FEASIBILITY OF UTILIZING OIL-SANDS FLUID COKE AS A SECONDARY SOURCE OF VANADIUM by Jing Feng A thesis submitted in conformity with the requirements for the degree of Master of Applied Science Department of Chemical Engineering and Applied Chemistry University of Toronto © Copyright by Jing Feng 2017 Feasibility of Utilizing Oil-Sands Fluid Coke as A Secondary Source of Vanadium Jing Feng Master of Applied Science Department of Chemical Engineering and Applied Chemistry University of Toronto 2017 ABSTRACT Oil-sands fluid coke (OSFC) is a major byproduct of upgrading Athabasca bitumen, which has a particularly high vanadium concentration (0.15 wt% and predominantly vanadyl porphyrins). This study explores the feasibility of extracting vanadium from OSFC. Chemical activation with KOH or NaOH converts organic vanadium in OSFC into water-soluble inorganic species. After chemical activation, water washing alone is able to dissolve over 98% of total vanadium in OSFC given enough time. Sequential washing enhances vanadium dissolution, shortens the washing process, and reduces the water usage by removing other elements (Ca, Ni, Fe, Al and Si) in the first stage. Overall, it is technically feasible to recover over 90% of vanadium in OSFC as calcium vanadate via alkali metal hydroxide chemical activation, sequential water washing and calcium precipitation of vanadium. This process would allow the recycle, reuse of alkali metal hydroxide, and produce highly porous activated carbon. ii ACKNOWLEDGEMENTS Firstly, I would like to express my greatest appreciation to my supervisor, Professor Charles Q. Jia, for his support, encouragement, and guidance in my research over the past years. I am very grateful for everything he has done for me and for my development. I would also like to thank Professor Donald W. Kirk for his kind advice throughout my entire research. They have always made time for me and they have always been there for me when I struggled. Next, I must thank Jocelyn Zuliani for the training in lab work. Along with all the members in Green Technology, Celine, Leyan, Randeep, Johnathon, and Daniel. I am sure without any of you, the time I have spent in the department would have been less enjoyable. I am very glad that I have met and worked with all these wonderful people. I am also very grateful to Dan Mathers and Jared Mudrik from ANALEST at Department of Chemistry, University of Toronto. They are always patient with my questions and concerns on analytical instruments, and thanks to their excellent training, I manage to learn a lot about instrument troubleshooting. Last but not least, I would like to acknowledge my dearest family. I want to thank them for unconditional support regardless of my path in academia. Their support and their understanding literally have helped me to go through any difficult times and to conquer any challenges. iii TABLE OF CONTENT ABSTRACT .................................................................................................................................... ii ACKNOWLEDGEMENTS ........................................................................................................... iii TABLE OF CONTENT ................................................................................................................. iv LIST OF TABLES ........................................................................................................................ vii LIST OF FIGURES ....................................................................................................................... ix CHAPTER 1. OVERVIEW ............................................................................................................ 1 1.1. INTRODUCTION .......................................................................................................... 1 1.2. RESEARCH OBJECTIVES ........................................................................................... 2 CHAPTER 2. LITERATURE REVIEW ........................................................................................ 3 2.1. VANADIUM ....................................................................................................................... 3 2.1.1. General Background ..................................................................................................... 3 2.1.2. Commercial Recovery Processes .................................................................................. 4 2.2. CHARACTERIZATION OF OIL-SANDS FLUID COKE ................................................ 4 2.3. CHEMICAL ACTIVATION ON FLUID COKE.............................................................. 13 CHAPTER 3. MATERIALS AND METHODS .......................................................................... 17 3.1. DETERMINATION OF TOTAL VANADIUM CONTENT IN OIL-SANDS FLUID COKE ........................................................................................................................................ 17 3.1.1. Direct Acid Leaching Using Various Acids ............................................................... 19 3.1.2. Direct Caustic Leaching Using 1M KOH Solution .................................................... 19 3.1.3. Dissolution of Ashed OSFC Using Aqua Regia ......................................................... 19 3.1.4. X-Ray Fluorescence (XRF) on Ashed OSFC ............................................................. 20 3.2. VANADIUM RECOVERY USING CHEMICAL ACTIVATION .................................. 20 3.2.1. Chemical Activation of OSFC .................................................................................... 22 3.2.2. Washing Process of Activation Product ..................................................................... 23 3.3. VANADIUM SEPARATION AND STREAM PURIFICATION .................................... 25 3.3.1. Solvent Extraction ....................................................................................................... 27 iv 3.3.2. Sequential Washing Using Water ............................................................................... 29 CHAPTER 4. RESULTS AND DISCUSSIONS .......................................................................... 30 4.1. DETERMINATION OF TOTAL VANADIUM CONTENT IN OIL-SANDS FLUID COKE 30 4.1.1. Direct Leaching of Raw Fluid Coke ........................................................................... 30 4.1.2. Acid Dissolution of Ashed OSFC Using Aqua Regia .......................................... 31 4.1.3. XRF Analysis on Ashed OSFC ............................................................................. 32 4.2. VANADIUM RECOVERY USING CHEMICAL ACTIVATION ............................. 34 4.2.1. Activation Yield and Characteristics of Activated Coke ............................................ 34 4.2.2. Fate of Vanadium During Chemical Activation and Subsequent Washing .......... 36 4.3. VANADIUM SEPARATION AND STREAM PURIFICATION ............................... 38 4.3.1. Solvent Extraction with Aliquat® 336........................................................................ 38 4.3.2. Sequential Washing Using Water ......................................................................... 40 CHAPTER 5. PROPOSED PROCESS OF VANADIUM RECOVERY VIA CHEMICAL ACTIVATION ON OSFC ............................................................................................................ 44 CHAPTER 6. CONCLUSIONS AND FUTURE RESEARCH ................................................... 46 CHAPTER 7. REFERENCES ...................................................................................................... 48 CHAPTER 8. APPENDICES ....................................................................................................... 53 APPENDIX 1 CALIBRATION CURVES ............................................................................... 53 Single-element ICP Standard Vanadium Calibration ........................................................... 53 Multi-element ICP Standard Vanadium Calibration ............................................................. 54 APPENDIX 2 XRF RAW DATA ............................................................................................. 63 APPENDIX 3 SAMPLE PELLETS OF ASHED OSFC FOR XPF ANALYSIS .................... 66 APPENDIX 4 CORRECTED XRF RESULTS ........................................................................ 67 APPENDIX 6 DETERMINATION OF KOH AND NAOH PELLET PURITY ..................... 68 APPENDIX 7 CALCULATION OF SOLVENT PREPARATION ........................................ 69 APPENDIX 8 DETERMINATION OF PARTITION COEFFICIENT AND MIXING TIME IN SOLVENT EXTRACTION ................................................................................................. 70 Methodology ......................................................................................................................... 70 Results and Discussions ........................................................................................................ 72 APPENDIX 9 OTHER ELEMENT CONCENTRATION IN SEQUENTIAL WASHING .... 73 v APPENDIX 10 OLI SIMULATION ON VANADIUM PRECIPITATION ........................... 74 vi LIST OF TABLES TABLE 1 VANADIUM WORLD ANNUAL PRODUCTION BY COUNTRY (HTTP://MINERALS.USGS.GOV) ....................................................................................... 3 TABLE 2 PROPERTY PROXIMATE ANALYSIS OF FLUID COKE FROM SYNCRUDE, WT% (FUIMSKY,1998) ........................................................................................................ 9 TABLE 3