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7.2.1.4 Copper Ferrocyanide and Copper Ferricyanide

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7.2.1.4 Copper Ferrocyanide and Copper Ferricyanide PLEASE TYPE THE UNIVERSITY OF NEW SOUTH WALES Thesis/Dissertation Sheet Surname or Family name: Fernando First name: Kapila Other name/s: Abbreviation for degree as given in the University calendar: Ph.D. School: School of Chemical Sciences and Engineering Faculty: Engineering Title: The Treatment of Cyanidation Tailings Using Ion Exchange Resin Abstract 350 words maximum: (PLEASE TYPE) This thesis explores the behaviour of metal cyanide complexes under oxidative acid conditions in ion exchange systems, with the objective of developing an ion exchange based process for the treatment of gold cyanidation tailings. The novel cyanide detoxification process developed from this study employs strong base ion exchange resins to extract cyanide from tailings. Variations in the stability of cyanide complexes are exploited to concentrate, recover, or destroy cyanide species loaded on the resin, through the use of an oxidative acid eluent containing H2O2 and H2SO4. This eluent removes all base metal cyanide complexes from strong base resins, while regenerating the resin. The spent eluent, containing the base metals recovered from the tailings, can be used as a source of such base metals. Copper can be recovered separately from other base metals if necessary. Low levels of precious metals present in the tailings are accumulated on the resin as the ion exchange bed is cycled between loading and elution stages. They can be recovered economically, so as to offset the cost of the tailings detoxification. Cyanide is initially concentrated as an alkaline solution, which can be detoxified within the process or recovered for recycling. This process was successfully tested at pilot scale by treating approximately 14,000 m^ of cyanide contaminated tailings solution, over 14 loading/elution cycles on a standard strong base ion exchange resin bed. This treatment reduced the total cyanide concentration of the contaminated solution from approximately 50 mg/L to an average of 1.5 mg/L. The reagent cost was approximately AUD 0.50 per m^ of treated liquor. When the resin was repeatedly loaded with mixed metal cyanide species and eluted with the oxidative acid eluent, a gradual deterioration of the ion exchange resin performance was noted. The reduction of net operating capacity of the columns due to resin deterioration was in the order of 1-3% per loading/elution cycle. The oxidation of resin catalysed by copper, the precipitation of metal hexacyanoferrates on the resin and the oxidation of Au(CN)2' to Au(CN)4" were identified as possible factors giving rise to the reduction of resin loading capacity. Declaration relating to disposition of project thesis/dissertation I hereby grant to the University of New South Wales or its agents the right to archive and to make available my thesis or dissertation in whole or in part in the University libraries in all fomns of media, now or here after known, subject to the provisions of the Copyright Act 1968.1 retain all property rights, such as patent rights. I also retain the right to use in future works (such as articles or books) all or part of this thesis or dissertation. I also authorise Univ^ity Microfiln}$^^^se the 350 abstract of my thesis in Dissertation Abstracts International (this is applicable to doctoral Signature Witness Date The Uni^rsity recognises that there may be exceptional circumstances requiring restrictions on copying or conditions on use. Requests for restriction for a period of up to 2 years must be made in writing. Requests for a longer period of restriction may be considered in exceptional circumstances and require the approval of the Dean of Graduate Research. FOR OFFICE USE ONLY Date of completion of requirements for Award: THIS SHEET IS TO BE GLUED TO THE INSIDE FRONT COVER OF THE THESIS (19180'^ THE UNIVERSITY OF NEW SOUTH WALES SCHOOL OF CHEMICAL SCIENCES AND ENGINEERING THE TREATMENT OF CYANIDATION TAILINGS USING ION EXCHANGE RESIN by Kapila Fernando, B.E Chemical Engineering (Hons.) A Thesis Submitted to the School of Chemical Sciences and Engineering in Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy The University of New South Wales NOVEMBER 2007 ORIGINALITY, COPYRIGHT AND AUTHENTICITY STATEMENT I hereby declare that this submission is my own work and to the best of my knowledge it contains no materials previously published or written by another person, or substantial proportions of material which have been accepted for the award of any other degree or diploma at UNSW or any other educational institution, except where due acknowledgement is made in the thesis. Any contribution made to the research by others, with whom I have worked at UNSW or elsewhere, is explicitly acknowledged in the thesis. I also declare that the intellectual content of this thesis is the product of my own work, except to the extent that assistance from others in the project's design and conception or in style, presentation and linguistic expression is acknowledged. I hereby grant the University of New South Wales or its agents the right to archive and to make available my thesis or dissertation in whole or part in the University libraries in all forms of media, now or here after known, subject to the provisions of the Copyright Act 1968. I retain all proprietary rights, such as patent rights. I also retain the right to use in future works (such as articles or books) all or part of this thesis or dissertation. I also authorise University Microfilms to use the 350 word abstract of my thesis in Dissertation Abstract International (this is applicable to doctoral theses only). I have either used no substantial portions of copyright material in my thesis or I have obtained permission to use copyright material; where permission has not been granted I have applied/will apply for a partial restriction of the digital copy of my thesis or dissertation. I certify that the Library deposit digital copy is a direct equivalent of the final officially approved version of my thesis. No emendation of content has occurred and if there are any minor variations in formatting, they are the result of the conversion to digital format. DEDICATION To my Mum and Dad, Gertrude and Raymond Fernando, for this achievement was only made possible because of their unwavering support and sacrifice. ACKNOWLEDGEMENTS Over IV2 years, there were many who contributed to this work. Some were involved directly, guiding and directing my research. Others supported in subtle ways, through encouragement and friendship, but were just as necessary for me to reach this milestone. To my academic supervisors It was a privilege to embark on this research project under Prof Tam Iran's direction and supervision. Tam, you taught me how to undertake independent research, balance creativity, and lateral thinking with the imperative to generate coherent arguments backed by tangible resuhs. You were a true mentor. I also want to thank Dr. Frank Lucien for his guidance and support, especially in the write-up of this thesis. Your insightful comments and decisive instructions were instrumental for me to present my thoughts in a coherent and lucid manner. To those at ANSTO, Imperial and May Day mines I am truly grateful to ANSTO and its management for supporting my research work. I especially acknowledge the support and encouragement from my supervisor, Lubi. Thank you for giving me the time to complete this project. I also would like to thank Clement, Bruce, and Kevin from Imperial Mining for supporting the pilot plant testing program. I am very grateful for Graham for his support while we were working at May Day mines. To my co-workers and researches I gratefully acknowledge the support of my co-workers and researchers who worked with me to explore various aspects of cyanide chemistry and ion exchange systems. Steve, Sarah, Ken, Grzegorz, Rueben, and Myong Jun, I enjoyed working with you at various stages of this research project. Thank you for your contribution to this work. To my colleagues at ANSTO Martin, Roland, Gordon, Melody, Enrique, Liz, Patricia, Robert, and Henri, I could not have completed this without your support. You all contributed to this project in various ways. You helped me to refme my thoughts, conduct experimental work, and carry out analyses. Most importantly, those of you who work directly with me were generally accommodating me when I was stressed out trying to juggle full time work and a Ph.D. program. Special thanks to Bob and Lorraine for making me see that this effort is worthwhile. To all my friends who encouraged and supported me over a IV2 year journey From my church and bible study groups: Tom, Caroline, Brian, Julie, Mike, Peter, Louise, Brett, Kristie, Dana, Sally, Tsola, Damian, Laura, and Craig. Thanks for your prayers and encouragement. I also want to thank Enoka, Niru, Mini, Mike, Aruna, Brendan, Natasha, Tom, San-San, Wendy, Michael, Matt, Tim, and James for their support. My high school buddies, Priantha, Hiran, and Manisha, thanks for putting up with an absentee friend. Finally, I am grateful to Hilary and Leah for proofreading and editing this thesis. I was fortunate to have the support and friendship of many during this journey. They helped me to achieve this goal while keeping me grounded in reality. My sincere gratitude is extended to all of you. ABSTRACT This thesis explores the behaviour of metal cyanide complexes under oxidative acid conditions in ion exchange systems, with the objective of developing an ion exchange based process for the treatment of gold cyanidation tailings. The novel cyanide detoxification process developed from this study employs strong base ion exchange resins to extract cyanide from tailings. Variations in the stability of cyanide complexes are exploited to concentrate, recover, or destroy cyanide species loaded on the resin, through the use of an oxidative acid eluent containing H2O2 and H2SO4.
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