed from mainly SS316L material. Austenitic
Stainless Steels such as AISI 304 and AISI 316 are part of a family of stainless steels with
nickel content which preserve the austenite crystal structure during cooling. Compared to
martenitic and ferritic stainless steels, austenitic stainless steel enjoys the advantages of being
The ‘L’ of 316L indicates that the particular stainless steel has lower carbon content than that
of unstabilized austenitic steels such as 316 and 304. When types 316 and 304, are subject to
high temperatures in the range of 550°C to 880ºC, chromium carbide tend to precipitate
along the grain boundaries, forming areas depleted of chromium below the minimum 12%.
These areas become susceptible to corrosion in and near these boundaries where the material
has become sensitized (Sinha, 1989). In operational power plants, these sensitized austenitic
steels have been found to fail by intergranular stress corrosion cracking (IGSCC) in the
tubing of boiler water reactors (R. L. Jones et al., 1993). By lowering the carbon content to
below 0.03%, the amount of M23C6 that forms is minimized. Furthermore, the addition of
molybdenum (Mo) in 316L SS as opposed to 304L SS which does not have Mo, improves
Table 2-2: Stainless steel AISI 316L composition (American Society for Metals, 1985)
C Mn Si Cr Ni P S Mo N
16.0 - 10.0 -
0.03 2.00 1.00 0.045 0.03 2.0 - 3.0 0.10
18.0 14.0
12
2.3 Corrosion and Fouling in Subcritical and Supercritical Water
Magnetite is an iron oxide mineral with the chemical composition of Fe3O4. It is also known
as a ferric-ferrous oxide as it is one part wüstite (FeO) and one part hematite (Fe2O3). It is
part of the spinel group which is a group of minerals that have a chemical composition of
a cubic (Anthony et al., 1997). Magnetite, which is the stable form of iron oxide in SCWR
conditions, is expected to be the dominant metal oxide formed in the core due to the presence
of iron in many high temperature alloys. It is a common corrosion product found on the tubes
Pourbaix diagrams, also known as Eh-pH diagrams indicate the stable regions for metal
species. Solid lines indicate the border between two species while the diagonal dashed lines
indicate the stable region for water. Above the upper dashed line, water is oxidized to oxygen
while below the lower line, water is reduced to hydrogen (D. A. Jones, 1996). The
2-1
2-2
Figure 2-2 is a Pourbaix diagram for iron and iron-chromium created from SUPCRT92.
Because of its dependence on temperature and pH, the borders for stable species will vary
13
from one temperature to another and change dramatically in supercritical conditions (Propp
et al., 1996).
2.20
Fe3+ FeO42-
1.45
FeO42-
0.70
Fe2O3 Fe2O3
2+
-0.05 Fe 2+
Fe
Fe3O4
Fe3O4
-0.88
Fe
Fe
-1.55 HFeO2
Eh(V)
2.20
Cr2O72- Cr2O72-
1.45 FeO42-
FeO42-
CrO42-
CrO2
0.70 CrO2
3+
CrO42-
Cr
Fe2O3
-0.05 Cr3+ Fe2O3
Fe2+ Cr2O3
-0.88 Cr2+ Cr2O3
CrO
Fe CrO33-
-1.55 Fe Cr
Cr
-2 2 6 10 14 -2 2 6 10 14
pH
Figure 2-2: Pourbaix diagram (a) Fe – H2O at 25ºC and 1 atm, (b) Fe – H2O at 374°C and
220 atm (c) Fe/Cr – H2O at 25°C and 1 atm, (d) Fe/Cr – H2O at 374ºC and 220
atm. Based on SUPCRT92 (Propp et al., 1996)
14
2.3.2 Magnetite and its Solubility in High Temperature and Pressure Water
The solubility of corrosion products play a primary role in corrosion and fouling in aqueous
systems (Kritzer, 2004). In particular, the solubility of magnetite, an iron oxide of the form
Fe3O4, in high temperature and pressure water is a crucial information to operators in the
power industry due to the prevalence of the mineral found on heated tube surfaces.
Solubility of magnetite in alkaline and acidic water conditions has been measured up to
300⁰C by several groups. Sweeton and Baes Jr. (1970) tested magnetite solubility with
varying pH using potassium hydroxide and hydrochloric acid while Tremaine and LeBlanc
(1980) adjusted pH with sodium hydroxide and hydrochloric acid. The dissolution of
magnetite requires the reduction of FeIII to FeII. The equilibrium equation is provided in
( ) ( ) ( ) 2-3
currently unavailable. There are several major problems which make measuring solubility of
magnetite extremely difficult. First, the low solubility of iron means that measurements must
be done in parts per billion and parts per trillion ranges. Preventing iron contamination of the
solution from tubing, pumps, valves, etc. becomes increasingly difficult as materials that
withstand supercritical conditions are limited to high temperature alloys which often have
15
To overcome the deficiency in experimental solubility data for magnetite, thermodynamic
studies utilizing the Helgeson-Kirkham-Flowers (HKF) extrapolation for the Gibbs free
energy at high temperature and pressure have been used to predict the solubility of magnetite
in supercritical conditions (Cook & Fatoux, 2009; Guzonas et al., 2009). In another study by
Burrill (2000), magnetite solubility data from Bohnsack was extrapolated from subcritical to
density. The simulation results are provided for comparison in Figure 2-3.
Figure 2-3: Magnetite solubility adapted from Cook and Fatoux (2009) for neutral pH water
at 25 MPa, Guzonas et al. (2009) for pH = 9.3 at 30 MPa, Burrill (2000) for
neutral pH at 25 MPa, and Sweeton and Baes Jr. (1970) experimental results.
16
All three solubility simulations show a drop in solubility between 350ºC to 400ºC as the
density of water drops and the water transitions from polar to non-polar solvent. For models
based on HKF, the solubility increases once again as the temperature increases even higher
after the initial drop. The HKF model has been successful in correlating equilibrium
constants for hundreds of inorganic aqueous species in high temperature and high pressure
water including supercritical water (Sue et al., 2002). Cook and Fatoux model was adopted
for the simulation in this study for this reason as well as because it used pressure closer to
those expected in a CANDU SCWR of 25 MPa. Under this model, minimum solubility is
reached at 400°C and 25 MPa under neutral pH conditions with an iron concentration of
Fe(OH)3 are expected to be the dominant dissolved species in the solution (Cook & Fatoux,
2009).
2.3.3 Corrosion
Due to significant changes in the thermal and chemical properties of water from subcritical to
supercritical water environment (Was et al., 2006). In supercritical water systems, general
corrosion and stress corrosion cracking are found to be one of the dominant corrosion
mechanisms (Was et al., 2007; Zhang et al., 2009). For general corrosion, the surface of the
alloy undergoes oxidation and forms metal oxide corrosion product. This can be of particular
dissolved oxygen are present, resulting in very high corrosion rates (Lister, 1980). It has been
17
found experimentally that at high temperatures, oxides are preferentially formed over
However, not all corrosion products are undesirable and the corrosion products can produce a
protective film that reduce the rate of corrosion of the underlying metal (Lister, 1980).
Corrosion of austenitic stainless steel and nickel alloys subject to supercritical water is
observed to form a multilayer oxide on the surface. These are found to be tens to hundreds of
nanometers thick after several hundred hours in a deaerated supercritical condition (Was et
al., 2007). In high temperature aqueous systems, iron ions diffuse to the outer surface while
oxygen from the solution diffuses into the metal alloy. This produces a duplex oxide
structure: a dense inner chromium-iron rich layer and a porous magnetite outer layer. The
inner chromium rich layer has a spinel structure and provides protection to the alloy while
the porous outer layer provides no further protection (Gao et al., 2007; Was et al., 2006).
Therefore, the corrosion rate is dependent on the oxygen diffusion through the inner layer
following an Arrhenius behavior in which the high temperature provides the activation
2.3.4 Fouling
Another method for corrosion products to form on the surface is the deposition of corrosion
products from the bulk solution through “ex-situ” fouling. Ex-situ fouling can be further
fouling, the bulk fluid is super-saturated with, for example, iron species which may have
come from other parts of the power plant where corrosion had occurred and been transported
18
to the surface of interest. Once these iron species reach the wall, super-saturation causes
particles to nucleate and deposit onto the wall. In particulate fouling, nucleation happens in
the bulk fluid and the corrosion products are carried to the wall as solid particles. Lister
(1980) hypothesized that the deposits of these ex-situ corrosion products may be the same
form as the outer layer oxide formed from the alloy. As the iron species diffuse from the
alloy to the surface, the iron first dissolves into the solution. Then, due to local super-
Ex-situ fouling of oxides onto heat transfer surfaces can be detrimental to power systems as
they can decrease thermal efficiency and increase the temperature of the heat transfer
material promoting earlier degradation (Lister, 1980). To track thermal efficiency issues due
pressurized water reactors (PWR) (Schwarz, 2001). The steam generator of a PWR is a heat
exchanger where the reactor coolant transfers the heat to the feed water / steam cycle. The
accumulation of deposits, mainly iron hydroxides and oxides was found to impair heat
transfer between the two systems. Schwarz (2001) compiled data from twelve Siemens steam
generators, many spanning over a decade and one for 27 years. Fouling was determined using
2-4
where Q is the thermal energy into the system, ΔTlog is the mean logarithmic temperature and
U is the overall heat transfer coefficient for the heat exchanger, calculated by equation 2.3.
19
2-5
where Rf is the fouling factor representing the additional thermal resistance due to the iron
oxide deposit. The thermal power Q was determined from the change in enthalpy of the
feedwater, derived by the inlet and outlet temperatures at constant pressure. Accuracy of the
fouling measurements was found to be highly sensitive on the accuracy of the steam
generator outlet temperature and pressure measurements. Using the heat exchanger and the
calculations described above, it was possible to observe the fouling rates on the steam
generator over its operational time. It was found that switching from phosphate-treatment to
an all-volatile treatment (AVT) with hydrazine to ensure high pH, significantly reduced the
fouling rate on the SG. The fouling factor increased gradually over time under phosphate-
treatment which occasionally would encounter a sharp drop after undergoing chemical
has been the subject of many previous studies. A classic study of particle deposition was
conducted by Thomas and Grigull (1974) using magnetite powder in high temperature and
pressure system. Their experiment used an electrical heater in a flow loop system and is one
of the few studies which reached supercritical conditions of 24.6 MPa and 471°C. They
observed that the deposition of magnetite in both subcritical and supercritical single phase
flow was approximately linear to Reynolds number and concentration which is an indication
that the deposition was mass transport limited (Thomas & Grigull, 1974). More recent
studies by Turner and Klimas (2000) and Basset et al. (2000) used sol-gel methods to form
20
narrow size-distribution magnetite particles for deposition experiments. Deposition
experiments have shown the effects and differences of deposition of single phase, boiling,
and non-boiling two phase flow. Under single-phase flow, removal was not found to be a
significant factor and only significant in sub-cooled boiling (Basset et al., 2000).
Since the proposal of the CANDU SCWR reactor design, deposition of corrosion products in
the reactor core has been identified as a problem by a number of researchers prompting
simulations for deposition to be developed. Using the solubility mentioned in section 2.2,
Burrill (2000) created a simulation with a CANDU 6 fuel channel design and the temperature
went from 350°C to 384°C at 25 MPa. Ferrous ions were assumed to diffuse towards the wall
and crystallize as magnetite deposits. Deposition was assumed to be mass transport limited
and the diffusivity coefficient of ferrous species was calculated using empirical formulations
by Miller (1982). Burrill (2000) determined that after one year of operation the peak deposit
was 108mg Fe/cm2 occurring 4m from the channel inlet. The effect of dissolved iron
concentration on deposition was also investigated by setting the concentration at the inlet of
the reactor core to 18.22 µg/L and 5 µg/L. The higher inlet concentration led to deposition
nearly six times higher than the lower concentration, suggesting that the uncertainty in
magnetite solubility can have a significant impact on the simulation results (Burrill, 2000).
In a similar study, Cook and Fatoux (2009) proposed the use of steam generator such as the
one used in a PWR for the CANDU SCWR to prevent corrosion products from travelling to
the steam turbine. A simulation using the HKF model for saturation of iron was used and the
21
velocities of 0.01 cm/s and 0.001 cm/s. The peak deposition thickness in the steam generator
was calculated to be up to 300µm or 50µm depending on the kinetic constant assumed. The
deposit decreased the efficiency of the steam generator by 4% after five years of operation
Once attached to the tube surface, adhesive forces prevent the particle from flowing back into
the fluid stream. Adhesive forces are generally classified into three categories; The first class
of adhesive forces is intermolecular forces which can include van der Waals, the second are
chemical bonds including hydrogen bonds, and the third is sintering effects such as diffusion.
As particles deposit, they are located in the viscous sub-layer, a very thin layer near the wall
where viscous effects are dominant and the flow is laminar (Cengel & Cimbala, 2006).
Detailed investigations of particulate removal by Cleaver and Yates (1973) have shown that
the viscous sub-layer is unsteady in turbulent flows, and that there are turbulent “bursts” that
can cause particle removal when the shear flow generate lift forces exceeding adhesive forces
of the particle and surface. In contrast, if the viscous sub-layer thickness is much greater than
the particle deposited, the viscous forces can rapidly dissipate the turbulent bursts (Cengel &
Cimbala, 2006; Turner et al., 1990). Previous studies for calculating removal rates have used
(equation 2-7).
22
̇ ̇ 2-6
The value ̇ is found experimentally, t is time [s] and λ is removal rate constant [1/s]
2-7
particulates outside the reactor core is also of great importance to the reliability and safe
Solid particle erosion (SPE) can be problematic in power generating systems where the
protective oxide layer of piping and other components are eroded by particles suspended in
the fluid stream (Crockett & Horowitz, 2010). SPE can contribute to increased maintenance
costs and the decrease in the thermal efficiency of a turbine which can be expensive (Dai et
al., 2007). For a SCWR, a direct cycle from the reactor core to the steam turbine is expected
and the problem of SPE may be enhanced due to lower solubility of oxides in supercritical
water and the formation of particulates. Another issue with corrosion products being
can form in the reactor core, attaching to fuel cladding and pressure tubes which are then
irradiated (Burrill, 1977). Once the particle exfoliates, it can travel to other parts of the
23
system outside the core and become a source of hazardous radiation to its operators and
The need for in-situ particulate sampling systems can be significant for power plant
applications. Information about the properties of the particle such as size, shape, hardness
and strength can lead to information about potential damage that particulates can have on
system components surfaces (McCabe et al., 1985). The composition of the particles give an
indication as to where they may be coming from (eg. fuel cladding, piping, etc.) as well as a
Furthermore, sampling at high temperature has been shown to provide better representation
of the particulates in the system. Turner and Klimas (2000) made measurements of
particulates before and after a filter and found that by placing the filter before the heat
exchanger, the concentration of iron was twice as large as when the filter was sampled cold.
Turner argued that such difference is likely due to thermophoresis where the particles diffuse
down a temperature gradient, therefore transported to the colder surface and attaching to the
heat exchanger wall. In addition, sampling ports in real power-generating systems are often
far away from the sampling line which can cause losses in the particulates found at the ports.
In PWR, it was found that 50-75% of particles were lost or dissolved in the solution due to
24
3 Heat Transfer and Deposition Modeling
3.1 Overview
A heat transfer and deposition model was created in MATLAB to aid in the design of the
experiments and to predict the effects of magnetite deposition on a CANDU SCWR fuel
cladding. Only particle deposition was considered in this model due to the lack of data on the
deposition rate constant for ferrous species in supercritical water. Simulation models were
also used to compare expected deposition thicknesses with those found in the experiments.
The heat transfer and deposition model for the CANDU SCWR and the experimental
simulation are based from the same code. However, due to different geometry and flow
characteristics, adjustments to the code were made where necessary. The MATLAB program
The test section in the once-through flow loop is electrically heated and the heat flux is
assumed to be constant throughout the test section. As a result, the enthalpy of the bulk fluid
is a linear function of the distance along the tube, and at any point, the enthalpy can be
3-1
̇
25
where H1 and H2 is the enthalpy [kJ/kg] at a distance Δx [m] away, ̇ is the mass flow rate
[kg/s], and q is the heat input per meter [kW/m]. The enthalpy of the inlet and outlet of the
test section is determined by using the inlet and outlet bulk fluid temperatures [⁰C] at the
specified pressure P [bar]. The bulk fluid temperatures were measured experimentally using
in-situ thermocouples before and after the test section, as described in detail in Chapter 4.
Heat transfer correlations developed for subcritical conditions are not applicable for
supercritical conditions due to the dramatic changes in the thermodynamic and transport
properties near the critical region. Therefore, a number of correlations have been developed
heat transfer generally require the use of either bulk or wall temperatures, however, there can
be dramatic changes in the heat transfer properties if bulk and wall temperatures are near the
pseudocritical region. Correlations such as those developed by Swenson et al. (1965) and
Yamagata et al. (1971) attempt to reflect these changes in the properties by using both wall
and bulk temperature to determine a suitable average. The equations provided by Swenson
are a relatively straightforward method for calculating the Nusselt number and has been
( ) 3-2
26
By using equation 3-2, one can determine the Nusselt number for finding the heat transfer of
the tube to fluid. This requires the Reynolds number as well as the Prandtl number found in
equation 3-3.
̅
3-3
̅ ∫ 3-4
A recent study by Bazargan and Fraser (2009) on the heat transfer correlation in supercritical
water in a horizontal pipe showed that many previous correlation used were insufficient in
predicting the Nusselt number accurately. Bazargan concluded that large variations in fluid
properties near the pseudocritical zone dramatically enhanced heat transfer. A comprehensive
explanation and discussion of the approach is described by Bazargan and Fraser (2009).
Both the correlation of (Swenson et al., 1965) and (Bazargan & Fraser, 2009) were
programmed in MATLAB for comparison between the empirical models and experimental
results. These results are presented in section 4.5.1. The Nusselt number calculated from the
correlations is then used to calculate the wall temperature using equation 3-5.
3-5
To determine the fluid properties at the wall, the wall temperature is required in the previous
calculation. Since this is the parameter which is currently unknown, a wall temperature must
27
first be predicted by the software. The program runs through an iterative loop, first
calculating the wall temperature with the initial guess, calculating the new wall temperature
and modifying the initial guess until the two temperature converges to within 0.1ºC.
As the particles begin to foul the inner wall of the tube, the deposits create a heat transfer
resistance between the fluid and tubing wall interface. The temperature at the wall calculated
from section 3.2.2 is therefore the temperature of the oxide/fluid layer as deposition occurs.
3-6
where koxide is the thermal conductivity of the fouling oxide (Holman, 2002). Magnetite
3-7
where T is the temperature of magnetite (Electric Power Research Institute Inc., 2003).
Calculating the outside wall temperature of the tube was necessary because the
thermocouples on the test section are measuring outside wall temperature. The tube has
internally generated heat from the low AC voltage and high current applied to the tube. The
28
equation for determining the external wall temperature with internally generated heat
( ) 3-8
where A is the ratio of the inner and outer radius found by equation 3-9.
3-9
Buoyancy effects were calculated for the experimental conditions to determine if it would
have an effect on the temperature profile of the tubing wall. Buoyancy effects can be
significant for fluids near the pseudocritical point due to large variations in the fluid density
at the bulk and wall temperatures (Bazargan et al., 2005). This can cause the low density
supercritical water to flow at the top of the tube while the denser subcritical water flows at
the bottom of the tube. Since the heat transfer coefficient varies dramatically from
supercritical to subcritical, this means that a difference in top and bottom surface
Buoyancy effects were calculated according to Petukhov et al. by a threshold value for the
Grashof number, which below the threshold the buoyancy can be neglected. The threshold is
defined as follows:
29
̅̅̅ ̅̅̅ 3-10
where
̅̅̅ 3-11
̅
3-12
where
̅ 3-13
Evaluation is done by determining if Grq < Grth or that the Grq/Grth is less than one.
30
Figure 3-1: Calculation of Grq/Grth for determination of the effects of buoyancy along the
test section using Bazargan et al. (2005)
Since Grq<Grth for all experiments run, buoyancy should not affect the temperature of the
outer wall.
Fouling is a complex phenomenon in which many of the parameters are unknown or specific
combination of particles formed in the bulk solution and crystallization of magnetite on the
tube wall. In order to develop a practical simulation with limited data available, certain
assumptions for the formation of magnetite and deposition characteristics are made and
presented. For the simulation under experimental conditions, particles are assumed to be of
uniform size and the formation is assumed instantaneous at the inlet of the test section. For
31
the CANDU SCWR simulation, the particles are assumed to form instantaneously after
super-saturation.
In addition, corrosion products which foul onto the heat transfer surface can come from the
tube surface itself or from the environment. For the case of the experimental simulation, only
ex-situ fouling will be considered since the experiments were run for a short period (40
minutes) making corrosion negligible. For CANDU SCWR simulation, corrosion is again
neglected because it will be highly dependent on the material used for the fuel cladding
There are five sequential steps in fouling; induction, transport, attachment, aging and finally
removal (Turner, 1993). For particulate fouling, the induction period is not important and is
primarily limited by transport and/or attachment. Early deposition models tended to use a
single mass flux term which depended on the concentration. A sticking probability ‘S’ was
used to take into consideration the probability of particles reaching the wall without sticking,
depending on the conditions of the particle of interest. In later models, the sticking
probability was replaced with equations of surface attachment. This is described in the Kern
and Seaton model which is most commonly used in particulate fouling (Epstein, 1987). The
deposition is said to be a two-step process; mass transport where the particle moves from the
bulk to near the surface, and an attachment process where the particle attaches to the wall.
Therefore, the deposition is the net resistance of the two processes and can be described by
32
3-14
where Kd, Kt and Ka is the effective, transport and attachment deposition velocity [m/s]
The term is the attachment deposition velocity and is believed to be caused by van der
Waals interactions as well as the electrical double layer when the particle is approximately
10nm from the surface (Turner, 1993). Van der Waals forces arise from dipole-dipole and
dipole-induced-dipole interactions between particle and wall (Turner & Klimas, 2000). These
forces are always attractive between a particle and wall in a water medium (Hong, 2007).
The electric double layer forms at the surface of an object that is immersed in a liquid. Solid
objects generally attain a surface charge when immersed in a liquid which can be formed
through the absorption of ions present in the liquid or the dissociation of molecules on the
surface of the object (Bott, 1995). This creates a redistribution of ions in the medium in near
vicinity to the immersed particle with similar charged ions being repelled and opposite
charged ions being attracted. Therefore, a second layer in the medium called the diffuse layer
is formed by coulomb forces with oppositely charged ions. As a particle approaches the wall,
the diffuse layers of the particle and wall in the solution overlap and create a potential
energy. If the charges are oppositely charged, the forces are attractive and the limiting rate is
the mass-transport velocity. If the charges are the same, the force is repulsive and depending
on the magnitude of the repulsive force, the overall deposition may be surface attachment
limited (Basset et al., 2000). In such case, the particle that approaches the wall will have to
33
overcome this potential energy barrier to attach to the wall. This follows an Arrhenius
⁄
3-15
When deposition is mass transfer controlled, Ka is much larger than Kt and the mass transport
3-16
For deposition onto the inside of a tube, the mass deposition rate along any section of the
̇ 3-17
where is the density of the particle fouling the surface. The deposition velocity is
3-18
34
⁄
( ) 3-19
where is the fluid density and is the wall shear stress and calculated by:
3-20
The friction factor f in a fully developed turbulent pipe flow can be calculated using the well-
known Colebrook equation. In many cases an approximate but explicit relation can be
substituted for the Colebrook friction equation using Haaland’s equation shown in the
equation below.
( ( ) ) 3-21
where is the roughness factor which is was taken to be 0.002 mm for a clean stainless steel
tube. The uncertainty in such a roughness factor can be as much as ±60% (Cengel &
Cimbala, 2006). As the tube begins to foul onto the surface, it is assumed that the roughness
of the tube was then the sum of the deposit and initial roughness:
3-22
The non-dimensional deposition velocity Kd+ was predicted from empirical equations fit by
Papavergos and Hedley (1984) for aerosol particles landing onto a flat plane. Experimental
work done by Teshima and Khan showed that these equations provided agreement for salt
35
( ) 3-23
Kd+ depends on both the dimensionless Schmidt number as well as heavily on the particle
3-24
3-25
Finally, the non-dimensional parameter relaxation time is calculated using the following
36
( ) 3-26
The regions of Kd+ can be categorized into three regions depending on the relaxation particle
time. For , the particle motion is dominated by Brownian diffusion and deposition is
inversely proportional to the size of the diffusing particle (Beal, 1970). As the particle size
increases, the relaxation particle time increases and momentum effects gain importance. The
deposition velocity reaches a minimum when is 0.2 and inertial coasting becomes the
dominant mechanism for transport which increases exponentially with diameter size. At even
higher relaxation particle times above 20, the particle inertia becomes very large and the
stopping distance exceeds the viscous and buffer layers. The stopping distance marks the
distance at which the particle will coast to the wall simply by their momentum. In this region,
the particles are no longer affected by the fluid forces, therefore reaching a constant value
Figure 3-2 was produced using the equations described above and shows the effects of
particle diameter and temperature on deposition velocity under the experimental conditions.
37
Figure 3-2: Effect of particle diameter and fluid temperature on deposition velocity for
experimental apparatus
To predict the rate of deposition that might occur in a CANDU SCWR, the design of a
CANDU ACR-700 was used as a baseline since the design for a SCWR pressure tube has yet
to be finalized. The CANFLEX 43-rod fuel bundle configuration which is used in the ACR-
700 provided geometric parameters for the heat transfer surfaces and is listed Table 3-1.
38
Table 3-1: SCWR and fuel assembly design parameters
As an approximation of a real fuel bundle which has complex geometry, the simulation
developed in this study was conducted by looking at a single fuel element and approximating
the fluid and thermal properties around the element without the influence of neighboring
elements. Temperature rise of the coolant was predicted by setting the fuel cladding wall as
the single source of heat to increase the enthalpy of the coolant linearly along the 6 m
distance.
For the hypothetical single fuel element developed in this study, the fuel bundle was
converted into an equivalent heated tube with the coolant flowing on the inside, and therefore
the MATLAB code used for this simulation is nearly identical to the simulation used for the
experiment with the exception of the parameters. The mass flow rate for a single fuel element
was calculated by the total flow rate in the reactor divided by the 43 fuel elements. An
effective diameter for a single fuel element was calculated by keeping the velocity of the
39
Pressure Tube Cladding
Coolant
Tbulk
Toxide
Tcladding
Figure 3-3: Cross-sectional view of CANFLEX 43 rod fuel bundle and drawing of
equivalent tube for simulation calculations (not to scale)
The surface most interesting for these deposition studies is on the fuel cladding which covers
the fuel pellets and prevents the uranium from coming into contact and contaminating the
water. The fuel cladding is often made zirconium alloys due to its low neutron absorption
property compared to other alloys. However, zirconium alloys are limited by their reduced
mechanical properties at high temperature and therefore may require other alloys as a
substitute for the fuel cladding for future SCWR. Results from the simulations are reported in
Chapter 6 and discussed considering the measurements described in the next few chapters.
40
4 Experiments
A once-through flow apparatus shown in the Figure 4-1 was operated for all high temperature
experiments reported in this study. The apparatus was originally constructed for running
experiments for supercritical water oxidation and therefore, system components were added
and/or modified to run the system for corrosion product transport experiments and simulate
supercritical water reactor conditions. A schematic of the entire system can be found in
Figure 4-2.
Back pressure
regulator
Control Panel
Effluent tank
Figure 4-1: SCW system used in all experiments located in the Mechanical Engineering
laboratories.
41
Nitrogen Nitrogen
Primary
Tank
Relief
Valve
P-1 T1 T2
Preheater 1 Preheater 2
Nitrogen
Pump 1
LTHP
Effluent Tank Filter
Secondary Line Heat
Exchanger
Pump 2
LTLP HTHP
Effluent Tank Filter Filter
42
The majority of the system tubing is constructed from 1/4” seamless AISI stainless steel 316L.
Tube fittings for the system use SS316 Swagelok fittings where contact with high temperature
and pressure water is present. A 20L plastic tank and a glass flask were used for the primary
feedwater tank and the injection solution tank respectively. It was important to keep oxygen
content low in the system favoring reducing conditions, and therefore the tanks were deaerated
A high pressure Bran Leubre positive displacement pump was connected to the primary tank for
delivering the majority of the fluid. Flow rates are manually controlled and can attain up to 8L/hr
at a pressure of 25.0 MPa. To suppress the fluctuations in the pressure due to the positive
Three ceramic preheaters with a combined total wattage of 8.6kW are located downstream of the
main pump which externally heat the fluid to the desired temperature before entering the test
section. The ceramic heaters are split into top and bottom halves allowing for easy access to the
An Eldex Laboratories high pressure pump (BB-4-VS) injects the ferrous precursor solution into
a flow-tee which joins the injection stream to the hot fluid stream. The pump has two heads, both
taking fluid from the injection tank and reconnecting through a tee at the outlet. The pump has a
manually adjustable flow rate using a Bodine Electric Company, RPM controller. To ensure
complete thermal and chemical mixing of the two fluids, a perforated stainless steel 304 was
43
placed inside the tube immediately prior to the bulk thermocouple. A detailed description of the
test section and the temperature measurements are given in section 4.7.
After the test section, a final tee splits the stream towards a secondary line consisting of a high
temperature, high pressure filter and the primary line connecting directly into a heat exchanger.
The secondary line has its own heat exchanger and a needle valve to cool and depressurize the
fluid to room temperature and ambient pressure. A low temperature, low pressure filter is located
On the primary line, a 2.0 m long tube and shell heat exchanger cools the hot supercritical fluid
flowing in the tube side with cold water flowing in the shell side. After the primary heat
exchanger, a low temperature high pressure filter and a back pressure regulator (TESCOM 26-
1762-24) are located immediately downstream to adjust the pressure of the system
4.2.1 Safety
The safety of the operator, as well as other laboratory personnel was considered of utmost
importance. Hence, online temperature and pressure monitoring with automatic shutdown control
was put into place. Temperature was monitored at five locations throughout the system to keep
temperatures below tube temperature ratings. If temperatures of the heated section were to
exceed 500⁰C, the controllers are programmed to trip the breaker causing all heaters to turn off
automatically while the primary pump remains online to remove residual heat from the system.
44
Pressure is also monitored by the controller and can turn off both the heaters and the pump if the
pressure exceeds 34.5 MPa, signaling a possible plug in the system due to fouling. In addition, a
pressure relief valve just downstream of the pump was set to open at 27 MPa.
If temperatures at the exit of the heat exchanger begin to rise, this may indicate the cooling water
may be off or have insufficient flow rates which may result in high temperature water/steam
exiting the system and potentially damaging downstream equipment. The controller was set to
automatically turn off the heaters if the temperature of the tube after the heat exchanger exceeded
50⁰C.
Pressure was monitored with a GP-50 pressure transducer (P-1 in Figure 4-2), calibrated by the
manufacturer with an accuracy of ±2% full scale output (FSO) of 34.5 MPa. These were read and
recorded manually from the control panel board. A Bourdon pressure gauge (P-2 in Figure 4-2)
downstream of the primary heat exchanger was also frequently checked as a safety measure.
The primary pump was first turned on and pressurized to the desired pressure. Flow rates of the
effluent were measured three times and averaged using a graduated cylinder and a stop watch.
Then the injection pump was turned on and after several minutes the flow rate was measured
once again. The calculated difference between the two averaged flow rates was the injection
45
4.2.4 Fluid Conductivity Measurements
standard (1413µS/cm). The conductivity meter has an accuracy of ±0.3% FSO. Conductivity of
the inlet of the primary tank was measured to check that the deionized water had low
conductivity indicating ions are not present. The conductivity meter was also used for high pH
experiments for measuring sodium hydroxide content in the tank. A detailed description of this
An Omega DOB21 measured the dissolved oxygen (DO) content in the two feedwater tanks. The
Due to the low solubility of magnetite, deposition of magnetite from a dissolved state was
expected to be slow, taking several years to form measurable deposit thicknesses. To create a
feasible experiment, it was necessary to introduce ferrous species artificially. To simulate ferrous
corrosion products, ferrous salts were mixed into deionized water and injected into the system.
The ferrous salts then form iron oxide particles after the process described here.
Formation of magnetite particles has been of interest in colloidal science for its industrial
applications, as well as through its presence in the power generating industry as corrosion
products from iron and steel (Zhao et al., 2009). Work of Sugimoto and Matijevic (1980)
46
introduced a procedure of producing spherical magnetite particles using ferrous hydroxide gels.
Later work by Adschiri et al. (1992) reported a rapid hydrothermal process using supercritical
processes for producing oxide particles became a popular method as it offered control over
morphology and composition depending on the precursor, temperature and density of the fluid.
Under supercritical conditions, reaction kinetics is very high and the formation of metal oxide
particles occurs rapidly due to its low solubility. In previous studies, Fe(NO3)3, Fe2(SO4)3, FeCl2
supercritical water. Fe(NH4)2H(C6H5O7)2 formed spherical magnetite (Fe3O), while all others
Both in the sol-gel method and rapid hydrothermal process, the metal oxide goes through two
reactions; first the metal salt undergoes hydrolysis in which the salt will react with water to form
a hydroxide and second, a dehydration process where the hydrogen is separated to form an oxide.
Dehydration occurs from the outer surface of the hydroxide particle and therefore smaller
particles may favor faster dehydration rates (Adschiri et al., 1992). These reactions are given in
4-1
4-2
In equation 4-1, B is the anion of the ferrous salt which is either Cl- or SO4- in this study. Due to
excess hydrogen ions, the solution is slightly acidic and the salt is said to be a lewis acid.
47
At higher temperatures, dehydration occurs in which the iron is oxidized from Fe2+ to Fe3+. This
forms magnetite if the environment is anaerobic while forming hematite or other hydroxides in
an aerobic environment. This is known as Schikorr reaction and is a common reaction which
4-3
Fe(NO3)3 in supercritical water. Adshiri (1992) also tested reaction rates and found that it formed
hematite nano-particles even when the reactor residence time was cut down to less than 1 second
although particles were smaller (<20 nm) suggesting that reaction times are very high (Adschiri
et al., 1992). Synthesis in supercritical conditions occur faster partly due to the lower dielectric
constant of water and the resulting enhancement of the reaction rate according to Born’s theory
Although Aschiri had used ferrous chloride in his experiment, it is believed that the system still
contained oxygen, making it a highly oxidizing environment under supercritical conditions. This
would explain why hematite was formed in Aschiri’s experiment with ferrous chloride.
Before each experiment, the primary pump was turned on and the system was flushed with
deionized water for about one hour. Both the primary and injection tanks were continually
48
sparged with nitrogen throughout the experiment to deaerate the system. The dissolved oxygen
sensor was placed in the injection tank to deaerate the solution until it reached 0.00ppm which
usually took one to two hours. Once the dissolved oxygen content reached the desired level in
the injection tank, the DO sensor was moved to monitor dissolved oxygen levels in the primary
The back-pressure regulator was adjusted until the pressure at the transducer was reading the
required pressure for the particular experiment. Although the pressure transducer is located
before the heaters and several feet away from the test section, it is assumed to that the readings
are representative of the pressure in the test section as the pressure drop between the two points
is small and negligible compared to the system pressure of 24 MPa. Flow rates of the primary
pump were measured and adjusted according to the required 3.0L/hr. The injection pump
connected to a tank of deionized water was turned on and the new flow rate was adjusted to
3.5L/hr using the injection pump. The pressure remained constant during this time and the
injection pump flow rate was calculated as the difference between the two flow rates. Once the
desired flow rate and pressure were achieved, the heaters were turned on and allowed to heat the
system to supercritical conditions. Temperatures of the bulk fluid inlet and outlet of the test
section were checked until the system reached steady state temperature. The injection pump was
momentarily turned off in order to switch the injection tank from deionized water to precursor
increase in the temperature profile of the test section due to reduced flow rates. Once the tank
with precursor solution was connected, the injection pump was turned on once again and the
temperature of the test section dropped to its original temperature. The flow rate at the exit was
49
measured once more to check if they were consistent from before. Each of the experiments ran
for approximately 40 minutes, with the exception of the low concentration ferrous chloride
experiment which lasted for 400 minutes at one tenth the concentration. Therefore, the total mass
For low heat flux, ferrous chloride experiment, a 1.0m, 1/8” x 0.028” outer diameter stainless
steel 316L tube at 6V was used rather than the 1.8m at 12V used for the rest of the experiments.
It was realized during this experiment that there was significant electrical resistance in the wiring
and heat loss through the mounting blocks such that the temperature rise in the test section was
very small. Therefore, for all subsequent experiments, the test section was modified to run at
1.8m and 12V yet maintain a maximum current under design ratings of 200A.
Experiments with magnetite particle injection was also initially tested using commercially
available magnetite powder by Sigma Aldrich (Iron (II,III) oxide, > 98% Fe3O4). The use of
prepared magnetite powder for the experiments offered several advantages over using a
precursor; the amount of magnetite particles in the system could be accurately known without the
need to determine yield rates and the size of the particles could also be externally controlled. The
magnetite powder had a diameter of 50 nm or less and was suspended in deaerated solution in
the injection tank. The solution was continually mixed with an electrically powered mixer to
prevent particle settlement. The magnetite particles were observed to agglomerate and stick to
the glass flask and tubing, lowering the overall concentration of magnetite powder in the
solution. To mitigate this problem, the pH of the solution was increased to 10 using sodium
50
hydroxide where the zeta potential of the solution/magnetite favored dispersion. However, the
magnetite nano-particles, therefore further experiment with magnetite slurry was not pursued.
After each experiment with the exception of experiments 7 and 8, the test section was removed
and replaced with a temporary tube and the system was chemically cleaned. For experiments 7
and 8, both the test section tube and the rest of the system underwent chemical cleaning. The
system was cleaned using 1N hydrochloric acid at 80⁰C for one hour before each test to ensure
that magnetite deposits were removed from the system. After cleaning with hydrochloric acid,
the entire system was flushed out with de-ionized water for several hours. When required,
mechanical cleaning of tubes and fittings was also conducted by disassembling the sections and
The electrical heater was designed and constructed to serve several purposes. First, the heaters
increase the temperature from subcritical to supercritical temperatures, allowing for a wide range
of temperatures and heat flux conditions which can be tested. Second, it offered an online
monitoring of fouling in the system. Deposits on the heat transfer surface would increase thermal
resistance which would be detected by an increase in temperature of the tube outer wall. By
modeling magnetite deposits and heat transfer characteristics, the deposition and removal rates
51
can be calculated. Calculated values can be compared to the deposition found in SEM images
The test section is electrically wired with current running directly through the tube causing the
electrical resistance of the 1/8” tube to dissipate power in the form of heat. It is assumed that the
electrical resistivity remains constant along the tube and therefore the heat flux into the water
will also remain constant along the tube. This method for heating the tube was chosen over
heating tapes and ceramic heaters for its uniform heat flux demonstrated by Teshima (1997) and
Khan (2005). The test section tube is connected to a 2400VA transformer with its primary coil
wired in series and secondary coil wired in parallel using 6V center taps. Power input was
provided by two of three legs of a three-phase delta-configured power supply, which supply a
voltage of 208V RMS to the transformer. Fuzzy Pro logic controllers monitored the temperatures
for both the preheaters and test section. These have PID control which read temperatures from
the thermocouples and send a signal for optimal power level to the solid-state rectifiers (SSR)
Metal oxide varistors (MOVs) were installed both at the inlet before and after the SSR to prevent
voltage spikes from damaging the SSR and transformer. The transformer connects to the tube
with one connection to the center and two ground wires to each of the ends. This is to prevent
any ground loops from forming within the system, which may create safety hazards. The
resistance of the 1/8” SS316L tube was measured to be on average ~0.13 Ω per meter, however
the effective resistance is reduced to a quarter of its value due to the parallel connection.
52
Thermal expansion of the tubing was also considered which can be as high as a few millimeters
from room temperature to experimental temperatures. The heat exchanger is free to move axially
a short distance, allowing thermal expansion to occur without introducing significant stress on
For both safety and protection of the equipment from voltage on the tube, secondary grounding
wires were attached at the inlet of the injection line and after the heat exchanger. Three tube
mounting blocks were constructed from SS303 for clamping the tube and the electrical conductor
together. These mounting blocks were specially designed and optimized to offer high thermal
resistance to decrease heat loss from the test section yet maintain high electrical conductivity for
the electrical path. Aluminum heat sinks were attached to the mounting blocks to dissipate any
excess thermal heat. The configuration of the test section and mounting blocks are provided in
Figure 4-3.
53
From main pump
Test section
From
injection
pump
Wall temperature
thermocouple Mounting
blocks
Tee with inlet
bulk
thermocouple
Heat exchanger
Temperature along the tube was measured using K-type Chromel/Alumel thermocouples with
twisted shield for protection against electrical noise. Although not as accurate as RTD, they are
very robust even at high temperature and can be calibrated to be accurate within less than 1⁰C.
Six thermocouples were connected to the control panel for input power control and safety
reasons. Eleven thermocouples were spot welded to the 1/8” test section tubing on the outside
wall. These thermocouples were placed on the top of the tube, however, since buoyancy is
negligible in these conditions, the location around the circumference of the tubing should not
have a significant impact on the temperature reading. Thermocouples were clamped onto the
54
outside wall of the outlet of heaters 1 and 2 and the tube downstream of the heat exchanger of the
main line. Bulk fluid temperatures were measured using Inconel sheathed, ungrounded probes
which were inserted at the Tees with the probe end approximately at the center of fluid flow. The
outlet bulk temperatures were fed into the control panel and were used to control the temperature
of the electrically heated section. A wiring and thermocouple placement diagram is shown in
Figure 4-4.
AC voltage and current into the heated tube sections were measured for calculating power input.
Although these measurements are not used for determining the enthalpy of the water, it provided
a secondary confirmation for ensuring temperature rise corresponding to the electrical power
provided by the system. A fluke clamp meter was used to measure AC current with resolution of
±0.1A. Measurements of the voltage across each half-section were performed with a Mastercraft
Input power calculations derived from current/voltage measurements closely matched input
power calculations using bulk temperature measurements, shown in the table below as the
electrical and thermal power respectively. The small discrepancy between the two values is
likely due to thermal loss to the mounting blocks and surrounding insulation, hence the electrical
power is slightly higher than the actual heat gained by the fluid.
First half of tube Second half of tube Power [W] Power [W]
Experiment
Current [A] Voltage [V] Current [A] Voltage [V] (electrical) (thermal)
1 54.3 10.00 51.5 9.93 1054 1025
55
Calibration of the thermocouples was conducted by measuring the outside wall temperatures
with the bulk inlet and outlet temperature of the test section set at a saturation temperature and
pressure, and the section was thermally insulated with no input power. This process was
completed before the experiment each time a new test section was installed. Temperature was
recorded for thermocouples and any significant temperature differences were noted. For the
thermocouples, the temperature measured usually fell within one or two degrees of expected wall
temperature. These were used to correct the temperature readings for any future measurements
Subsequently, the accuracy of the temperature profile calculated by the MATLAB simulation
with inlet and outlet temperatures at 350⁰C and 400⁰C respectively. The measured and calculated
temperatures using correlations of Swenson and Bazargan are shown in Figure 4-6.
56
Omega 1200 High Speed
Isolated Measurement System
Flow
15 cm
Mounting
blocks
Parallel
Transformer
Series
SSR
Fuzzy Pro logic Fuzzy Pro logic
controller controller
Figure 4-4: Electrical wiring, heater controls and location of surface welded thermocouples and bulk fluid thermocouples
57
Figure 4-5: Saturation temperature of 231.51ºC at 417psi, calibration for Experiment #1
58
It was observed from the comparison that Swenson’s correlation predicted temperatures well
transfer enhancement at bulk fluid temperatures above 380°C. Therefore, all subsequent
simulations presented in this study use Swenson’s correlation for determining the heat transfer
coefficient. The temperatures read were quite stable (std = 0.7⁰C for experiment #1) and
therefore, any temperature differences due to fouling can be measured with an accuracy to 1⁰C.
Temperature measurements of the test section thermocouples were recorded using a data
acquisition hardware and computer. The Omega Multiscan 1200 has 24 electrically isolated
channels and two internal channels which are used for cold junction compensation. The 16-bit
temperature measurements offer 3.12 uV or 0.1⁰C resolution. Electrically isolated channels were
needed for the temperature measurements since the thermocouples were welded and electrically
connected to parts of the test section which are at various voltage potentials. AC line rejection
and averaging helped to reduce noise caused by the AC voltage applied to the test section in the
measurement. Temperature data is sampled at 20kHz frequency and the data was sent to
automatically averaged over a 5 second period and then outputted to the text file which was later
analyzed in MATLAB.
A Hitachi S-3000N in the Frank Forward Materials Engineering building at UBC was used for
SEM imaging, with the exception of those photographs which are labeled as Hitachi 2300 SEM,
59
To observe the morphology of the deposit on the tube inner-wall surface, the test section was cut
into 1.5cm long samples using a 1/8” tube cutter. The sample was then carefully cut in the
middle of the tube by grinding halfway through the tube until there was exposure to the other
inner wall. Then the tube was bent slightly to open the section and the sample was placed into a
Three filters were constructed and installed at various locations in the system to collect particles
formed in supercritical water. After each experiment, the filters were removed and analyzed with
SEM/EDX with the objective of determining particle size, shape, and composition.
The main body for the low temperature, high pressure (LTHP) filter holder shown in Figure 4-8
was constructed from stainless steel 316L. The filter was designed and constructed with the
60
intention of allowing future filter holders to be constructed from any material and allow for easy
assembly and reassembly after each experiment (see Appendix B for details). The metal spiral
wound sealant allows the filter to reach high temperature and pressure applications and
compensates for uneven or scratched surfaces of the mating parts. Glass fiber filters were
inserted into the LTHP filter to collect particles in the primary line after the heat exchanger as
well as to protect the back pressure regulator which was sensitive to particulate fouling. After
each experiment, the glass filter was carefully removed, left to dry overnight, and was gold
Figure 4-8: SS316L LTHP filter installed after the heat exchanger
61
A high temperature, high pressure (HTHP) holder was made from Swagelok 316L fittings shown
in Figure 4-9. A stainless steel 304 perforated metal with a porosity of 22% and a hole diameter
of 0.02” was fitted into the holder to provide back support for the filter. Glass fiber filters were
initially tested in supercritical water, however, the filters were destroyed when exposed to
supercritical water. It is thought that at high temperature and pressure, the glass fiber mechanical
properties degrade significantly and the pressure drop across the filter may have caused it to
break down. It was decided that the glass fiber filters would be used to collect particles only at
low temperatures. In replacement of glass fiber filters, sintered silver membranes from SPI
supplies with absolute retention pore size of 0.2 µm and thickness of 50 µm were used for high
temperature applications. The thin filter makes it ideal for higher flow rates and the conductive
properties of the silver membrane make it excellent for SEM/EDX and XRD analysis. The filter
Figure 4-9: HTHP filter with silver membrane and SS304 back support
62
Finally, a polypropylene 25mm Swin-Lok filter holder was used for the low temperature, low
pressure (LTLP) filter shown in Figure 4-10. The same glass fiber filters used in the LTHP filters
were also used for the LTLP filter. A summary of the properties of the glass and sintered silver
Figure 4-10: Glass fiber membrane and Swin-Lok LTLP filter holder
SEM and EDX analysis were taken of clean filters to determine its composition, and therefore
providing information about the background of the filters. This helps to identify which elements
63
found on the filter are coming from the particle and which are the background of the filter. The
silver membrane was found to be composed of only silver and oxygen. The glass fiber filter had
64
Figure 4-11: SEM photograph of clean silver membrane, 0.2µm pore size, using a Hitachi
S3000N SEM
65
Figure 4-13: SEM photograph of clean glass fiber filter, 0.7µm pore size, a Hitachi S2300 SEM
Figure 4-14: EDX of glass fiber filter to determine elemental composition of background
66
4.5.4 Deposit Thickness and Strength of Oxide Adhesion
To quantify the mass of magnetite deposited on the tube, two techniques for magnetite removal
was used; mechanically using an ultrasonic cleaner and chemically using acid wash procedures.
5.0 cm sample tubes were cut at 30.0cm intervals along the test section for magnetite deposition
quantification. For ultrasonic cleaning, the sample tube was immersed in 25.0mL of 1N
hydrochloric acid at room temperature and cleaned in a Cole-Parmer ultrasonic cleaner for 20
minutes. The sample tube was then removed and the solution was heated on a bunsen burner
with a watch plate and evaporated in a fume hood. Once the beaker was completely dry, it was
washed with 25.0mL of 1% nitric acid solution. 2.0mL was taken from the sample and diluted in
another sample container of 25.0mL, 1% nitric acid. This was repeated once more to achieve
three sets of sample solutions which have of 1×, 13.5× and 182.25× dilution ratios.
For acid wash, the sample tube was immersed in 15.0mL of 1N preheated hydrochloric solution
(≈75°C) for 2 minutes. The sample tube is then removed from the solution and the solution is
further heated to evaporate it completely. The beaker was then washed using the same procedure
A Varian AA240 Atomic Absorption Spectroscopy (AAS) was used to analyze iron
concentrations according to the Beer-Lambert law. Calibration of the AAS was conducted by
first measuring the absorbance using standards of known concentration. For these experiments,
the calibration was done with 0.0, 1.0, 2.0, 5.0, and 7.5mg/L of iron standards in 1% nitric acid
67
matrix. All sample solutions were also digested in a 1% nitric acid matrix. The detection limit of
atomic absorption spectroscopy for iron is approximately 0.1 mg/L (Willard et al., 1969).
Since stainless steel 316L also contains iron, there would be dissolution of iron from the tubing
itself and not just the deposited magnetite. To account for this, clean tubes without deposits were
exposed to the same conditions as those of the sample tubes and its iron content was measured
using AAS. This was done for both the ultrasonic cleaning and acid wash procedures and the
resulting iron concentration from the clean samples were subtracted from the raw sample tube
concentration.
A mass balance of the entire system was pursued by measuring the concentration of ferrous
species in the effluent, filters and test section. Effluent concentrations were determined by taking
20.0mL samples and analyzing them using Atomic Absorption Spectroscopy in a similar manner
to the test section; first by dissolving any possible magnetite that might have passed through the
filter, evaporating the solution, and re-dissolving in 1% nitric acid matrix. For experiments with
ferrous chloride, the effluent samples were taken during the experiment directly from the system
effluent. It was determined that due to changing deposition/exfoliation rates over time, an
averaged effluent concentration would be more representative for mass balance purposes.
Therefore for all ferrous sulfate experiments, the effluent was stored in the high-density-
polyethylene (HDPE) tank until the experiment was completed and a sample was taken of the
total effluent. In addition, for all ferrous sulfate experiments, sulfate was known to interfere with
the AAS in measuring iron, therefore as a way of mitigating this, a copper sulfate of 0.1 mol/L
and 1% nitric acid matrix was used for these standards and sample solutions.
68
5 Results and Discussion of Experiments
A total of eight experiments and one blank were conducted using the SCW once-through flow
apparatus. After each experiment, filters, effluent, and tube samples were analyzed using SEM
and AAS to determine significant findings. A brief summary of the results is provided in Table
5-1 while a more detailed overview and collection of all results can be found in Appendix C.
The two precursors used were ferrous chloride tetrahydrate (FeCl2·4H2O) from Fisher Scientific
and ferrous sulfate heptahydrate (FeSO4·7H2O) from BDH. The experiments are broken down
into the following categories: reference condition, effect of heat flux, high pH, low concentration
Concentration
Tube Heat [mmol Fe2+/L]
Pressure Bulk Temperature
Run Category length Flux pH
[MPa]
[m] [kW/m2] Dissolved
Inlet [⁰C] Outlet [⁰C] Precursor
Fe2+
1 Reference 23.7 1.8 350 400 102 3 5.48 FeCl2·4H2O
2 Reference 23.9 1.8 350 397 97 3.5 4.97 FeSO4·7H2O
3 Heat Flux 22.4 1.0 372 376 24 3 5.31 FeCl2·4H2O
4 Heat Flux 23.0 1.8 371 376 13 3.5 5.04 FeSO4·7H2O
5 Heat Flux 23.3 1.8 384 383 - 3.5 5.32 FeSO4·7H2O
6 High pH 23.8 1.8 350 396 97 9 5.11 FeSO4·7H2O
7 High pH 23.7 1.8 200 370 92 9 5.17 FeSO4·7H2O
8 Concentration 23.7 1.8 350 395 96 3 0.56 FeCl2·4H2O
- Blank 23.7 1.8 351 399 99 Neutral 0.00 -
69
5.1 Reference Condition
Experiments were run with ferrous chloride and ferrous sulfate precursors with the test section at
maximum heat flux of approximately 100 kW/m2. These were considered to be reference
experiments that all other experiments could be compared to. Temperatures of the bulk fluid inlet
and outlet were 350°C and 400°C respectively at 23.7MPa. The injection tank consisted of 1L of
precursor in deaerated, deionized water while the primary tank had deaerated, deionized water,
producing an acidic solution (pH≈3) once both fluids were mixed. The injection method is
The transient temperature of the test section outer wall for reference condition with ferrous
chloride precursor is shown in Figure 5-1. As mentioned in Chapter 4, the large spike and
subsequent fall in the temperature at 15-20 minutes is due to the momentary shutoff/on of the
injection pump for switching the supply line from deionized water to ferrous chloride solution.
supercritical temperature (1.65m from the inlet), the wall temperatures increase rapidly at the
70
Injection
Figure 5-1: Temperature measurements of test section vs. time for reference condition with
ferrous chloride precursor (Experiment #1)
Fouling was observed by the sharp rise in temperature as well as an increase in system pressure
to 26.2 MPa during the injection period as a result of restricted flow. The temperature profile at
the 1.65m location has an asymptotic fouling behavior similar to those found in several studies of
iron oxide fouling (Müller-Steinhagen et al., 1988; Newson et al., 1983; Thomas & Grigull,
1974). It was speculated that the removal rate increases as the deposition thickness increases,
since the bond at the top layer of the surface weakens as the deposit grows higher and is more
likely to be removed by the shear force of the fluid (Newson et al., 1983). Another explanation
presented by Thomas and Grigull (1974) suggested that the initial high deposition rate was due
to the particles adhering to the troughs in an initially rough tube. As deposition continued, the
71
troughs would be filled and the tube surface would become effectively smooth and more difficult
High fouling rates observed at the 1.65m location from the inlet was converted to an equivalent
magnetite deposition thickness at the asymptotic temperature. This was found to be 0.47 mm or
1.5g of magnetite in a 15 cm long section of the tube. Such high fouling rates are unlikely with
only magnetite fouling, and therefore the high increase in temperature may be a product of mixed
considered as the solubility of any salt, including ferrous chloride would be very low in
supercritical conditions.
Temperature measurements for ferrous sulfate precursor showed variations in the test section
temperature but also in the bulk fluid temperatures (Appendix C. 2). This may be due to
inconsistent flow rate of the injection pump for this experiment. Once this was taken into
consideration, it was concluded that no significant fouling was observed from the temperature
measurements.
In the experiment with a ferrous chloride precursor, it was determined after the experiment that
the secondary line was at a significantly lower flow rate than initially set. The HTHP and LTLP
filter was visibly unchanged and showed very few particles collected through SEM images. On
the other hand, the HTHP filter for the ferrous sulfate precursor had a very fine but visible black
film on the silver membrane after the experiment. SEM analysis of the HTHP filter revealed
72
significant amount of particles collected, with particle diameters ranging from less than a micron
to several microns in diameter. These particles are much larger than those seen by Adschiri et al.
(2000) in hydrothermal synthesis of iron oxide particles which observed the formation of ~50nm
diameter particles. However, there is a possibility that the larger particles were captured by their
SEM images of the test section revealed that the ferrous chloride precursor produced magnetite
particles early in the test section. The particles which deposited near the inlet were smaller with
few larger micron-sized particles. Further down the test section at higher temperatures, the
particles deposited grew in size to several microns in which deposition was dense and compact.
Figure 5-2: SEM photograph of magnetite deposit on test section tube surface, 0.15 m location.
Reference condition with ferrous chloride precursor (Experiment #1)
73
Figure 5-3: SEM photograph of magnetite deposit on test section tube surface, 0.60 m location.
Reference condition with ferrous chloride precursor (Experiment #1)
Figure 5-4: SEM photograph of magnetite deposit on test section tube surface, 1.20 m location.
Reference condition with ferrous chloride precursor (Experiment #1)
74
Figure 5-5: SEM photograph of magnetite deposit on test section tube surface, 1.65 m location.
Reference condition with ferrous chloride precursor (Experiment #1)
X-ray diffraction (XRD) was conducted on the oxide deposits found in the test section tube by
mechanically removing the deposit. Figure 5-6 and Figure 5-7 show XRD results for ferrous
chloride and ferrous sulfate precursors respectively. For ferrous chloride, a General Area
Detector Diffraction System (GADDS) using a copper radiation operated at 40kV and 40mA
scanned the deposit from 21.4⁰ to 71.8⁰ at 0.050⁰ increments. A diffracted beam graphite
monochromator and Hi-Start detector was used for producing and detecting the signal. Signals
were relatively weak and the peaks were broad due to the small quantity of deposit that was
75
Figure 5-6: XRD of tube deposits of test section, reference condition ferrous chloride precursor
(Experment #1)
Figure 5-7: XRD of tube deposit of test section, reference condition ferrous sulfate precursor
(Experiment #2)
76
For ferrous sulfate reference experiment, a D-8 Advance X-ray Diffractometer using a copper
anode tube operated at 40kV and 40mA, scanned the filter from 5.0⁰ to 70.0⁰ at 0.040⁰
increments. A diffracted beam graphite monochromator and NaI scintillation detector was used
for producing and detecting the signal. XRD of the deposit indicated a mixture of magnetite and
hematite which may have formed due to oxygen contamination during the experiment (see
Figure 5-7).
To determine the deposition thickness along the test section, cleaning methods described in
section 4.5.4 were applied to the sample tubes. This is similar to chemical analysis methods for
Between ferrous chloride and ferrous sulfate precursors, the amount and location of the deposit
was relatively similar. At lower temperatures near the inlet, the deposit was found to be less and
the deposit thickness grew as the temperature increased towards the outlet of the test section.
Ultrasonic cleaning was able to remove the majority of the deposit, however, some of the deposit
remained intact to the tube and was only removed after the acid wash procedure. It was observed
that for tube sections which were subject to supercritical temperatures, depositions remained
intact and were much more difficult to remove than those exposed to subcritical temperatures.
This suggests an increase in the oxide adhesive strength to the surface at supercritical conditions,
shown by the increased amount of magnetite which was removed only after an “aggressive”
77
In a study conducted by Yeon et al. (2006), the deposition characteristic of hematite particles
onto a heated zircaloy tubing was found to change by adding ferrous species to the solution.
Under single phase flow conditions, there was almost no deposition of hematite particles onto a
zircaloy surface unless the particles were mixed with ferrous ions. The deposit was found to form
two layers on the surface; a top layer which was easily removed with ultrasonic cleaning using
distilled water and an inner layer which was only removed after ultrasonic cleaning with
concentrated acid. Yeon et al. (2006) concluded that the top layer was formed from particle
deposition while the inner layer was formed from the precipitation of ferrous ions. Therefore, the
crystallization of dissolved ferrous species formed a stronger bond to the surface which then
allowed the loosely attached particles to stick to the wall. In the case of the ferrous precursors in
supercritical water, the higher strength of the oxide in supercritical conditions is believed to be
due to small amounts of crystallization occurring at the interface between particles and the tube
78
Figure 5-8: Deposit thickness on test section for reference condition with ferrous chloride
precursor (Experiment #1)
Figure 5-9: Deposit thickness on test section for reference condition with ferrous sulfate
precursor (Experiment #2)
79
5.2 Effect of Heat Flux
Experiments were run with low heat flux and no heat flux conditions and are compared with the
reference condition. Low heat flux of approximately 20 kW/m2 in the test section was conducted
for both ferrous chloride and ferrous sulfate precursor, with temperature ranging from 371°C to
376°C. A third experiment under no heat flux condition had ferrous sulfate precursor solution
Temperature measurements were taken for the low heat flux conditions, however, no significant
SEM analysis showed sub-micron to several micron-sized particles scattered along the
membrane similar to those seen in the reference conditions for ferrous sulfate (see Figure 5-10).
The filter shows particles of various shapes and sizes, some which appear to be crystalline.
20.0keV area EDX was applied on the filter which confirmed the presence of iron oxide along
with silver from the background as shown in Figure 5-11. The absence of other metal oxides
such as nickel, chromium, or molybdenum oxides support the assumption that corrosion of the
stainless steel 316L test section under experimental conditions is negligible. The HTHP filter for
ferrous sulfate at low heat flux was fairly uniform magnetite particles of 1 µm size with
agglomerates of smaller particles on HTHP filter suggesting that the type of precursor has some
80
Figure 5-10: SEM photograph of particles collected on HTHP filter, 5.0k magnification, for low
heat flux with ferrous chloride precursor (Experiment #3)
Figure 5-11: EDX of HTHP filter for low heat flux with ferrous chloride precursor
81
Figure 5-12: SEM photograph of particles collected on HTHP filter, 5.0k magnification, for low
heat flux with ferrous sulfate precursor (Experiment #4)
Figure 5-13: SEM photograph of particles collected on HTHP filter, 5.0k magnification, for no
heat flux with ferrous chloride (Experiment #5)
82
For the experiment run with ferrous sulfate with no heat flux and supercritical temperature, the
particles on the HTHP filter were of larger diameter than in low heat flux experiments and some
of these larger particles also appear to have an octahedral structure as seen in Figure 5-13, which
is a common crystal structure for magnetite (Anthony et al., 1997). XRD was carried out on the
HTHP silver membrane filter of Experiment #3 to determine the crystal structure of the
deposited particles. Results show that the peaks match very well with those of magnetite and
comparison of these peaks to other iron oxide such as hematite indicated that these were not
present in the sample. Carbon graphite is also present in the sample and is believed to have been
detected due to the carbon tape used on the filter for SEM.
Figure 5-14: XRD of deposit on HTHP filter for low heat flux with ferrous chloride precursor
(Experiment #3)
83
5.2.3 Deposit Analysis
Deposition thickness of the test section for ferrous sulfate precursor under low and no heat flux
conditions were examined and the results are found in Appendix C. SEM images of the tubes
show very little deposition and these findings are confirmed using cleaning methods.
Figure 5-15: Deposit thickness on test section, low heat flux with ferrous sulfate precursor
(Experiment #4)
The effect of heat flux compared to reference condition suggests that lower heat flux results in
lower deposition. This compares to previous models which showed that deposition had a direct
influence from heat flux (Electric Power Research Institute Inc., 2003). In previous studies,
5.04mg of Fe kg/L was 30% lower on an unheated surface than one with heat flux of 400kW/m2
84
Although the original Kern and Seaton model does not account for the influence of heat flux on
particle deposition, there have been several attempts in later studies to include heat flux by
Steinhagen et al., 1988). Thermophoresis has been shown to create a measurable change in the
deposition of a particle onto a heated surface for particles as large as 11 µm (Epstein, 1997),
velocity is dependent on the fluid properties and temperature gradient and can be calculated
5-1
5-2
The constant k is 1.8 for gases and 0.26 for liquids, λp and λl represent the conductivity of the
particle and liquid respectively (Epstein, 1997). The overall deposition velocity accounting for
( ) 5-3
The equation resulted in values for the thermophoretic velocity of Kth in the range of 10-10 m/s,
much smaller than the mass transport velocity of 10-4 m/s for these experiments, suggesting that
85
In addition to thermophoresis, high heat flux conditions usually result in higher surface
temperature given constant flow rates, which provide the activation energy required for the
particle to stick to the wall. In an experiment with alumina particles depositing on a heated
surface, Müller-Steinhagen et al. (1988) observed that an asymptotic fouling resistance had a
maximum at any given heat flux for a fixed flow rate, concentration and bulk temperature. To
model the data, Müller-Steinhagen included both thermophoresis and activation energy into the
Kern and Seaton model. The model showed that the increase in heat flux initially resulted in the
decreasing deposition with increasing heat flux. In general, the correlation over-predicted
deposition velocities and a correction factor had to be introduced to give a reasonable fit to the
experimental data. Such a procedure demonstrates the difficulty in accurately modeling the
Although the Arrhenius term predicts lower deposition rates for lower heat flux conditions, it
fails to adequately explain the extent to which deposition rate decreased in these experiments
temperature may also affect the structure of the deposit, making it more porous and loosely
packed in certain conditions. It is not known if this is affected by absolute wall temperature or by
the wall-liquid temperature difference. If it is assumed that the lower heat flux results in loosely
packed deposits which can easily be subject to removal, this may explain the lower deposition of
the low heat flux condition observed in this study. However, further research would be required
86
in order to make any conclusions regarding if heat flux has a direct influence on the deposit
structure.
Current CANDU reactors normally operate with a pH of 9 ~ 10 using a simple water chemistry
of lithium hydroxide for pH control (Burrill, 2000). Two experiments were conducted with
ferrous sulfate as a precursor but at a higher pH of 9 (at room temperature). The experiments
were run with temperatures running at 350°C to 400°C and 200°C to 370ºC.
The pH of the system was increased by adding sodium hydroxide salt to the feedwater. At first,
ferrous sulfate and sodium hydroxide was mixed in the injection tank and the pH was measured
immediately produced particles in the system which would cause problems with the injection
pump. As an alternative approach, sodium hydroxide solution was introduced in the primary tank
and allowed to mix with the ferrous sulfate in-situ of the system. Due to size limitations of the
main tank, sodium hydroxide was added to the first tank after heating the entire system. The
sodium hydroxide was weighed and mixed into a deaerated tank and a sample was drawn from
the tank. The conductivity was measured and compared to the amount of sodium hydroxide
required using a calibration curve shown in Figure 5-16. A linear regression gave the equation 5-
5-4
87
Figure 5-16: Calibration of the conductivity meter for determining NaOH concentration in
primary tank
The pH could not be measured directly in the system due to the high temperature and pressure of
the solution at the mixing tee. Instead, the pH of the ferrous sulfate solution was determined by
using data from Arden (1950) for ferrous sulfate and sodium hydroxide solution. Conditions in
Arden’s experiment are similar to the conditions in this study. The solution was deaerated to
eliminate the presence of oxygen and ferric ions which have been found to create large errors in
the pH measurements. Oxygen in the system promotes the formation of ferrosic hydroxide, a
ferric ion compound instead of the desired ferrous hydroxide (Arden, 1950).
The conductivity of the primary tank after dissolving sodium hydroxide was 2.02 and 2.10
mS/cm which correspond to a concentration of 10.49 and 10.91 mmol/L for experiments #6 and
88
#7 respectively. The ratio of Na to Fe was calculated with equation 5-4 taking into consideration
̇ ̇ 5-5
̇ ̇
The molar ratio of Na to Fe was compared to data with Arden (1950) and the pH was determined
Figure 5-17: Predicted pH of the system using data from Arden (1950)
For the experiment with the test section heated from subcritical to supercritical, large
temperature changes were found at locations 0.15 m and 1.20 m while a steady temperature rise
was found near the outlet at 1.65m. The temperature at the 1.20 m location approached 500°C
89
after 30 minutes which was considered too high and the power to the test section was
momentarily turned off to cool the section. Once the temperature dropped to below 400°C, the
test section was turned on once more to continue the injection at the original temperatures until
Injection
Figure 5-18: Temperature measurements of test section vs. time for high pH with ferrous sulfate
precursor (Experiment #6). Power turned off briefly at t = 48 minutes.
Temperature measurements at 0.15 m from the inlet suggest that deposits exfoliated from the
tube surface relatively easily and quickly. These deposition-removal cycles found in the
temperature was also observed by Khan (2005) with the injection of sodium carbonate in
supercritical water. These occurred with combined particle and crystallization deposition and
signaled a weaker adhesion to the tube wall than pure crystalline deposit.
90
5.3.2 Filter Analysis
Observing the particles captured on the HTHP and LTHP filters under an SEM, revealed that the
particle sizes are consistently much smaller than in the reference case, falling in the 100-200nm
diameter range. Formation of smaller particles in higher pH solution are confirmed by literature
studies using sol-gels. Sugimoto and Matijevic (1980) displayed that under excess OH- ions, the
magnetite particles formed were small, tens of nanometer in diameter and had a cubic
morphology. On the other hand, large magnetite particles of 1.1 µm formed under 0.03M excess
Fe2+ conditions.
The LTHP filter for both experiments had a significant amount of small particles deposited on
the glass fiber. In experiment #7, it can be seen that the deposit was enough to completely cover
Figure 5-19: SEM photograph of particles collected on HTHP filter, 10.0k magnification, for
high pH, ferrous sulfate (Experiment #6)
91
Figure 5-20: SEM photograph of particles collected on LTHP filter, 2.0k magnification, for high
pH, ferrous sulfate (Experiment #6)
Figure 5-21: SEM photograph of particles collected on HTHP filter, 5.0k magnification, for high
pH, subcritical, ferrous sulfate (Experiment #7)
92
Figure 5-22: SEM photograph of particles collected on LTHP filter, 2.0k magnification, for high
pH, subcritical, ferrous sulfate (Experiment #7)
SEM images of the tube surface after the test section was disassembled confirm that there was
very few particles attached to the surface. Furthermore, deposit thickness determination using
cleaning methods indicate that the deposit is less than 1 µm shown by Figure 5-23.
93
Figure 5-23: Deposit thickness on test section (Experiment #6)
As mentioned in Section 2.3.3, the particles that deposit on the tube are submerged in the viscous
sub-layer which dissipates turbulent bursts responsible for particle removal. The viscous sub-
layer thickness was calculated for the high pH at supercritical experiment using equation 5.5
5-6
The calculations showed that this distance was approximately 25 µm at 200°C, 14 µm at 350°C,
and 6 µm at 400ºC under the experimental conditions. In the case of Experiment #6 at 0.15m
location, the deposition-removal cycles had an average temperature change of 12°C from the
initially clean state. This corresponded to a calculated thickness of the deposit right before the
removal of 42 µm.
94
The cool down procedure was repeated in a similar manner for all experiments for direct
comparison between the experiments. Significant amount of particles were found in the effluent
of the system during the cooling/depressurization for both high pH experiments, indicating that
removal rates post-injection were much higher for this deposit. This may be attributed to the
increase in flow rate during depressurization. Turner et al. (1990) suggested that the change in
flow rates are a larger factor in removal rates compared to steady state conditions.
The experiment with lower concentration of 0.5 mmol/L and proportionally longer duration of
400 minutes was conducted to determine the effects of concentration on deposition without
changing the total amount of ferrous species injected. All three filters showed ferrous-chromium
exfoliation occurring in the system indicating corrosion of the tube. Hence, the results from this
A blank test was also run with reference conditions but without a precursor. SEM analysis of the
HTHP and LTLP filters showed almost no particles collected as expected. The LTHP filter had
few particles which likely exfoliated from the heat exchanger, but the amount was insignificant
A summary of the significant results from each of the experiments are provided in Table 5-2.
95
Table 5-2: Results summary table - Part I
Filters
Parameter Precursor Tube Samples SEM
HTHP LTHP LTLP
1 Reference FeCl2 Almost no Large amount Almost no Small particles at inlet,
case for particles of submicron particles large micron sized
ferrous and some particles at high
chloride micron sized temperatures
particles
2 Reference FeSO4 Nanometer to Very Small Almost no Small and few deposits
case for several micron particles of particles found at inlet, large deposits
ferrous unknown size at center of test
sulfate section
3 Low heat flux FeCl2 Several micron Very Small N/A consistent micron sized
size particles of particles found at inlet
unknown size and outlet of test
section
4 Low heat flux FeSO4 Consistent ≈ 1 Very Small Almost no Very few deposits
micron size particles of particles found
unknown size
96
Table 5-3: Results summary table - Part II
3 No difference found N/A N/A Recovery Analyzed HTHP Test section is 1.0m long, test
of 52% Filter, found section not examined using
magnetite cleaning method
6 Temperature rise at Less than No difference Recovery N/A Large amount of black particles
supercritical 1µm of 53% found in the effluent after
temperatures, oxide thickness cooling the system
deposition and
exfoliation found at
subcritical
7 No difference found N/A N/A Recovery N/A Did not dissassemble test
of 39% section for this experiment
8 No difference found N/A N/A Recovery N/A Did not dissassemble test
of 83% section for this experiment
No difference found N/A N/A N/A N/A Did not dissassemble test
section for this experiment
97
A mass balance calculation was completed for all experiments, however, not all sections for each
experiment were analyzed and therefore, are presented to provide an approximation only. The
majority of the experiments had good recovery of the ferrous species injected into the system
with the exception of experiment #7 which was below 50%. To determine the yield of magnetite
for input into the simulation, the iron content found in the effluent was subtracted from the total
injected amount. Hence, it was assumed that the iron mass which was not recovered had
deposited as magnetite particles onto other surfaces within the system not analyzed, such as the
heat exchanger or the tube fittings between the mixing tee and test section. Mass balance for
future experiments may be improved by cleaning the heat exchanger after each experiment and
analyzing the iron concentration in the cleaning solution. The equation for recovery and yield are
5-7
5-8
In experiment #6 and #7, it was found that the effluent contained significant amount of oxide
particles which passed through the LTHP filter, perhaps due to overloading. The experiment
produced a higher yield of iron oxide particles indicated by the relative number of particles
collected on the HTHP filter. To gain insight into the yield in the high pH experiments, the
effluent from experiment #7 was first filtered using a Fisherbrand filter (Grade - P2) to separate
the residue from the filtrate. The residue and filtrate were independently analyzed using AAS. It
was found that the effluent was 57% particulate matter. Therefore, for experiments #6 and #7,
98
the same percentage of particulate matter in the effluent was assumed and the amount was added
99
6 Results and Discussion of Simulations
Simulations were run with parameters from experiments and these were compared to
experimental deposition thickness obtained from the cleaning method. The magnetite
concentration used for the simulation was obtained from the yield estimated from mass balance
in Table 5-4, while the average particle size was estimated from the SEM images of the tube
deposit and filters. For the reference conditions, the average particle size was estimated to be 4
µm and 1 µm for ferrous chloride and ferrous sulfate precursors respectively. For these reference
condition experiments, the simulation results predicted magnetite deposition reasonably well.
The simulation predicted similar deposition thickness for each case, however, with larger
particles the peak deposit shifted closer towards the inlet of the test section.
(a) (b)
Figure 6-1: Comparison between simulation and experimental for reference conditions (a)
Experiment #1, ferrous chloride with average particle size = 4 µm, magnetite
concentration = 200 mg/L (b) Experiment #2, ferrous sulfate with average particle
size = 1µm, magnetite concentration = 299 mg/L.
100
For low heat flux conditions, the deposition thickness was overestimated by nearly a factor of
four. However, the simulation did predict a lower deposition rate compared to the other
experiments and a uniform deposition rate along the test section compared well to experimental
(a) (b)
Figure 6-2: Comparison between simulation and experimental for ferrous sulfate experiments
with (a) Experiment #4, low heat flux with average particle size = 1 µm, magnetite
concentration = 108 mg/L and (b) Experiment #5, no heat flux with average particle
size = 2 µm, magnetite concentration = 89 mg/L.
Finally, for the experiments at high pH, the simulation greatly overestimated the deposition
thickness. This is likely due to the removal that occurred during and after the deposition process
described in section 5.3.3. Higher removal rates in the high pH conditions suggest that the
deposit had a weaker adhesion to the tube. As discussed in section 5.1.3, the strength of oxide
adhesion was enhanced with the precipitation of ferrous species, and one explanation is that the
101
reduced amount of dissolved ferrous ions in the solution resulting from the high yield of particles
formed under high pH condition may have caused the formation of a weak deposit. A second
possibility is that the formation of molten sodium hydroxide salts had formed and deposited
along with the magnetite particles in supercritical conditions. During cool down, the molten salt
would have re-dissolved in the water, possibly carrying the magnetite particles along with it.
Figure 6-3: Comparison between simulation and experimental for Experiment #6, high pH,
ferrous sulfate. Simulation was run with an average particle size = 0.15µm,
magnetite concentration = 321 mg/L.
In all cases, the simulation overestimated the deposition of magnetite suggesting that surface
supercritical water.
102
6.2 Simulation for CANDU SCWR
As one of the design criteria in the proposed SCWR, the maximum fuel cladding temperature
cannot exceed 850⁰C (Naidin et al., 2009). This is to ensure that the material’s mechanical and
chemical properties can withstand the aggressive environment of supercritical water. Li et al.
(2009) developed a 3-dimensional heat transfer simulation for a CANFLEX fuel bundle in a
SCWR which showed that the maximum temperature of the cladding can reach as high as
The CANDU SCWR deposition simulation developed in this study does not account for oxide
growth from the fuel cladding. This is due to the fact that the alloy for the fuel cladding has not
been decided and the rate of oxide growth from the alloy varies dramatically depending on the
material (Was et al., 2006). Additionally, only the surface temperature of the fuel cladding
exposed to supercritical water is calculated since the design criteria of maximum fuel cladding is
Figure 6-4 shows the expected fuel cladding-surface temperature with a heat flux of 1000
kW/m2 with no deposition (see Table 3-1 for simulation parameters). The fluid enters the test
section at 350ºC and 25MPa, saturated with 11µg/L of ferrous ions. As the temperature
increases beyond the pseudocritical temperature, the solubility drops in accordance with
Figure 2-3 and particles form in the bulk fluid. Figure 6-5 shows the temperature profile of the
fuel bundle after one year of operation assuming a particle diameter of 150 nm.
103
Figure 6-4: Bulk fluid and fuel cladding-surface temperature without particle deposition
Figure 6-5: Bulk fluid and fuel cladding-surface temperature after 1 year of operation with
magnetite particles of 150 nm diameter
104
Figure 6-6: Magnetite deposition thickness on fuel cladding after 1 year of operation for 150
nm and 1 µm average particle diameters
In Figure 6-6, the effects of particle diameter is compared between 150 nm and 1 µm. The
experimental results from section 5.3 suggest that at a pH ≈ 9-10 where a typical CANDU
reactor operates (Burrill, 2000), the formation of small, ~100 nm particles are likely. For the 1
µm scenario where 0.279 ≤ tp+ ≤ 8.284, inertial coasting is the dominant mechanism for
deposition and the deposition velocity is approaching maximum rate. On the other hand, for
the particle diameter of 150 nm where 0.006 ≤ tp+ ≤ 0.215, the deposition mechanism changes
from diffusion to inertial coasting inside the reactor core and the deposition velocity remains
105
Since the simulation was based from 1 fuel element, the cladding temperature represents an
average among all 43 actual elements. The Li et al. (2009) simulation which looked at all 43
elements, found that cladding-surface temperatures can vary by several hundred degrees
depending on the fuel element. The highest fuel cladding temperature of 802.2⁰C occurred at
the 4 m location where an increase of 19.6⁰C due to fouling was found by this study.
Therefore after several years of operation, fouling on the fuel cladding may cause
temperatures to exceed the design criteria of 850⁰C if magnetite deposition considerations are
Calculation of the deposit thickness found in the simulation by Burrill (2000) discussed in
section 2.3.4 suggest a peak deposit of 297 µm assuming mass transport of ferrous ions in a
CANDU SCWR after one year of operation. This is in relatively good agreement to the results
presented in this study considering several key differences in the parameters and assumptions
in the model; a slightly higher saturation concentration of 18µg/L (Burrill, 2000) compared to
11 µg/L, temperature of core outlet of 384°C (Burrill, 2000) compared to 625°C, and the use
Similarly, the transport and deposition model of Cook and Fatoux (2009) concluded a deposit
thickness of 22.8 µm near the outlet of a CANDU SCWR reactor. The arbitrary deposition
velocity assumed by Cook and Fatoux of 10-5 m/s which is slightly lower than the 4.2×10-5 –
28.7×10-5 m/s range for the deposition velocity calculated here using mass transport for 150
found from this study fits reasonably well with the model by Cook and Fatoux.
106
6.3 Limitations of the Simulation
In Chapter 5, surface attachment resistance and removal rates were found to be important
factors in the deposition of magnetite particles in supercritical water. However, these were
surface attachment and removal term. Therefore, for the situation where surface attachment
and removal terms are unknown, mass transport models provide a relatively good estimate on
the upper limit for deposition rate. Similar results were found by Turner and Klimas (2000)
who examined magnetite particle deposition onto Alloy 600 under single-phase forced
convection at high temperature and pressure water. Significant deviations were found between
calculated and measured deposition velocities, all of which the mass transport model
overestimated deposition rates. Surface attachment was determined to be the main limitation
in this experiment while removal was found to be insignificant. Turner measured the
isoelectric point for both magnetite and Alloy 600 and determined that they have the same
sign of charge in high temperature alkaline water resulting in a repulsive force between the
particle and surface, thereby significantly limiting deposition (Turner & Klimas, 2000).
Therefore, it is possible that the magnetite particles formed in these experiments in subcritical
On the other hand, surface attachment behaviour can be significantly different in supercritical
water. The electric double layer force was calculated by Ghosh et al. (2006) as a function of
temperature in subcritical and supercritical water at 25MPa. These forces were found to
decrease significantly in supercritical water due to its low dielectric constant. On the other
hand, Van der Waals attraction potential was shown to increase as temperature increased in
107
subcritical water, and further increase in supercritical water (Ghosh et al., 2006). This would
suggest that in supercritical water, double layer and Van der Waals forces should not limit
deposit growth. Instead, the lower deposition would most likely be the result of the removal
process. This may be particularly important for particulate fouling which has a weaker bond
Another limitation to the model is that the nucleation and growth of the particles was assumed
difficult to model the interactions of particles in a complex system (Bott, 1995). Although the
formation of nanometer sized particles can be very fast (Adschiri et al., 1992), SEM images
along the test section has shown that micron-sized particles require time to grow. Therefore,
better models could be produced by including crystal growth along the test section.
108
7 Conclusion
In this study, fouling and transport of magnetite particles in supercritical water were examined
experimentally and through computer simulation models. Experimental work was conducted
with the objective of utilizing several online and offline techniques for characterizing the
deposition and transport phenomena under different heat flux, temperature ranges, and pH
adapted for producing magnetite particles in deaerated supercritical water using ferrous chloride
and ferrous sulfate as precursors. EDX analysis of the particles collected on the filter clearly
show an iron oxide composition and XRD of the tube and filter deposits confirm the formation of
magnetite.
implemented in the test section to infer the deposition thickness on the tube wall. Deposits led to
an increase in outer wall temperature under supercritical conditions during the injection of
ferrous chloride with no pH adjustment and ferrous sulfate at high pH. It is speculated that the
mixed deposition of magnetite and precipitated ferrous precursor was the source of very high
fouling rates in supercritical water. For high pH ferrous sulfate condition, deposition-removal
cycles were observed at subcritical temperatures which are believed to be only magnetite
particulate fouling. These cycles continued throughout the injection with complete removal
occurring when deposit thickness approached 42 µm. It was observed that removal during cool
down was particularly important for high pH experiments where sub-micron sized particles of
109
Using ultrasound and acid wash cleaning procedures, a qualitative method for determining
deposit strength was developed. Results suggest that under supercritical conditions, the
particulate deposit had a stronger adhesion to the tube and required an aggressive cleaning
procedure to completely remove the deposit. It is possible that the precipitation of ferrous species
between the depositing particle and surface was responsible for the stronger bond. In addition,
SEM imaging of the test section showed the morphology of the deposit varied along the tube
All four techniques individually provide unique data on the particles while the combination of
the techniques give an overall understanding of deposition/transport in the system. The online
thermal resistance monitoring provided valuable information about deposition and removal
cycles, while particle size and adhesive strength could only be determined from offline methods.
In the future, high temperature high pressure filters could be implemented in full scale SCW
systems which could provide valuable information on the effects of water chemistry on corrosion
product transport. On the other hand, destructive testing techniques such as surface SEM and
cleaning methods would likely be useful for small test setup experiments such as the one
Simulation using heat and mass transport equations produced comparable predictions to
experiments for the deposition thickness in the test section. In all cases, the simulation
overestimated the deposit thickness, particularly for the high pH experiment where high removal
was observed experimentally. The results suggest that both surface attachment and removal rates
should be included in the simulation model which would effectively reduce the deposition
110
thickness. In supercritical conditions, the effects of surface attachment forces become less
significant and removal is likely to be the dominant limitation to deposition. However, difficulty
in modeling both removal and surface attachment stems from the lack of fundamental theory for
Finally, the simulation was adapted to predict fouling rates in a hypothetical CANDU SCWR.
The design parameters of a current ACR-700 fuel bundle along with proposed SCWR parameters
provided a baseline for the simulation. Thermodynamic solubility predictions using HKF models
from literature were used to predict the concentration of magnetite particles which would form in
the reactor core. These simulations (assuming mass-transfer limited deposition) suggested that
fouling may lead to an increase of fuel cladding-surface temperatures of up to 23.9⁰C after one
year of operation assuming the formation of submicron particles. At 4 m down from the inlet, the
temperature rise is expected to be 19.6ºC, raising the peak temperature of one section from
802.2ºC to 823.7ºC. This temperature increase in the fuel cladding can potentially be a
significant problem for long term operation of a CANDU SCWR, and therefore requires further
research.
111
8 Recommendations
This study showed that fouling and transport of corrosion products can be a significant issue for
the development of a Generation IV CANDU SCWR. Therefore there is a need for developing
new techniques and instruments for monitoring and characterizing deposition and transport,
particularly for magnetite particles. It remains a challenging task to produce these instruments
which can withstand the high temperature and pressure of supercritical water. The following
provide recommendations for further development for the techniques presented in this study.
Use nickel alloys for test section tube material which will provide better resistance to
hydrochloric acid and are immune to sulfuric acid, both a byproduct of the hydrolysis of
ferrous chloride and sulfate respectively, making it more suitable for hydrothermal
Experiments of longer duration would be useful for validating the online thermal
become an issue when the thermocouples are exposed to high temperature for extended
period of time.
Experiments of very long durations (>1000 hrs) could simulate deposition and transport
of corrosion products without the need for artificially introduced ferrous species. Instead,
the water could be saturated with ferrous species at 350°C which is then pumped into a
test section for deposition. This would require a fully automated system and the system
piping would need to be constructed from an iron free alloy or lined with ceramic or
glass.
112
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119
Appendices
%-------------------------------------------------------------------------
% Section 1: User defined inputs
%---------------------------------------------------------------------------
% Section 2: Runtime Variables
%--------------------------------------------------------------------------
% Section 3: Constants
120
% Other Variables
% KFe3O4 Thermal conductivity of Fe3O4 [W/mK]
% Tw1 Temperature at the bulk/surface interface
% Tw2 Temperature at the point between the oxide and alloy
% Tw3 Outside wall temperature and is measured experimentally
%--------------------------------------------------------------------------
% Section 4: Set Initial Values
%--------------------------------------------------------------------------
% Section 5: Main part of the code
for j = 2:Nlength+1,
% Track and print to display
count = 1 + count
121
dm(j) = 0;
rfoul(j) = 0;
end
%--------------------------------------------------------------------------
% Section 6: Plotting
xnew = dx:dx:tlength; %For graphs which does not need value at x=0
for k=1:Nlength,
yfoul(k) = thickness(k+1)*1000000;
end
subplot(2,2,2)
semilogy(x,TP,x,0.2,x,20)
xlabel('Length [m]')
ylabel('tp*')
title('tp* vs Length')
subplot(2,2,3)
plot(x,Tb)
xlabel('Length [m]')
ylabel('Temperature [(Khan)C]')
title('Bulk Temperature vs Length')
subplot(2,2,4)
plot(x,Cb*1000000)
xlabel('Length [m]')
ylabel('Concentration [mg/kg]')
title('Concentration vs Length')
122
ylabel('Temperature (C)')
%--------------------------------------------------------------------------
% Section 6: Reporting to MATLAB display
thickp = thickness'*1000000;
xp = x';
Bulkfluid = Cb(Nlength+1);
section_mass = zeros(10,1);
count1 = 1;
count2 = 1;
for p=1:Nlength,
section_mass(count1) = section_mass(count1)+dm(p);
if count2 == (Nlength/10)
count1 = count1+1;
count2 = 1;
else
count2 = count2+1;
end
end
section_mass_mg = section_mass*1000000
total_mass_mg = Cb(1)*flowrate*runtime_min*1000000/60
deposited_mass_mg = sum(section_mass_mg)
mass_to_filter_mg = total_mass_mg - deposited_mass_mg
deposited_percentage = deposited_mass_mg*100/total_mass_mg
concentration_tank2_mgL = Cb(1)*(flowrate/flowrate_pump2)*1000000
total_mass_g = Cb(1)*flowrate*runtime_min*1000/60
transpose(thickness);
hflux
123
Functions
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
% Buoyancy Effects Calculation
% Bouyancy Calculations based from Petukhov, evaluated by Bazargan
% Written by Keigo Karakama
% Date created: April 18, 2011
% Last modified: July 19, 2011
g = 9.81;
Tf = (Tw + Tb)/2;
rhoF = XSteam('rho_pT' ,P,Tf);
rhoB = XSteam('rho_pT' ,P,Tb);
rhoW = XSteam('rho_pT' ,P,Tw);
Hw = XSteam('h_pT' ,P,Tw);
Hb = XSteam('h_pT' ,P,Tb);
k = XSteam('tc_pT' ,P,Tb);
mu = XSteam('my_pT' ,P,Tb);
Pr = (Hw-Hb)*1000*(mu/k)/(Tw-Tb);
Refun_pipe(m,d,mu);
B = (1/rhoF)*(rhoB - rhoW)/(Tw-Tb);
Grth = (3*10^-5)*(Reb^2.75)*(Pr^0.5)*(1+2.4*(Reb^-0.125)*(Pr^(2/3)-1));
Grq = g*B*hflux*d^4/((mu/rhoB)^2*k);
A = Grq/Grth;
end
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
% Deposition Velocity
% Written by Keigo Karakama
% Date created: January 9, 2011
% Last modified: January 20, 2011
124
dmdt = rho_oxide*Kt*(Cb-Csat)*pi*di*dx;
end
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
% Deposition Velocity
% Written by Keigo Karakama
% Date created: January 9, 2011
% Last modified: January 10, 2011
rhof= XSteam('rho_pT',P,Tb);
mu = XSteam('my_pT',P,Tb);
Re = Refun_pipe(m,di,mu);
eps = 0.000002 + thickness;
f = frictionfun(eps,di,Re);
u = 4*m/(rhof*pi*di^2);
U = u*sqrt(f/8);
D = diffusioncoefficient(Tb,mu,dp);
TP = rhop*(rhof*U*dp/mu)^2/(18*rhof);
Sc = Scfun(mu,rhof,D);
end
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
% Diffusion Coefficient
% Written by Keigo Karakama
% Date created: January 9, 2011
125
% Last modified: January 9, 2011
function D = diffussioncoefficient(T,mu,dp)
kB = 1.38065*10^-23;
Tk = T + 273;
D = kB*Tk/(3*pi*mu*dp);
end
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
% Fluid/thermal Properties Function
% Written by Keigo Karakama
% Date created: August 23, 2010
% Last modified: October 9, 2011
% First estimate to Tw
Tw = Tb + 1;
Tw_old = Tb + 2;
126
Pr = Prfun(viscosity,cp,k);
Nu = Nufun(Re,Pr,rhoB,rhoW,Tb,P);
hconv = Nu*k/di;
% Initial guess of Tw
Tw = Tb + 1;
Tw_old = Tb + 2;
hconv = Nu*k/di;
Tw_old = Tw;
Tw = Twfun(hflux,Nu,k,Tb,di);
Tw = (Tw+Tw_old)/2;
end
end
end
127
[A,Grth,Grq] = bouyancy(Tw,Tb,Reb,di,P,m,hflux);
end
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
% Friction Factor Calculation
% Written by Keigo Karakama
% Date created: January 12, 2011
% Last modified: January 12, 2011
%
% Note: Uses explicit relation developed by S.E.Haaland
function f = frictionfun(eps,di,Re)
% Re = Reynolds number
% di = diameter of inside of tube [m]
% eps = roughness value of tube [m]
f = (-1.8*log10((6.9/Re)+(eps/(3.7*di))^1.11))^-2;
end
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
% Nusselt number function
% Written by Keigo Karakama
% Created: November 28, 2010
% Modified: December 9, 2010
function Nu = Nufun(Re,Pr,rhoW,rhoB,Tb,P)
% Re = Reynolds number
% Pr = Prandtl number
% rhoW, rhoB = fluid density at wall and bulk respectively [kg/m^3]
% Tb = Bulk fluid temperature [C]
% P = Pressure [bar]
Tcritical = 374;
Pcritical = 221;
end
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
% Prandtl Function
% Written by Keigo Karakama
% Date created: August 23, 2010
% Last modified: August 23, 2010
128
function prandtl = Prfun(viscosity,cp,k)
prandtl = cp*viscosity/k;
end
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
% Reynolds Pipe Function
% Written by Keigo Karakama
% Date created: August 23, 2010
% Last modified: December 9, 2010
reynolds = 4*m/(pi*D*viscosity);
end
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
% Schmidt Number = viscous diffusion rate / mass diffusion rate
% Written by Keigo Karakama
% Date created: January 9, 2011
% Last modified: January 9, 2011
function Sc = Scfun(mu,rho,D)
Sc = mu/(rho*D);
end
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
% Thickness of deposit calculation
% Written by Keigo Karakama
% Date created: December 1, 2010
% Last modified: January 24, 2011
% Equation from Holman (see reference)
function t = thicknessfun(m_oxide,rho_oxide,r2,dx,dt)
129
% m_oxide = mass of deposit [kg]
% rho_oxide = density of oxide [kg]
% r2 = radius [m]
t = r2 - sqrt(r2^2 - m_oxide*dt/(rho_oxide*pi*dx));
end
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
% External Wall Temperature
% Program to calculate the outside wall temperature with internal heat
% Written by Keigo Karakama
% Date created: December 1, 2010
% Last modified: December 1, 2010
function To = twecalc(Ti,hflux,k,di,do)
A = di/do;
To = Ti + hflux*(di/2)/(2*k)*((A^2-log(A^2)-1)/(1-A^2));
end
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
% Oxide/Wall temperature
% Written by Keigo Karakama
% Date created: December 1, 2010
% Last modified: January 24, 2011
% Equation from Holman (see reference)
function To = twocalc(Ti,hflux,k,di,do)
To = Ti + hflux*do*log(do/di)/(2*k);
end
%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%%
130
Appendix B: Filter Parts Drawings
131
132
Appendix C: Results of Experiments
Comments:
(1) Flow rates of the secondary line were found to be significantly lower than originally set and
therefore there was very little filter deposits.
133
Injection
Figure C-1: Temperature measurements of test section vs. time for reference condition with
ferrous chloride precursor. (Experiment #1)
Figure C-2: SEM photograph of particles collected on HTHP filter, 2.0k magnification, for
reference condition with ferrous chloride precursor. Low flow rate in secondary line
resulting in very few particles collected. (Experiment #1)
134
Figure C-3: SEM photograph of particles collected on LTHP filter, 1.8k magnification, for
reference condition with ferrous chloride precursor. (Experiment #1)
Figure C-4: SEM photograph of particles collected on LTLP filter, 2.0k magnification, for
reference condition with ferrous chloride precursor. Low flow rate in secondary line
resulting in very few particles collected. (Experiment #1)
135
(a)
(b)
(c)
(d)
Figure C-5: SEM photograph of magnetite deposit on test section tube surface, (a) 0.15 m, (b)
0.60 m, (c) 1.20 m, and (d) 1.65 m location. (Experiment #1)
136
Figure C-6: Deposit thickness on test section for reference condition with ferrous chloride
precursor. (Experiment #1)
Figure C-7: Comparison between simulation and experimental for reference condition ferrous
chloride. Simulation was run with an average particle size = 4 µm, magnetite
concentration = 200 mg/L.
137
C. 2. Reference Condition, Ferrous Sulfate
138
Injection
Figure C-8: Temperature measurements of test section vs. time, temperature fluctuations were
found in both the inlet and outlet bulk temperatures which may be attributed to the
inconsistent flow. (Experiment #2)
Figure C-9: SEM photograph of particles collected on HTHP filter, 2.0k magnification, for
reference condition with ferrous sulfate. (Experiment #2)
139
Figure C-10: SEM photograph of particles collected on LTHP filter, 2.0k magnification, for
reference condition with ferrous sulfate. (Experiment #2)
Figure C-11: SEM photograph of particles collected on LTLP filter, 2.0k magnification, for
reference condition with ferrous sulfate. (Experiment #2)
140
Figure C-12: SEM photograph of magnetite deposit on test section tube surface, (a) 0.15 m, (b)
0.60 m, (c) 1.20 m, and (d) 1.65 m location. (Experiment #2)
141
Figure C-13: Deposit thickness on test section for reference condition with ferrous sulfate
precursor. (Experiment #2)
Figure C-14: Comparison between simulation and experimental for reference condition ferrous
sulfate. Simulation was run with an average particle size = 1 µm, magnetite
concentration = 190 mg/L.
142
C. 3. Low Heat Flux, Ferrous Chloride
Comments:
(1) Experiment used a 1 m long test section and lower line voltage.
(2) LTLP filter had not been added yet to the system for this experiment.
143
Injection
Figure C-15: Temperature measurements of test section vs. time for low heat flux ferrous
chloride precursor. (Experiment #3)
Figure C-16: SEM photograph of particles collected on HTHP filter, 2.0k magnification, for low
heat flux with ferrous chloride precursor. (Experiment #3)
144
Figure C-17: SEM photograph of particles collected on LTHP filter, 2.0k magnification, for low
heat flux with ferrous chloride precursor. (Experiment #3)
Figure C-18: SEM photograph of particles collected on LTLP filter, - magnification, for low heat
flux with ferrous chloride precursor. (Experiment #3)
145
(a)
(b)
(c)
Figure C-19: SEM photograph of magnetite deposit on test section tube surface, (a) 0.10 m, (b)
0.30 m, and (c) 0.90 m location. (Experiment #3)
146
Data Not Available
Figure C-20: Deposit thickness on test section for low heat flux ferrous chloride precursor.
(Experiment #3)
147
C. 4. Low Heat Flux, Ferrous Sulfate
148
Injection
Figure C-21: Temperature measurements of test section vs. time for low heat flux with ferrous
sulfate precursor. (Experiment #4)
Figure C-22: SEM photograph of particles collected on HTHP filter, 2.0k magnification, for low
heat flux ferrous sulfate precursor (Experiment #4)
149
Figure C-23: SEM photograph of particles collected on LTHP filter, 2.0k magnification, for low
heat flux ferrous sulfate precursor. (Experiment #4)
Figure C-24: SEM photograph of particles collected on LTLP filter, 2.0k magnification, for low
heat flux ferrous sulfate precursor. (Experiment #4)
150
(a)
(b)
(c)
(d)
Figure C-25: SEM photograph of magnetite deposit on test section tube surface, (a) 0.15 m, (b)
0.60 m, (c) 1.20 m, and (d) 1.65 m location. (Experiment #4)
151
Figure C-26: Deposit thickness on test section for low heat flux ferrous sulfate precursor.
(Experiment #4)
Figure C-27: Comparison between simulation and experimental for low heat flux, ferrous sulfate.
Simulation was run with an average particle size = 1 µm, magnetite concentration =
108 mg/L.
152
C. 5. No Heat Flux, Ferrous Sulfate
Comments:
(1) Because there was no net heat flux in this experiment, thermal resistance measurements on
the test section were not taken.
153
Image Not Available
Figure C-28: Temperature measurements of test section vs. time for no heat flux with ferrous
sulfate precursor. (Experiment #5)
Figure C-29: SEM photograph of particles collected on HTHP filter, 2.0k magnification, for no
heat flux with ferrous sulfate precursor. (Experiment #5)
154
Figure C-30: SEM photograph of particles collected on LTHP filter, 2.0k magnification, for no
heat flux with ferrous sulfate precursor. (Experiment #5)
Figure C-31: SEM photograph of particles collected on LTLP filter, 2.0k magnification, for no
heat flux with ferrous sulfate precursor. (Experiment #5)
155
(a)
(b)
(c)
(d)
Figure C-32: SEM photograph of magnetite deposit on test section tube surface, (a) 0.15 m, (b)
0.60 m, (c) 1.20 m, and (d) 1.65 m location. (Experiment #5)
156
Figure C-33: Deposit thickness on test section for no heat flux with ferrous sulfate precursor.
(Experiment #5)
Figure C-34: Comparison between simulation and experimental for no heat flux with ferrous
sulfate precursor. Simulation was run with an average particle size = 2 µm,
magnetite concentration = 89 mg/L.
157
C. 6. High pH, Ferrous Sulfate
158
Injection
Figure C-35: Temperature measurements of test section vs. time for high pH with ferrous sulfate
precursor. (Experiment #6)
Figure C-36: SEM photograph of particles collected on HTHP filter, 2.0k magnification, for high
pH with ferrous sulfate precursor. (Experiment #6)
159
Figure C-37: SEM photograph of particles collected on LTHP filter, 2.0k magnification, for high
pH with ferrous sulfate precursor. (Experiment #6)
Figure C-38: SEM photograph of particles collected on LTLP filter, 2.0k magnification, for high
pH with ferrous sulfate precursor. (Experiment #6)
160
(a)
(b)
(c)
(d)
Figure C-39: SEM photograph of magnetite deposit on test section tube surface, (a) 0.15 m, (b)
0.60 m, (c) 1.20 m, and (d) 1.65 m location. (Experiment #6)
161
Figure C-40: Deposit thickness on test section for high pH with ferrous sulfate precursor.
(Experiment #6)
Figure C-41: Comparison between simulation and experimental for high pH, ferrous sulfate.
Simulation was run with an average particle size 0.15 µm, magnetite concentration
= 321 mg/L.
162
C. 7. High pH & Subcritical, Ferrous Sulfate
Comments:
163
Injection
Figure C-42: Temperature measurements of test section vs. time for high pH & subcritical with
ferrous sulfate precursor. (Experiment #7)
Figure C-43: SEM photograph of particles collected on HTHP filter, 2.0k magnification, for high
pH & subcritical with ferrous sulfate precursor. (Experiment #7)
164
Figure C-44: SEM photograph of particles collected on LTHP filter, 2.0k magnification, for
high pH & subcritical with ferrous sulfate precursor. (Experiment #7)
Figure C-45: SEM photograph of particles collected on LTLP filter, 2.0k magnification, for high
pH & subcritical with ferrous sulfate precursor. (Experiment #7)
165
C. 8. Low Concentration, Ferrous Chloride
Comments
166
Injection
Figure C-46: Temperature measurements of test section vs. time for low concentration with
ferrous chloride precursor. (Experiment #8)
Figure C-47: SEM photograph of particles collected on HTHP filter, 2.0k magnification, for low
concentration with ferrous chloride precursor. (Experiment #8)
167
Figure C-48: SEM photograph of particles collected on LTHP filter, 2.0k magnification, for low
concentration with ferrous chloride precursor. (Experiment #8)
Figure C-49: SEM photograph of particles collected on LTLP filter, 2.0k magnification, for low
concentration with ferrous chloride precursor. (Experiment #8)
168
C. 9. Blank Run
Comments
169
Figure C-50: Temperature measurements of test section vs. time for high pH & subcritical with
ferrous sulfate precursor. (Experiment #9)
Figure C-51: SEM photograph of particles collected on HTHP filter, 2.0k magnification, blank
run. (Experiment #9)
170
Figure C-52: SEM photograph of particles collected on LTHP filter, 5.0k magnification, blank
run. (Experiment #9)
Figure C-53: SEM photograph of particles collected on LTLP filter, 2.0k magnification, blank
run. (Experiment #9)
171
Appendix D: Filter Flow Rates
Filter 1 2 3 4 5 6 7 8
Flow Rate [L/hr] HTHP 0.034 0.21 0.21 0.20 0.21 0.23 0.27 0.24
LTHP 3.506 3.33 3.39 3.339 3.285 3.265 3.195 3.255
LTLP 0.034 0.21 - 0.201 0.21 0.23 0.27 0.24
2
Area of Filter Sample [cm ] HTHP 0.71 0.71 0.71 0.71 0.71 0.71 0.71 0.71
LTHP 2.85 2.85 2.85 2.85 2.85 2.85 2.85 2.85
LTLP 4.91 4.91 4.91 4.91 4.91 4.91 4.91 4.91
Time of Injection [min] 42 39 44 40 40 37 40 400
2
Volume per Area [L/cm ] HTHP 0.033 0.191 0.216 0.188 0.196 0.199 0.252 2.244
LTHP 0.861 0.759 0.872 0.781 0.768 0.706 0.747 7.614
LTLP 0.005 0.028 - 0.027 0.029 0.029 0.037 0.326
Ratio LTHP/HTHP 25.8 4.0 4.0 4.2 3.9 3.6 3.0 3.4
172
Appendix E: Atomic Absorption Spectroscopy
The concentration of iron in each sample using AAS was determined from the calibration curve
found in Figure E-1and Figure E-2 which produced equations E-1 and E-2 respectively.
Figure E-1: Calibration curve for iron concentration using AAS, nitric acid matrix
E-1
173
Figure E-2: Calibration curve for iron concentration using AAS, nitric acid and copper sulfate
matrix
E-2
The uncertainty in the thickness of the deposit was estimated from the uncertainty of several
sources in the calculation including tube length, calibration curve, background concentration, and
volume error.
Uncertainty in volume = 5%
174