Synergistic Co-processing of Red Mud mining waste and alkaline Black Liquor from the Pulp and

143 Pages·2015·4.22 MB·English

by  Chris Gissane

Synergistic Co-processing of Red Mud mining waste and alkaline Black
Liquor from the Pulp and Paper Industry

by
Christopher Francis George Gissane

A Thesis
presented to
The University of Guelph

In partial fulfillment of requirements
for the degree of
Master of Science
in
Chemistry

Guelph, Ontario, Canada
© Christopher Gissane, April, 2015
ABSTRACT
SYNERGISTIC CO-PROCESSING OF RED MUD MINING WASTE AND ALKALINE
BLACK LIQUOR FROM THE PULP AND PAPER INDUSTRY

Christopher Francis George Gissane Advisor:
University of Guelph, 2015 Professor Marcel Schlaf

This thesis focused on the explorative study of synergistically co-processing Red Mud and
Black Liquor under varying temperatures, pressures, reaction times, and material ratios. The goal
being to generate a treated Red Mud with a substantially lower pH and increased carbon content
that would be more environmentally tolerable and allow for the consideration of using the treated
material as a viable soil additive and/or allow for the remediation and revegetation of Red Mud
storage sites. Using a factorial design of experiments approach the study identified the most
influential reaction parameters affecting the monitored responses. By applying a central
composite design to those results, the optimum reaction conditions to achieve the desired results
for pH, carbon content and several other characteristics were realized. Additionally, the design
and construction of a unique explosion resistant high pressure hydrogenation laboratory was also
undertaken as part of this thesis.
To my Mom and Dad
iii
ACKNOWLEDGEMENTS
First, I would like to thank my advisor, Dr. Marcel Schlaf. I am very grateful of the
opportunities that you have given me as both a graduate and an undergraduate student. The last
two years have definitely have been a test of patience for the both of us getting the new
laboratory completed but I am grateful you trusted me to take the lead on the project. That
opportunity allowed me to gain experience and learn from mistakes that few in my position ever
get the chance to do. You have taught me to look at the world with a more analytical mindset and
it has been a privilege to work for you and alongside you.
Special thanks to everyone in the electronics and machine shops, especially Ian, Steve,
and Case, for all of their help with the various aspects of the projects.
I am appreciative to the many members of the Schlaf group I have had the pleasure to
know, as well as to my friends throughout the department, for all of their support. I was fortunate
enough to have worked alongside a number of highly talented chemists, all of whom assisted me
to improve my skills every day. I can only hope that my future endeavors bring workplace
dynamics as memorable and rewarding as those I have enjoyed here.
Last, though far from least, I would like to thank my friends and family. I am very
fortunate to have such a select group of people in my life that showed such interest in my work
and helped me in so many ways over the years and to listen to my ranting over all the issues that
kept cropping up.

iv
Table of Contents
1 INTRODUCTION .............................................................................................................................. 1
1.1 Motivation ....................................................................................................................................................... 1
1.2 Aluminium Industry ....................................................................................................................................... 2
1.2.1 The Bayer Process ........................................................................................................................................ 2
1.2.2 Red Mud Waste ............................................................................................................................................ 4
1.2.2.1 Disposal Techniques and Environmental Issues .................................................................................. 4
1.2.2.2 Multi-Functional Catalyst Potential ..................................................................................................... 6
1.3 Pulp and Paper Industry ................................................................................................................................ 7
1.3.1 Lingocellulosic Biomass .............................................................................................................................. 7
1.3.1.1 Cellulose .............................................................................................................................................. 8
1.3.1.2 Hemicellulose ...................................................................................................................................... 8
1.3.1.3 Lignin .................................................................................................................................................. 9
1.3.2 Major Pulping Processes15,16 ...................................................................................................................... 13
1.3.2.1 Kraft Pulping ..................................................................................................................................... 13
1.3.2.2 Sulfite Pulping ................................................................................................................................... 14
1.3.2.3 Soda Pulping ..................................................................................................................................... 15
1.3.3 Black Liquor Waste.................................................................................................................................... 17
1.3.3.1 Composition and Properties .............................................................................................................. 17
1.3.3.2 Disposal Techniques .......................................................................................................................... 19
1.4 Overview of Projects .................................................................................................................................... 21
1.4.1 Project I: Design and Construction of the High Pressure Hydrogenation Lab ........................................... 21
1.4.2 Project II: Neutralization of Red Mud using Strong Black Liquor as a reagent ......................................... 22
2 RESULTS AND DISCUSSION – PROJECT I .............................................................................. 23
2.1 Infrastructure Design Features ................................................................................................................... 23
2.2 High Pressure Reactors ................................................................................................................................ 27
2.2.1 Reactor Installation and Validation ............................................................................................................ 29
2.2.2 Comparison of Temperature and Pressure Response to Theoretical Values using NIST software ............ 30
3 RESULTS AND DISCUSSION – PROJECT II ............................................................................. 34
3.1 A Counterintuitive Approach ...................................................................................................................... 35
3.2 24 Factorial Design ........................................................................................................................................ 37
3.2.1 Initial Observations .................................................................................................................................... 41
3.2.1.1 pH of Black Liquor in storage ........................................................................................................... 41
3.2.1.2 Precipitate formation from the aqueous liquid phase ........................................................................ 42
3.2.1.3 pH values ........................................................................................................................................... 45
3.2.1.4 Coloured aqueous phase .................................................................................................................... 46
v
3.2.1.5 Recovered Solid Phase ...................................................................................................................... 48
3.2.2 Significant Factors and Interactions ........................................................................................................... 50
3.2.2.1 pH of Solid Phase .............................................................................................................................. 52
3.2.2.2 pH of Aqueous Phase ........................................................................................................................ 53
3.2.2.3 Mass of Aqueous Phase ..................................................................................................................... 54
3.2.2.4 Carbon Content of Solid Phase .......................................................................................................... 54
3.2.2.5 Water Content of Aqueous Phase ...................................................................................................... 55
3.2.2.6 Magnetic Susceptibility ..................................................................................................................... 55
3.2.2.7 Sodium Concentration in the Solid Phase ......................................................................................... 56
3.2.2.8 Summary ........................................................................................................................................... 57
3.3 Central Composite Design ........................................................................................................................... 58
3.3.1.1 pH of Solid Phase .............................................................................................................................. 60
3.3.1.2 pH of Aqueous Phase ........................................................................................................................ 63
3.3.1.3 Mass of Aqueous Phase ..................................................................................................................... 64
3.3.1.4 Carbon Content of Solid Phase .......................................................................................................... 64
3.3.1.5 Water Content of Aqueous Phase ...................................................................................................... 65
3.3.1.6 Magnetic Susceptibility ..................................................................................................................... 65
3.3.1.7 Sodium Concentration in Red Mud ................................................................................................... 65
3.3.1.8 Statistical relevance of the data ......................................................................................................... 66
3.3.2 Optimum Reaction Conditions ................................................................................................................... 67
3.3.3 Summary .................................................................................................................................................... 69
3.4 Experimental ................................................................................................................................................. 71
3.4.1 Factorial Design Calculations .................................................................................................................... 71
3.4.2 General Procedure for Co-processing Reactions ........................................................................................ 72
3.4.3 Analytical Instrumentation ......................................................................................................................... 73
4 SUMMARY OF RESULTS ............................................................................................................. 75
REFERENCES .......................................................................................................................................... 77
APPENDIX............................................................................................................................................... 79
Appendix A: Select Micro-GC Traces ..................................................................................................................... 80
A1: Micro-GC trace of 1000ppm C1 – C6 alkane standards ................................................................................... 81
A2: Micro-GC trace of 1000 ppm C2 – C6 alkene standards .................................................................................. 81
A3: Micro-GC trace of lab atmosphere reference ................................................................................................... 82
A4: Micro-GC trace of DoE reaction, representative over all reactions conducted ................................................ 82
A5: Micro-GC trace of acid digestion white precipitate recovered from aqueous phase post- reaction using 2M
HCl (representative of all applicable reactions) ...................................................................................................... 83
Appendix B: 3D Autogenic Pressure Response as a Function of Time and Temperature for Multi-Reactor
System and REFPROP Water Vapour Pressure Plots ........................................................................................... 84
B1: Bach autogenic pressure response as a function of time and temperature with 50, 100 and 150mL of water .. 85
B2: Escher autogenic pressure response as a function of time and temperature with 50, 100 and 150mL of water
................................................................................................................................................................................. 86
vi
B3: Gödel autogenic pressure response as a function of time and temperature with 50, 100 and 150mL of water 87
B4: Theoretical Pressure-Temperature Response for Water vapour contained in an ideal closed system within the
range of the High Pressure Reactor specifications. ................................................................................................. 88
B5: Theoretical pressure-temperature response for water vapour contained in an ideal closed system near the
limits of the high pressure reactor specifications. ................................................................................................... 89
Appendix C: Spectral data for aqueous phases ...................................................................................................... 90
C1: 1H NMR of red aqueous phase obtained on a 400 MHz spectrometer using D O as the solvent. .................... 91
2
C2: 1H NMR of red aqueous phase obtained on a 400 MHz spectrometer using D O as the solvent and water
2
suppression NMR program. .................................................................................................................................... 92
C3: 13C NMR of red aqueous phase obtained on a 400 MHz spectrometer using D O as the solvent .................... 93
2
C4: 1H NMR of purple aqueous phase obtained on a 400 MHz spectrometer using D O as the solvent ................ 94
2
C5: 1H NMR of purple aqueous phase obtained on a 400 MHz spectrometer using D O as the solvent and water
2
suppression. ............................................................................................................................................................. 95
C6: 13C NMR of purple aqueous phase obtained on a 400 MHz spectrometer using D O as the solvent ............... 96
2
Appendix D: Pareto charts, residual plots, main effects plots, interaction plots, and cube plots from DoE
analysis ....................................................................................................................................................................... 97
24 Factorial Design .................................................................................................................................................. 98
D1: Pareto chart, residual plot, main effects plot, interaction plot, and cube plot for pH of solid phase before
(Top) and after (Middle) reduction of terms for calculation ............................................................................... 98
D2: Pareto chart, residual plot, main effects plot, interaction plot, and cube plot for pH of aqueous phase before
(Top) and after (Middle) reduction of terms for calculation ............................................................................... 99
D3: Pareto chart, residual plot, main effects plot, interaction plot, and cube plot for mass of aqueous phase
before (Top) and after (Middle) reduction of terms for calculation .................................................................. 100
D4: Pareto chart, residual plot, main effects plot, interaction plot, and cube plot for carbon content of solid
phase before (Top) and after (Middle) reduction of terms for calculation ........................................................ 101
D5: Pareto chart, residual plot, main effects plot, interaction plot, and cube plot for water content of aqueous
phase before (Top) and after (Middle) reduction of terms for calculation ........................................................ 102
D6: Pareto chart, residual plot, main effects plot, interaction plot, and cube plot for magnetic susceptibility
before (Top) and after (Middle) reduction of terms for calculation .................................................................. 103
D7: Pareto chart, residual plot, main effects plot, interaction plot, and cube plot for sodium concentration in the
solid phase before (Top) and after (Middle) reduction of terms for calculation .............................................. 104
Central Composite Design .................................................................................................................................... 105
D8: Residual plot, Contour plots, and response surface plots for pH of solid phase ........................................ 105
D9: Residual plot, Contour plots, and response surface plots for the pH of aqueous phase ............................. 106
D10: Residual plot, Contour plots, and response surface plots for the mass of aqueous phase ........................ 107
D11: Residual plot, Contour plots, and response surface plots for the carbon content of solid phase .............. 108
D12: Residual plot, Contour plots, and response surface plots for the water content of aqueous phase........... 109
D13: Residual plot, Contour plots, and response surface plots for the magnetic susceptibility ........................ 110
D14: Residual plot, Contour plots, and response surface plots for the sodium concentration in the solid phase
.......................................................................................................................................................................... 111
D15: Optimized reaction parameters predicted by Minitab®’s response optimizer ......................................... 112
D16: Overlaid contour plots of response factors highlighting the optimum results while holding reaction time
fixed at 0.5 hrs (Top), 1.75 hrs (Middle), and 3 hrs (Bottom) .......................................................................... 113
Appendix E: SOP for High Pressure Reactors ...................................................................................................... 114
vii
Appendix F: Gas Sensor Alarm Response Procedures and Hydrogenation Lab Information distributed to
EHS, Physical Resources and Campus Police/Fire Dispatch Centre .................................................................. 126

viii
List of Charts
Chart 2-1: High temperature range vs. pressure plots for water validation experiments and NIST
prediction calculations .................................................................................................................. 33

ix
List of Figures
Figure 1-1: Illustration of alumina refining using the Bayer Process 3 ........................................... 2
Figure 1-2: Representation of cellulose polymer and glucose repeating units ............................... 8
Figure 1-3: Representation of hemicellulose polymer with repeating xylose units and other
possible sugar monomers. ............................................................................................................... 9
Figure 1-4: Representations of Lignin monomers .......................................................................... 9
Figure 1-5: Example of branched lignin structure within lignocellulosic biomass14.................... 10
Figure 1-6: Chemical structures of common turpentine components ........................................... 18
Figure 2-1: Watchtower control screen for multi-reactor system ................................................. 29
Figure 3-1: Pictures of the coloured aqueous phases recovered from various reactions. Examples
of the darken colours (Top), dark red (Top Left), rusty red (Top Middle), dark purple (Top
Right); observed darkening of coloured solution during reaction workup (Bottom), initial colour
(Bottom Left), after five minutes (Bottom Right) ........................................................................ 48

x