Amin Pourmohammadbagher

193 Pages·2016·3.86 MB·English

Effects of Surface Contamination and Water Chemistry on the Behaviors of Illite,
Kaolinite and Montmorillonite in Organic and Aqueous Media

by

Amin Pourmohammadbagher

A thesis submitted in partial fulfillment of the requirements for the degree of

Doctor of Philosophy

in

Chemical Engineering

Department of Chemical and Materials Engineering
University of Alberta

© Amin Pourmohammadbagher, 2016
Abstract:
Clays, due to their specific surface area and electrical charge density, are among the most active
minerals in aquifers, oil and gas reservoirs, and tailings ponds. Clays, in tailings, are a significant
ongoing environmental concern in the mining and oil sands production industries and clay
rehabilitation following contamination poses challenges episodically. Important problems, such
as limited oil recovery during petroleum exploration, involve the interaction of process fluids
with minerals, which constitute reservoir pore walls. Detailed understanding of the fundamentals
of clay behaviors contributes to better environmental impact mitigation strategies, to the
development of production processes for heavy oils and bitumen with lower environmental
impacts, to the treatment of tailings from mined bitumen, and to the mitigation of impacts from
oil spills in natural environments.
Probes, such as solution calorimetry are sensitive to species transfer to and from clay surfaces.
Outcomes can be interpreted unambiguously, when these data are supplemented with TGA and
SEM measurements. Systematic calorimetric measurements provide a framework for parsing the
synergistic and antagonistic impacts of trace (i.e., ppm level) components on the surface
compositions of clays in diverse natural and process environments.
In this study, the effects of clay surface contamination, solvent contamination, and the effects of
water chemistry (temperature, pH, salinity) on the enthalpy of solution of kaolinite, illite and
montmorillonite clays in toluene, n-heptane, pyridine and deionized water were investigated.
Clay contamination included pre-saturation of clays with water, organic liquids, and asphaltenes.
Solvent contamination included addition of trace water to organic liquids and trace organic
liquids to water. A quantitative mass and energy balance modeling framework was developed for
ii
interpreting the enthalpy of solution outcomes that isolates terms for solvents and trace
contaminant sorption/desorption and surface energy effects. Mechanistic and quantitative
insights underlying the surface properties of clay dispersions in tailings ponds, and the behaviors
of these clays in diverse industrial and natural environments are discussed.

iii
Preface:
Chapter 2 of this thesis has been published as A. Pourmohammadbagher and J.M. Shaw, “Excess
enthalpy and excess volume for pyridine + methyldiethanolamine and pyridine + ethanolamine
mixtures” at the Journal of Chemical & Engineering Data.
Chapter 3 has been published as A. Pourmohammadbagher and J.M. Shaw, “Probing
Contaminant Transport to and from Clay Surfaces in Organic Solvents and Water Using Solution
Calorimetry” at the Journal of Environmental Science & Technology.
Chapter 4 has been submitted to Energy & Fuels as A. Pourmohammadbagher and J.M. Shaw,
“Probing asphaltene contamination of kaolinite and illite clays: A calorimetric study”.
Chapter 5 has been submitted to Energy & Fuels as A. Pourmohammadbagher and J.M. Shaw,
“Probing the role of water chemistry on the behavior of clays using solution calorimetry”.
I was responsible for experimental measurements, modeling and analysis as well as the
manuscript composition. It is noteworthy to mention that none of these journal papers and
chapters would have been possible without J.M. Shaw’s assistance.

iv
Dedication

To my beloved wife, my parents and my brother

v
Acknowledgements
I owe every single achievement of my life to my parents who have always been there for me
regardless of the circumstances. I am also extremely thankful to my wife for her unlimited and
wholehearted support, her patience, and unconditional love.
I would like to express my deep sense of thanks and gratitude to my supervisor, Professor Shaw.
His dedication and keen interest above all his overwhelming attitude to help his students played
the main role in completing my work. His timely advice and meticulous scrutiny have helped me
to a great extent to accomplish this task. I also thank profusely for the time and the effort the
members of the supervisory and examining committees have spent on reviewing this thesis.
I really appreciate the assistance and support from Mildred Becerra. She is one of the greatest lab
managers I’ve ever seen. I am thankful that I had the pleasure of working with and using her
help. I also appreciate the assistance and support from Linda Kaert who has been most kind to
me. I want to extend my appreciation to Gayle Hatchard from the Nanofabrication and
Characterization Facility (nanoFab) of the University of Alberta; my co-op students (Michelle
Liu, Gabriel Wong, Jordon French); my WISEST student (Abigayle Peterson); Jeoffrey Ollinger
and Jun Zhao.
I gratefully acknowledge financial support from the sponsors of the NSERC Industrial Research
Chair in Petroleum Thermodynamics: the Natural Sciences and Engineering Research Council of
Canada (NSERC), Alberta Innovates Energy and Environment Solutions, BP Canada,
ConocoPhillips Canada Resources Corp., Nexen Energy ULC, Shell Canada Ltd., Total E&P
Canada Ltd., Virtual Materials Group.

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Table of Contents

CHAPTER 1: INTRODUCTION................................................................................................ 1
1.1 TAILINGS ............................................................................................................................ 2
1.1.1 Challenges and Environmental Concerns ..............................................................................3
1.1.2 Tailings Water ....................................................................................................................4
1.1.3 Tailings Solids ....................................................................................................................5
1.1.4 Treatment Technologies ......................................................................................................5
1.2 OIL SANDS: A SPECIAL CASE .......................................................................................... 6
1.3 COLLOIDAL AND SURFACE CHEMISTRY BASICS ....................................................... 7
1.3.1 Clay Minerals .....................................................................................................................7
1.3.2. Electrical Double Layer ......................................................................................................8
1.3.3 Mechanisms Leading to Particle Aggregation .......................................................................9
1.3.3.1 Coagulation ........................................................................................................................................................... 9
1.3.3.1.1 Double Layer Compression ....................................................................................................................... 9
1.3.3.1.2 Surface Charge Neutralization ................................................................................................................ 10
1.3.3.2 Flocculation ........................................................................................................................................................ 11
1.4 OBJECTIVES ..................................................................................................................... 12
1.5 THESIS OUTLINE ............................................................................................................. 13
REFERENCES ......................................................................................................................... 15

CHAPTER 2: EXCESS ENTHALPY AND EXCESS VOLUME FOR PYRIDINE +
METHYLDIETHANOLAMINE AND PYRIDINE + ETHANOLAMINE MIXTURES ... 22
2.1 INTRODUCTION ............................................................................................................... 23
2.2 EXPERIMENTAL SECTION ............................................................................................. 24
2.2.1 Materials .......................................................................................................................... 24
2.2.2 Apparatus and Procedure ................................................................................................... 24
2.2.2.1 Calorimetry Measurements .............................................................................................................................. 24
2.2.2.2 Density Measurements...................................................................................................................................... 29
2.3 RESULTS AND DISCUSSION ........................................................................................... 31
2.3.1 Excess Enthalpy ................................................................................................................ 31
2.3.2 Excess Volume ................................................................................................................. 37
2.4 CONCLUSIONS ................................................................................................................. 42
ACKNOWLEDGEMENTS....................................................................................................... 43
REFERENCES ......................................................................................................................... 44

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CHAPTER 3: PROBING CONTAMINANT TRANSPORT TO AND FROM CLAY
SURFACES IN ORGANIC SOLVENTS AND WATER USING SOLUTION
CALORIMETRY........................................................................................................................ 47
3.1 INTRODUCTION ............................................................................................................... 49
3.2 EXPERIMENTAL .............................................................................................................. 51
3.2.1 Materials .......................................................................................................................... 51
3.2.2 Thermogravimetric Analysis (TGA) ................................................................................... 52
3.2.3 Solution Calorimetry ......................................................................................................... 52
3.2.4 Interpretative Framework for Calorimetric and Thermogravimetric Data .............................. 53
3.3 RESULTS AND DISCUSSION ........................................................................................... 55
3.3.1 Thermogravimetric Analysis .............................................................................................. 55
3.3.2 Enthalpy of Solution of Clays in Organic Solvents .............................................................. 57
3.3.2.1 Impact of Clay Contamination ........................................................................................................................ 57
3.3.2.2 Impact of Organic Solvent Contamination with Water ............................................................................... 59
3.3.3 Enthalpy of Solution of Clays in Water............................................................................... 61
3.3.4 Effect of Trace Contamination on the Surface Energy of Clays ............................................ 63
3.3.5 Enthalpy of Solution Evaluation Framework for Clays ........................................................ 64
3.3.5.1 Evaluation of Generalizable Parameters ........................................................................................................ 65
3.3.5.2 Working Equations for the Enthalpy of Solution of Clays ......................................................................... 69
3.4 ENVIRONMENTAL IMPLICATIONS .............................................................................. 70
ACKNOWLEDGEMENTS....................................................................................................... 71
NOMENCLATURE .................................................................................................................. 72
REFERENCES ......................................................................................................................... 74

CHAPTER 4: PROBING THE IMPACT OF ASPHALTENE CONTAMINATION ON
KAOLINITE AND ILLITE CLAY BEHAVIORS IN WATER AND ORGANIC
SOLVENTS: A CALORIMETRIC STUDY ............................................................................ 79
4.1 INTRODUCTION ............................................................................................................... 81
4.2 EXPERIMENTAL .............................................................................................................. 83
4.2.1 Materials .......................................................................................................................... 83
4.2.2 FTIR Spectroscopy ........................................................................................................... 84
4.2.3 Scanning Electron Microscopy........................................................................................... 84
4.2.4 Thermogravimetric Analysis (TGA) ................................................................................... 84
4.2.5 Solution Calorimetry ......................................................................................................... 85
4.2.6 Interpretative Framework for Calorimetric and Thermogravimetric Data .............................. 85
4.3 RESULTS AND DISCUSSION ........................................................................................... 89
4.3.1 Detection of Asphaltenes on Clay Surfaces ......................................................................... 89
4.3.2 Observation of As-received and Asphaltene Coated Clay Particles ....................................... 91
4.3.3 Calorimetric Evaluation of the Asphaltene Coating Procedure.............................................. 94
4.3.4 Thermogravimetric Analysis (TGA) ................................................................................... 95
4.3.5 Enthalpy of Solution of Asphaltene Coated Clays................................................................ 96
4.3.5.1 Impact of clay contamination .......................................................................................................................... 96
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4.3.5.2 Impact of organic solvent contamination with water................................................................................... 97
4.3.5.3 Impact of water contamination with organic liquids ................................................................................... 99
4.3.6 Generalizing the Parameters of the Solution Enthalpy Model ............................................. 100
4.3.7 Working Equations for the Enthalpy of Solution of Asphaltene Coated Clays ..................... 103
4.4 ENVIRONMENTAL IMPLICATIONS ............................................................................ 104
ACKNOWLEDGEMENTS..................................................................................................... 105
NOMENCLATURE ................................................................................................................ 105
REFERENCES ....................................................................................................................... 108

CHAPTER 5: PROBING THE ROLE OF WATER CHEMISTRY ON THE BEHAVIOR
OF CLAYS IN PROCESS AND NATURAL ENVIRONMENTS USING SOLUTION
CALORIMETRY...................................................................................................................... 113
5.1 INTRODUCTION ............................................................................................................. 115
5.2 EXPERIMENTAL ............................................................................................................ 117
5.2.1 Materials ........................................................................................................................ 117
5.2.2 Thermogravimetric Analysis (TGA) ................................................................................. 117
5.2.3 pH measurements............................................................................................................ 117
5.2.4 Solution Calorimetry ....................................................................................................... 118
5.2.5 Interpretative Framework for Calorimetric and Thermogravimetric Data ............................ 118
5.3 RESULTS AND DISCUSSION ......................................................................................... 119
5.3.1 Labile water content of clays............................................................................................ 119
5.3.2 Enthalpy of Solution........................................................................................................ 120
5.3.2.1 Effect of water temperature............................................................................................................................ 120
5.3.2.2 Effect of water pH ........................................................................................................................................... 122
5.3.2.3 Effect of water salinity at pH=7 .................................................................................................................... 125
5.3.2.4 Joint effect of water salinity and pH............................................................................................................. 125
5.4 CONCLUSIONS ............................................................................................................... 128
ACKNOWLEDGEMENTS..................................................................................................... 131
REFERENCES ....................................................................................................................... 132

CHAPTER 6: CONCLUSIONS AND RECOMMENDATIONS ......................................... 137
6.1 CONCLUSIONS ............................................................................................................... 137
6.2 FUTURE WORK .............................................................................................................. 138

BIBLIOGRAPHY ..................................................................................................................... 140
APPENDIX A. SUPPORTING INFORMATION OF CHAPTER 3 ................................... 164
APPENDIX B. SUPPORTING INFORMATION OF CHAPTER 4 ................................... 168
APPENDIX C. SUPPORTING INFORMATION OF CHAPTER 5 ................................... 171

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List of Tables

Table 1.1 The environmental, economic, and social challenges in tailings management7 .........................4

Table 2.1 Experimental values of excess enthalpy HE at mole fraction x, 25 °C and atmospheric pressure
for the liquid mixture heptane (1) + toluene (2)a .......................................................................... 28
Table 2.2 Redlich–Kister coefficients, for equations 2.1-2.5, and the standard deviations for (heptane +
toluene), (pyridine + MDEA), and (pyridine + MEA) mixtures at 25°C......................................... 29
Table 2.3 H∞ values for the liquid mixture heptane (1) + toluene (2) at 25 °C and atmospheric pressure 29
Table 2.4 Experimental values of density ρ and excess volume VE at mole fraction x, 25 °C and
atmospheric pressure for the liquid mixture heptane (1)+ toluene (2)a ........................................... 31
Table 2.5 Experimental values of excess enthalpy HE at mole fraction x, 25 °C and atmospheric pressure
for the liquid mixture pyridine (1)+ MEA (2)a ............................................................................. 34
Table 2.6 Experimental values of excess enthalpy HE at mole fraction x, 25 °C and atmospheric pressure
for the liquid mixture pyridine (1)+ MDEA (2)a........................................................................... 35
Table 2.7 H∞ values for the liquid mixtures pyridine (1) + MDEA (2) and pyridine (1) + MEA (2) at 25
°C and atmospheric pressure ...................................................................................................... 36
Table 2.8 Critical constants for components. ...................................................................................... 37
Table 2.9 Experimental values of density ρ and excess volume VE at mole fraction x, 15, 25 and 80 °C
and atmospheric pressure for the liquid mixture pyridine (1)+ MDEA (2)a. ................................... 39
Table 2.10 Experimental values of density ρ and excess volume VE at mole fraction x, 15, 25 and 80 °C
and atmospheric pressure for the liquid mixture pyridine (1)+ MEA (2)a ....................................... 40

Table 3.1 Kaolinite and illite properties ............................................................................................. 51
Table 3.2 Mass loss (mass fraction) for as-received clays and clays saturated at 60 °C on heating from 20
to 150 °C at 5 °C/min ................................................................................................................ 57
Table 3.3 Measured and at 60 °C and atmospheric pressure ............................. 67
Table 3.4. Clay surface coverage by solvents and trace contaminants for kaolinite and illite clays
following immersion at 60 °C and atmospheric pressure .............................................................. 68
x