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Carbonylation of Nickel and Iron from Reduced Oxides and Laterite Ore

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Carbonylation of Nickel and Iron from Reduced Oxides and Laterite Ore The University of New South Wales Faculty of Science School of Materials Science and Engineering Carbonylation of Nickel and Iron from Reduced Oxides and Laterite Ore Submitted in partial fulfilment of the requirements for the degree of Doctor of Philosophy by Yongli Cui December 2015 To my parents and wife COPYRIGHT STATEMENT '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.' Date AUTHENTICITY STATEMENT '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.' Signed ........... Date ................. ORIGINALITY 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.' Signed Date II THE UNIVERSITY OF NEW SOUTH WALES Thesis/Dissertation Sheet Surname or Family name: CUI First name: YONGLI other name/s: Abbreviation for degree as given In the University calendar: PhD School: School of Materials Science and Engineering Faculty: Science Title: Carbonylation of Nickel and Iron from Reduced Oxides and Laterite Ore Abstract 350 words maximum: The PhD project was undertaken within the ARC Discovery Grant (Project No. DP1094880) which examined a novel approach to processing of laterite ores based on the selective reduction of the ore and extraction of nickel by carbonylation of the selectively reduced ore. The project undertook a systematic study of carbonylation of pure nickel and iron, and carbonylation of selectively reduced laterite ore to develop a further understanding of carbonylation reactions and feasibility of extraction of nickel from laterite ore by carbonylation. The project studied the effects of operational parameters on carbonylation of nickel and iron obtained by reduction of pure oxides and in the selectively reduced Australian laterite ores, including temperature, carbon monoxide pressure, gas flow rate, particle size, and the effect of sulphur-containing catalysts. The non-catalytic carbonylation of nickel at I 00 °C and CO pressnre 27 atm was close to completion in about 5.5 hours. Carbonylation of pure iron was slow; the extent of iron carbonylation at 100 °C and CO gauge pressure up to 55 atm was less than 5.0%. The extent of cobalt carbonylation nnder these conditions was less than 0.5%. Sulphur containing catalysts accelerated the carbonylation reaction. The time for a complete carbonylation of nickel was shortened from 5.5 hours in the non- catalytic reaction to 2 hours in the catalytic carbonylation at 100 °C and CO pressure 14 atm. The extent ofcarbonylation of nickel from the selectively reduced laterite ore at 100 °C and CO pressure 41 atm was below 50% (ore particle size 53-200 µm). The use of catalysts in the carbonylation of selectively reduced ore was inefficient. The rate of reaction increased significantly with decreasing particle size; the carbonylation of nickel in the ore with the particle size 38-53 and 75-90 µm, was close to completion after 4 hours reaction. Results of a systematic study of the carbonylation of nickel and selectively reduced latcrite ores are significant for further understanding of carbonylation reactions. Promising results were obtained for further development of technology of extraction of nickel from late rite ores by the carbonylation process. 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 forms of media, now or here after known, subject to the provisions of the Copyright Act 1968. I 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 University Microfilms to use the 350 word abstract of my thesis in Dissertation Abstracts International (this is applicable to doctoral theses only) . Signature Witness Date The University 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 reauire 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 Acknowledgements This project was made possible by funding from the Australian Research Council ( ARC )and the Commonwealth Scientific and Industrial Research Organisation ( CSIRO ). The project code is DP1094880. Assistance during this project has come in many forms, both in technical and moral support. I am indebted to my supervisor Professor Oleg Ostrovski and co- supervisor Dr. Guangqing Zhang for believing in me and their advice and support during the project. I would like to thank Dr. Jianqiang Zhang and Sharif Jahanshahi for their advice during project reviews. The technical staff was invaluable in their help and support for experimental work, Mr. John Sharp for equipment maintenance; Mr. Anthony Zhang and Dr. Rahmat Kartono for lab safety support; Dr. Yu Wang for XRD analysis; Dr. Deming Zhu and Dr. Leah Koloadin for SEM/EDS analysis; Ms. Rabeya Akter and Ms. Dorothy Yu for ICP-OES analysis, Dr. George Yang for metallography and lab assistant; Mr. Danny Kim and Ms. Jane Gao for I.T. support. The administrative staff was generous with their time and kind works, helping with more than just paperwork, Mrs. Lana Strizhevsky, Ms. Qing Xia and Mrs. Judy Lim for their help with general administrative issues. I have greatly enjoyed the opportunity to work with all the talented and dedicated people in our group as: Dr. Yan Li, Dr. Xiaohan Wan, Dr. Xing Xing, Mr. Le Yu, Mr. Jun Yang, and Mrs. Jing Zhang. Your encouragement and advice inspired this work. Finally, I would like to thank all my family members especially my wife Mrs. Jieqing Gan for their mental support and constant encouragement throughout the whole course of my PhD study. IV Abstract Australia has abundant deposits of laterite ores which role in production of nickel is increasing with rising demand for nickel and depletion of sulphide reserves. Laterite ores cannot be efficiently upgraded prior to pyrometallurgical or hydrometallurgical processing what leads to significant challenges in extraction of nickel. The PhD project was undertaken within the ARC (Australian Research Council) Discovery Grant (Project No. DP1094880) which examined a novel approach to processing of laterite ores based on the selective reduction of the ore and extraction of nickel by carbonylation of the selectively reduced ore. Selective reduction of the laterite ore was studied by J. Yang in his PhD project (Yang, 2014). The ultimate aim of this project was to establish the feasibility of extraction of nickel by carbonylation of selectively reduced laterite ore. The project undertook a systematic study of carbonylation of pure nickel and iron, and carbonylation of selectively reduced laterite ore to develop a further understanding of carbonylation reactions and extraction of nickel from laterite ore by carbonylation. Specific objectives of this study included: 1) to study the effects of reaction parameters on carbonylation of nickel and iron, including reaction temperature (80-100 oC), carbon monoxide (gauge) pressure (0- 56atm), gas flow rate (0.14-0.50 L·min-1), nickel mass (0.8-3.2g) and particle sizes (0.29 – 2.67 µm), and the effect of sulphur-containing catalysts (sulphur, iron sulphide and hydrogen sulphide); 2) to study the non-catalytic and catalytic carbonylation of laterite ores; the impacts of reduction conditions; and effects of reaction parameters; 3) to develop further understanding of kinetics and mechanisms of carbonylation processes. Pure metals and nickel-iron mixture were prepared by the reduction of associated oxides by hydrogen at 500oC (gas flow rate 1.0 L·min-1); the degree of reduction of oxides was over 98%. Two types of Australian laterite ores supplied by CSIRO were examined (labelled by CSIRO): BCS ore containing 1.35 wt% Ni, 10.4 wt% Fe and 0.038 wt% Co, V particle size 53-200 µm; and MIN ore with particle sizes 38-53 µm, 75-90 µm, 140-200 µm, and 355-495 µm, containing 1.68-2.37 wt% Ni, 8.90-11.8 wt% Fe and 0.135-0.144 wt% Co).
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