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Physicochemical Studies of Oxide Zinc Mineral Flotation Mineral Zinc Oxide of Physicochemicalstudies 2008:17 DOCTORAL T H E SIS Seyed Hamid Hosseini Seyed Physicochemical Studies of Oxide Zinc Mineral Flotation Physicochemical Studies Physicochemical of Oxide Zinc Mineral Flotation Seyed Hamid Hosseini Luleå University of Technology Department of Chemical Engineering and Geosciences 2008:17 Division of Mineral Processing Universitetstryckeriet, Luleå 2008:17|: 102-1544|: - -- 08⁄17 -- DOCTORAL THESIS Physicochemical Studies of Oxide Zinc Mineral Flotation Seyed Hamid Hosseini Division of Mineral Processing Department of Chemical Engineering and Geosciences Luleå University of Technology March 2008 To My Wife & My Son Abstract At the present, zinc is produced mostly from zinc sulphide ores because the sulphides are easy to separate from the gangue by conventional flotation techniques. In the case of oxide zinc ores, there is often no selectivity in terms of zinc recovery. The objective of the present study is to investigate the influence of different cationic, anionic and mixed collectors on the flotation of smithsonite mineral and an oxide zinc ore at various concentrations and pH values. The present thesis consists of three parts: i) characterization of smithsonite mineral and oxide zinc ore from the Angooran ore deposit, Iran, ii) physicochemical studies on smithsonite sample including zeta-potential, contact angle, microflotation tests and adsorption studies using diffuse reflectance FTIR (DRIFT) and X-ray photoelectron spectroscopy (XPS) techniques in the presence of cationic, anionic and mixed collectors (cationic/anionic) and iii) flotation behavior of oxide zinc ore from the Angooran ore in the presence of cationic, anionic and mixed collectors. The results of XPS and EDX on ore samples in different size fractions showed no significant variations in zinc percentage on bulk and surface of samples. The smithsonite flotation in the presence of dodecylamine after sulphidization using sodium sulphide shows a maximum recovery (94 %) at around pH 11.5. Among the anionic collectors used i.e. oleic acid, hexylmercaptan, KAX alone and KAX in the presence of sodium sulphide and copper sulphate, oleic acid indicates a maximum flotation recovery (93 %) at around pH 10. Regarding the mixed collector flotation, the recovery increases with increasing KAX concentration i.e. the flotation recovery enhanced to 96 %. Also the recoveries and contact angles are much higher compared to KAX and DDA alone are used. The spectroscopic data are interpreted in the light of flotation, zeta potential and contact angle results. The qualitative and quantitative evaluation of the adsorbed layer which determines the extent of surface hydrophobicity or hydrophilicity, are performed using spectroscopic methods (FTIR and XPS). The DRIFT and XPS spectra confirm the adsorption of dodecylamine, oleic acid, hexylmercaptan, KAX and mixed collector (KAX+DDA) on the smithsonite surface. These results are consistent with the zeta-potential, contact angle and also microflotation results. The studies on oxide zinc ore indicate a maximum bench scale flotation recovery of 84.5 % with zinc grade 24.5% in the presence of dodecylamine at pH 11.5. There are no significant variations in recovery of cationic and anionic and mixed collectors, however, amine and mixed collector flotation show to be more selective than anionic collectors. The recoveries with mixed collectors show that increasing KAX leads to improve the flotation recovery. Keywords: Smithsonite, Oxide zinc ore, Cationic collector, Anionic collectors, Mixed cationic/anionic collector, Zeta-potential, Contact angle, Microflotation, Batch Flotation, FTIR, XPS I Acknowledgements I would like to express my true gratitude to my supervisor Prof. Eric Forssberg for his continuous guidance, encouragement and invaluable discussions and also for giving me the opportunity to pursue my doctoral studies. I acknowledge Prof. K. Hanumantha Rao, Luleå University of Technology, Division of Mineral Processing, for his valuable comments and also the review of my doctoral thesis. I would like to thank Prof. Pär weihed, Head of Department of Chemical Engineering and Geosciences and Dr. Bertil Pålsson, Head of Mineral Processing Division, for their helps to finalize my doctoral thesis. I would like to thank Calcimine Co., Zanjan, Iran for providing the samples, which were used in this work, and also for giving some suggestions concerning my research work. I am very grateful to Prof. M. Sadrzadeh, Tehran University, Tehran, Iran for providing me an opportunity to do chemical analyses. I acknowledge Mr. Urban Jelvestam and all colleagues at the Department of Material Science, Chalmers University of Technology, Gothenburg, Sweden for their helps in the laboratory for XPS measurements and special thanks to Dr. Karl Arnby who was PhD student at the Department of Chemical Engineering, Chalmers University of Technology, Gothenburg, Sweden, being very friendly and for his help to measure zeta-potential. I would like to thank Dr. Andrei Shchukarev, Department of Inorganic chemistry, Umeå University, Umeå, Sweden for the XPS measurements. I would like to give my thanks to Mrs. Maine Ranheimer for her help in my FTIR experiments and to Mr. Ulf Nordström for his help in the laboratory. I wish to convey my thanks to all of my friends and colleagues at Departments of Chemical Engineering and Geosciences, Luleå, Sweden, especially the fruitful discussions with Dr. Nourreddine Menad concerning my research works have been very helpful and my thanks also extend to all Iranian friends at Luleå University of Technology, especially to Dr. Hamid Reza Manouchehri, Peyman Roonasi for their attentions and to Pejman Oghazi for his chatting and his kind helps in my everyday life. I would like to thank Dipl. Ing. Majid Ghameshlu, Siemens A.G., Vienna, Austria for encouraging me to start my PhD studies. I am very thankful Dipl. Ing. Nasser Hoshyar, Abniroo Consulting Engineering Co., Tehran, Iran for his supports during my life and also this research work. I am very grateful to my parents, my brother, my sister and also my wife’s parents for their blessings for the success in my life. Finally but most of all, I am deeply indebted to my wife, Pantea and my sweet son, Parsa for their constant love and patience during my research works. Seyed Hamid Hosseini December 2007 Luleå, Sweden II List of Publications This thesis is based on the work contained in the following papers, referred to by Roman numerical in the text: Paper I Adsorption Studies of Smithsonite Flotation Using Dodecylamine and Oleic acid S. Hamid Hosseini and Eric Forssberg Minerals and Metallurgical Processing, SME, Vol.23, No.2, 2006, 87-96 Paper II Smithsonite Flotation Using Potassium Amyl Xanthate and Hexylmercaptan S. Hamid Hosseini and Eric Forssberg Mineral Processing and Extractive Metallurgy, Trans. Inst. Min Metals. C, Vol.115, No. 3, 2006, 107-112 Paper III XPS & FTIR Study of Adsorption Characteristics Using Cationic and Anionic Collectors on Smithsonite S. Hamid Hosseini and Eric Forssberg Journal of Minerals and Materials Characterization and Engineering, Vol.5, No.1, 2006, 21-45 Paper IV Physicochemical Studies of Smithsonite Flotation using Mixed Cationic/Anionic Collector S. Hamid Hosseini and Eric Forssberg Minerals Engineering, Vol.20, Issue 6, 2007, 621-624 Paper V Flotation Behavior of Oxide Zinc Ore from Angooran Deposit, Iran in the Presence of Cationic/Anionic and Mixed (Cationic/Anionic) Collectors S. Hamid Hosseini and Eric Forssberg European Journal of Mineral Processing & Environmental Protection, Vol.6, No.3, 2006 (In press) Paper VI Comparison Between the Bulk & Surface Composition of the Samples from Angooran lead & zinc Mine, Zanjan Province, Iran S. Hamid Hosseini, Ulf Södervall and Eric Forssberg Proceedings of the 6th Conference on Environment and Mineral Processing, Ostrava, Czech Republic, June 2002, pp.289-294 III Paper VII Mineral Processing Possibility of Oxide Lead & Zinc Minerals from Angooran Deposit in Zanjan province, Iran S. Hamid Hosseini and Eric Forssberg Proceedings of the IX Balkan Mineral Processing Congress, Istanbul, Turkey, September 2001, pp.221-226 List of abbreviation Abbreviation Meaning DDA Dodecylamine DRIFT Diffuse Reflectance Infrared Fourier Transform EDX Energy Dispersive X-ray Analyzer FTIR Fourier Transform Infrared Spectroscopy HLS Heavy Liquid Separation HMS Heavy Media Separation HM Hexyl mercaptan or Hexanethiol KAX Potassium Amyl Xanthate OA Oleic acid XPS X-ray Photoelectron Spectroscopy XRD X-ray Diffraction XRF X-ray Fluorescence IV Table of Contents 1. INTRODUCTION ........................................................................................................................................1 2. BACKGROUND...........................................................................................................................................2 2.1 SOLUBILITY AND STABILITY OF OXIDE ZINC MINERALS IN AQUEOUS MEDIA.........................................2 2.2 SOLUTION CHEMISTRY OF REAGENTS ....................................................................................................2 2.2.1 Cationic Collector (dodecylamine).................................................................................................................... 3 2.2.2 Anionic Collectors ............................................................................................................................................ 5 2.2.2.1 Oleic acid...................................................................................................................................................
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