Investigation of the Mobility and Extraction Potential of Vanadium and Coupled Metals (Nickel and Lead) in Oily Sludge Matrix under Electrokinetic Conditions Ammar Badawieh A Thesis In the Department of Building, Civil, and Environmental Engineering Presented in Partial Fulfillment of the Requirements For the Degree of Doctor of Philosophy (Civil Engineering) at Concordia University Montreal, Quebec, Canada January 2016 © Ammar Badawieh, 2016 CONCORDIA UNIVERSITY SCHOOL OF GRADUATE STUDIES This is to certify that the thesis prepared By: Ammar Badawieh Entitled: Investigation of the Mobility and Extraction Potential of Vanadium and Coupled Metals (Nickel and Lead) in Oily Sludge Matrix under Electrokinetic Conditions and submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy (Civil Engineering) complies with the regulations of the University and meets the accepted standards with respect to originality and quality. Signed by the final examining committee: Chair Dr. R. Bhat External Examiner Dr. Shiv. O. Prasher External to Program Dr. G. Vatistas Examiner Dr. A. M. Hanna Examiner Dr. Z. Chen Thesis Co-Supervisor Dr. M. Elektorowicz Thesis Co-Supervisor Dr. H. El-Sadi Approved by Dr. F. Haghighat, Graduate Program Director 2016 Dr. A. Asif, Dean, Faculty of Engineering and Computer Science Investigation of the Mobility and Extraction Potential of Vanadium and Coupled Metals (Nickel and Lead) in Oily Sludge Matrix under Electrokinetic Conditions Ammar Badawieh, Ph.D. Concordia University, 2016 Abstract Oily sludge is a viscous complex mix of hydrocarbons, water, metals, and suspended fine solids. This by-product’s persistent toxic composition poses serious environmental concerns, making its containment one of the biggest challenges facing petroleum industries. The main objective of this research was to monitor and trace target heavy metals (with particular focus on vanadium) mobilized in a petroleum sludge matrix under electrokinetic conditions. This exploratory study would facilitate furthering reclamation procedures, and presents the prospect of converting oily sludge into high quality added- value products. The research was carried out in three experimental and analytical phases. Phase 1 consisted of the formulation of adequate Upstream/Downstream petroleum waste, where three target metals, namely vanadium, lead and nickel were considered. In Phase 2, electrokinetic (EK) technology was used to separate valuable oily sludge components, and mobilize metals. A series of EK cells containing sole and mixed metals permitted investigating the synergistic and antagonistic effects of the three target metals (V, Ni, and Pb). Phase 3 focused on behaviour and mobility of metals in the separated matrices. In this phase, a combination of procedures including, Fourier Transform Infrared (FTIR) analysis, and X-Ray diffraction (XRD) were applied simultaneously. Rheological tests confirmed iii electro-demulsification and phase separation in oily sludge matrices. Furthermore, Ethylenediamine-Tetraacetate acid (EDTA), and Diisooctyldithiophosphini acid (Cyanex 301) were compared in the metal supercritical fluid extraction (SFE) process in order to enhance metals’ extraction from the oily sludge matrix. The results obtained in this research provide insight into the mobility of target heavy metals (V, Ni, and Pb) in an oily sludge matrix under EK treatment. Furthermore, vanadium was found to be an accelerator for the separation of oily sludge components under EK conditions. The results demonstrated an excellent vertical and horizontal electro-separation of phases in the upstream cells. In the downstream oily sludge, the presence of non-polar solvents affected the separation process. However, in both upstream and downstream cells, metal mobility created interesting scenarios, such that metals accumulated in the specific areas of the matrix. This mapping of metals would permit on their further removal. This research leads to development of a new oily sludge management system (EK-SEF-Cyanex 301), which would not only help in the reclamation of sludge, but may also create a stream of revenue from the recovery of metals (particularly vanadium). iv Acknowledgments I would like to express my deepest gratitude and appreciation to my thesis advisor Prof. Maria Elektorowicz for her guidance, constant encouragement, and patience during course of dissertation. My sincere thanks are addressed to my Co-supervisor Dr. Haifa Al-Sadi for her comments, suggestions, and valuable advice. I wish to acknowledge the assistance of Dr.Rosalia Chifrina for her comments and suggestions, Dr. Yacine Boumghar and his research team from CEPROCQ (College de Maisonneuve) in Montreal for allowing generously the use of their laboratories, and my colleague Dr. Shadi Hasan for providing the raw material for this research. I would like to acknowledge a financial support for this research from the Discovery Grant awarded to Dr. .Elektorowicz, by the Natural Science and Engineering Research Council (NSERC) of Canada. Special thanks to my dear friends Zaid Ghouleh, and Charles Desjardin for them being of great help whenever I needed them. v Dedication I would like to express my heartfelt thanks for the unconditional love and limitless support from my wonderful parents, my amazing wife, Hanin, beautiful kids, Hashem and Zena, great brothers, Emad and Husam, and my lovely sister Sara. vi Table of Contents Glossary .......................................................................................................................... xvii Chapter 1 Introduction ........................................................................................................ 1 Chapter 2 Literature Review ............................................................................................... 5 2.1 Petroleum oily sludge ........................................................................................... 5 2.1.1 Components and characteristics ......................................................................... 6 2.1.2 Quantities ............................................................................................................ 7 2.1.3 Hazardous effect ................................................................................................. 7 2.1.4 Oily sludge as a controlled Haz-Mat .................................................................. 8 2.1.5 Canadian federal and provincial petroleum wastes disposal regulations ........... 9 2.2 Heavy metals ........................................................................................................... 12 2.2.1 Vanadium .......................................................................................................... 13 2.2.1.1 Physical and chemical properties ............................................................... 13 2.2.1.2 Sources and behavior in soil ...................................................................... 14 2.2.1.3 Vanadium applications and effects ............................................................ 14 2.2.2 Nickel ................................................................................................................ 15 2.2.2.1 Physical and chemical properties ............................................................... 15 2.2.2.2 Sources and behavior in soil ...................................................................... 16 2.2.2.3 Nickel applications and effects .................................................................. 16 2.2.3 Lead .................................................................................................................. 18 2.2.3.1 Physical and chemical properties ............................................................... 18 2.2.3.2 Sources and behavior in soil ...................................................................... 18 2.2.3.3 Lead applications and effects ..................................................................... 19 2.3 Heavy metals in petroleum sludge .......................................................................... 21 2.4 Emulsions ................................................................................................................ 23 2.5 Oily sludge management ......................................................................................... 25 2.5.1 Recycling .......................................................................................................... 25 2.5.2 Filtration ........................................................................................................... 26 2.5.3 Treatment with fly ash ...................................................................................... 26 vii 2.5.4 Incineration ....................................................................................................... 27 2.5.5 Coking .............................................................................................................. 28 2.5.6 Biological treatment.......................................................................................... 29 2.5.6.1 Biodegradation of Oily Sludge .................................................................. 29 2.5.6.2 Composting ................................................................................................ 30 2.5.7 Landfarming ..................................................................................................... 31 2.5.8 Centrifugation ..................................................................................................