The Use of Magnetite Ore in Advanced Ironmaking
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The University of New South Wales Faculty of Science School of Materials Science and Engineering The Use of Magnetite Ore in Advanced Ironmaking Submitted for the degree of Doctor of Philosophy By Yury Kapelyushin October 2017 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.' 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.’ i 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.’ ii In Recognition of Scientists Past, Present and Future And Their Contribution Towards a Better, More Knowledgeable, Informative, Intelligent and Inclusive World, For the Overall Betterment And Uplifting of Future Generations And Our Unique Planet Earth iii THE UNIVERSITY OF NEW SOUTH WALES Thesis/Dissertation Sheet Surname or Family name: Kapelyushin First name: Yury Other name/s: Abbreviation for degree as given in the University calendar: PhD School: MATERIALS SCIENCE AND ENGINEERING Faculty: SCIENCE Title: The Use of Magnetite Ore in Advanced Ironmaking Abstract 350 words maximum: The PhD project has been undertaken within the ARC Linkage Project LP120200634 “The use of magnetite ore in advanced ironmaking” (Partner Organisation POSCO). The project’s ultimate aim was to develop further understanding of reduction of magnetite ore under FINEX® conditions. The project studied reduction of magnetite and magnetite doped with alumina, reduction and swelling of two magnetite ores and reduction of a mixture of magnetite and hematite ores. Reduction behaviour was studied in a fixed-bed reactor and in-situ using high temperature XRD (HT XRD) analysis. Reduction of magnetite doped with alumina (3, 6 and 12 mass % Al2O3) was studied using CO-CO2 gas mixture at 750 °C and 850 °C. Alumina had a strong effect on the magnetite reduction. Reduction of un-doped magnetite was developed topochemically with formation of a dense iron shell. However, reduction of alumina-doped magnetite to wüstite proceeded with formation of a network- like structure which consisted of criss-crossed plates of wüstite. Reduction of magnetite ore concentrates was studied using CO-CO2 and CO-CO2-H2 gas mixtures at varied temperatures and gas compositions. Addition of H2 to the CO-CO2 gas mixture accelerated the reduction in first 10-30 min reaction. Significant swelling of magnetite ore pellets was observed in the reduction by CO-CO2 gas mixture. Addition of H2 to the CO-CO2 gas mixture decreased swelling. Swelling of magnetite ore during the reduction was attributed to the breakout of iron layer caused by the increase of the inner pressure in the voids at the wüstite/iron phase boundary. o Phase development in the process of reduction by CO-CO2 gas mixture at 750 and 850 C was studied in-situ using HT- XRD analysis with Rietveld refinement of the HT-XRD spectra. The compositions of the Fe3O4 - FeAl2O4 solid solution, and concentrations of carbon in γ -iron were determined from the lattice constants of the solutions. New data on the effect of alumina on the reduction of magnetite, mechanisms of reduction and swelling of magnetite ore, unique data on the phase development obtained in HT XRD analysis constitute a significant contribution to further understanding of reduction processes. 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). 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 require the approval of the Dean of Graduate Research. FOR OFFICE USE ONLY Date of completion of requirements for Award: iv Acknowledgments The PhD project was made possible with funding from the ARC Linkage Project (LP120200634) and Partner Organisation POSCO. I would like to express my sincere thanks to everyone who has generously assisted me in any way during this project and I apologise in advance, if unintentionally, I have left anyone out. Special thanks go to my parents Lyudmila Ikonnikova and Eugene Kapelyushin whose unshakable confidence, endless patience and wholehearted support for me throughout my studies, made everything possible. Special mention also goes to Dr Xing Xing who was pivotal in the early stages and whose invaluable assistance helped me to create the framework so I could competently commence my experiments. Thanks also go to Professional Officer Mr. John Sharp who was most helpful in assembling the necessary laboratory equipment, gas tubes and fittings central to the experiments. Dr Yu Wang’s help and advice made it possible to run difficult high-temperature XRD experiments and I am much in his debt. Dr Jason Scott was likewise of great assistance, especially in providing and allowing use in my research of his measurements of the BET surface area of samples used. Technical officers Sarah Kelloway and Irene Wainwright provided valuable assistance with LECO analysis. The special skills of EMU administrative staff Karen Privat and Yin Yao were of great benefit in demonstrating to me the proper usage of electronic microscopes, which allowed me to make wonderful SEM images. The administrative staff members of our school Qing Xia and Laura McNally were very kind and extremely helpful in finding a solution to numerous organisational issues. I am extremely grateful to technical officers Anthony Zhang and Dr Rahmat Kartono for all their help, especially in the moving and arranging of gas cylinders and other cumbersome laboratory items. Jane Gao and Danny Kim were also invaluable in assisting me to connect the printer and fixing other mishaps with electronic equipment. I v am also thankful to technical Officer George Yang who demonstrated to me the best format to prepare samples for the microscopy, and for his never ending assistance to ensure I had a workable, clean and tidy working area. I would like to express my sincere gratitude to Professor Yasushi Sasaki for his unstinting assistance and valuable help with arranging high-temperature XRD experiments, for his patience during our long discussions of the experimental results, and for his overall support in collating the data. I am much indebted also to my co-supervisor Jianqiang Zhang for all his support and assistance over the lifetime of this research project. This PHD project was also greatly assisted and made entirely possible through the efforts of my supervisor Oleg Ostrovski, who directed and supported me throughout, and ensured I was proceeding in a disciplined and well organized manner during the entirety of this PhD project. Mr David Martin Clifford has assisted in proof reading and revising the thesis, and also helped to correct English grammar. vi Project Publications [1]. Kapelyushin, Y., Xing, X., Zhang, J., Jeong, S., Sasaki, Y. and Ostrovski, O., Effect of Alumina on the Gaseous Reduction of Magnetite in CO/CO2 Gas Mixtures, Metallurgical and Materials Transactions B; 2015, vol. 46B, pp. 1162-1174. [2]. Kapelyushin, Y., Sasaki, Y., Zhang, J., Jeong, S. and Ostrovski, O., In-Situ Study of Gaseous Reduction of Magnetite Doped with Alumina Using High-Temperature XRD Analysis, Metallurgical and Materials Transactions B; 2015, vol. 46B, pp. 2564-2572. [3]. Kapelyushin, Y., Sasaki, Y., Zhang, J., Jeong, S. and Ostrovski, O., In-situ study of gaseous reduction of magnetite doped with alumina using high temperature XRD analysis”, Asia Steel Conference, 5 – 8 Oct, 2015, Yokohama, Japan.