Đất hiếm ở Việt Nam được phát hiện từ những năm 1956 và được đầu tư tìm kiếm, đánh giá, thăm dò từ năm 1957 đến nay. Các kết quả điều tra, đánh giá đã chỉ ra Việt Nam là nước có tiềm năng lớn về đất hiếm. Các mỏ đất hiếm ở Việt Nam có quy mô từ trung bình đến lớn, chủ yếu là đất hiếm nhóm nhẹ (nhóm lantan ceri), có nguồn gốc nhiệt dịch và tập trung ở vùng Tây Bắc Việt NamLimit of LiabilityDisclaimer of Warranty: While the publisher and author have used their best efforts in preparing this book, they make no representations or warranties with respect to the accuracy or completeness of the contents of this book and specifically disclaim any implied warranties of merchantability or fitness for a particular purpose. No warranty may be created or extended by sales representatives or written sales materials. The advice and strategies contained herein may not be suitable for your situation. You should consult with a professional where appropriate. Neither the publisher nor author shall be liable for any loss of profit or any other commercial damages, including but not limited to special, incidental, consequential, or other damages. Wiley
Rare Metal Technology 2015 144th Annual Meeting & Exhibition March 15-19, 2015 • Walt Disney World • Orlando, Florida, USA N e w proceedings volumes from the TMS2015 Annual Meeting, available from publisher John Wiley & Sons: • 6th International Symposium on High-Temperature Metallurgical Processing • Advanced Composites for Aerospace, Marine, and Land Applications II • Advances in the Science and Engineering of Casting Solidification • Characterization of Minerals, Metals, and Materials 2015 • Drying, Roasting, and Calcining of Minerals • Energy Technology 2015 • EPD Congress 2015 • Friction Stir Welding and Processing VIII • Light Metals 2015 • Magnesium Technology 2015 • Rare Metal Technology 2015 • TMS 2015 Supplemental Proceedings To purchase any of these books, visit www.wiley.com TMS members: Log in to the Members Only area of www.tms.org and learn how to get your discount on these and other books offered by Wiley V J Rare Metal Technology 2015 Proceedings of a symposium sponsored by The Minerals, Metals & Materials Society (TMS) held during TIMIS2015 144th Annual Meeting & Exhibition March 15-19, 2015 Walt Disney World • Orlando, Florida, USA Edited by: Neale R Neelameggham Shafiq Alam | Harald Oosterhof Animesh Jha | David Dreisinger Shijie Wang Wl LEY TMS Copyright © 2015 by The Minerals, Metals & Materials Society All rights reserved Published by John Wiley & Sons, Inc., Hoboken, New Jersey Published simultaneously in Canada No part of this publication may be reproduced, stored in a retrieval system, or transmitted in any form or by any means, electronic, mechanical, photocopying, recording, scanning, or otherwise, except as permitted under Section 107 or 108 of the 1976 United States Copyright Act, without either the prior written permission of The Minerals, Metals, & Materials Society, or authorization through payment of the appropriate per-copy fee to the Copyright Clearance Center, Inc., 222 Rosewood Drive, Danvers, MA 01923, (978) 750-8400, fax (978) 750-4470, or on the web at www.copyright.com Requests to the Publisher for permission should be addressed to the Permissions Department, John Wiley & Sons, Inc., I l l River Street, Hoboken, NJ 07030, (201) 748-6011, fax (201) 748-6008, or online at http:// www.wiley.com/go/permission Limit of Liability/Disclaimer of Warranty: While the publisher and author have used their best efforts in preparing this book, they make no representations or warranties with respect to the accuracy or completeness of the contents of this book and specifically disclaim any implied warranties of merchantability or fitness for a particular purpose No warranty may be created or extended by sales representatives or written sales materials The advice and strategies contained herein may not be suitable for your situation You should consult with a professional where appropriate Neither the publisher nor author shall be liable for any loss of profit or any other commercial damages, including but not limited to special, incidental, consequential, or other damages Wiley also publishes books in a variety of electronic formats Some content that appears in print may not be available in electronic formats For more information about Wiley products, visit the web site at www.wiley.com For general information on other Wiley products and services or for technical support, please contact the Wiley Customer Care Department within the United States at (800) 762-2974, outside the United States at (317) 572-3993 or fax (317) 572-4002 Library of Congress Cataloging-in-Publication Data is available ISBN 978-1-119-07830-2 Printed in the United States of America 10 Wl LEY TIÜS TABLE OF CONTENTS Rare Metal Technology 2015 Preface About the Editors Session Chairs ix xi xvii Rare Metal Processes Industrial Practice of Biohydrometallurgy in Zambia J Wang, H Zhao, W Qin, X Liu, and G Qiu Industrial Oxygen and Its Advanced Application Technology for Hydrometallurgy Process W Zhongling, Z Deliang, L Yongguo, T Le, Y Qing, and T Niehoff 11 Electrochemical Removal Impurity of NaCl from LiCl-KCl Melts B Li, M Shen, Y Chen, and Q Wang 19 Modern Beryllium Extraction: A State-of-the-Art Kro 11 Reduction Plant E Vidal, J Yurko, and K Smith 27 How to Recover Minor Rare Metals from E-Scrap T Nakamura 37 Solvent Extraction of Cu2+ with Laminar Flow of Microreactor from Leachant Containing Cu and Fe J Feng, L Chuanhua, P Jinhui, Z Libo, and J Shaohua 45 Precious Metals Extraction of Gold from a Low-Grade Double Refractory Gold Ore Using Flotation-Preoxidation-Leaching Process Y Yang, S Liu, B Xu, Q Li, T Jiang, and P Lv 55 Gold Extraction from a High Carbon Low-Grade Refractory Gold Ore by Flotation-Roasting-Leaching Process Y Yang, Z Xie, B Xu, Q Li, and T Jiang 63 Gold Leaching from a Refractory Gold Concentrate by the Method of Liquid Chlorination C Li, H Li, X Yang, S Wang, and L Zhang 71 The Effects of Common Associated Sulfide Minerals on Thiosulfate Leaching of Gold Y Yang, X Zhang, B Xu, Q Li, T Jiang, and Y Wang 79 v Hydro metallurgical Extraction of Precious, Rare and Base Metals Using an Oxidizing Acid Chloride Heap Leach D Dreisinger, N Verbaan, C Forstner, and R Fitch Recovery of Platinum Group Metals Using Perovskite-Type Oxide K Nagai, H Kumakura, S Yanai, and T Nagai Research on Process of Hydrometallurgical Extracting Au, Ag, and Pd from Decopperized Anode Slime Y Yang, W Yin, T Jiang, B Xu, and Q Li 87 101 107 Rare Earth Metals Status of Separation and Purification of Rare Earth Elements from Korean Ore J Kim, H Kim, M Kim, J Lee, and J Kumar 117 Optimization of Rare Earth Leaching 127 G Wallace, S Dudley, W Gleason, C Young, L Twidwell, J Downey, H Huang, R James, and E Rosenberg Numerical Simulation of the Mass Transfer for Rare-Earth Concentrate in Leaching Process T Liu, Y Sheng, T Yang, B Wang, L Han, and Q Liu Apatite Concentrate, A Potential New Source of Rare Earth Elements T Sun, M Kennedy, G Tranell, and R Aune Rare Earth Elements Gallium and Yttrium Recovery from (KC) Korean Red Mud Samples by Solvent Extraction and Heavy Metals Removal/Stabilization by Carbonation T Thriveni, J Kumar, C Ramakrishna, Y Jegal, and J Ahn Rare Earth Element Recovery and Resulting Modification of Resin Structure S Dudley, M Chorney, W Gleason, E Rosenberg, L Twidwell, and C Young Ultra High Temperature Rare Earth Metal Extraction by Electrolysis B Nakanishi, G Lambotte, and A Allanore vi 135 145 157 169 177 Vanadium-Molybdenum-Tungsten A Novel Technology of Vanadium Extraction from Stone Coal M Wang, X Wang, and B Li 187 Mechanical Activation of Processing of Egyptian Wolframite A Abdel-Rehim and M Bakr 193 Leaching of Vanadium from the Roasted Vanadium Slag with High Calcium Content by Direct Roasting and Soda Leaching X Yan, B Xie, L Jiang, H Guo, and H Li 209 Solvent Extraction of Vanadium from Converter Slag Leach Solution by P204 Reagent T Zhang, Y Zhang, G Lv, Y Liu, G Zhang, and Z Liu 217 Effect of Solution Compositions on Optimum Redox Potential in Bioleaching of Chalcopyrite by Moderately Thermophilic Bacteria H Zhao, J Wang, W Qin, and G Qiu 225 Poster Session Research on Quality Improvement of Titanium Sponge by Process Optimization L Li, K Li, Q Miao, and C Wang 231 Recovery of Rare Earth Elements from NdFeB Magnet Scraps by Pyrometallurgical Processes Y Bian, S Guo, K Tang, L Jiang, C Lu, X Lu, and W Ding 239 Study on Electrolysis for Neodymium Metal Production G Lee, S Jo, C Lee, H Ryu, and J Lee 249 Experimental Investigation of Recycling Rare Earth Metals from Waste Fluorescent Lamp Phosphors P Eduafo, M Strauss, and B Mishra 253 Author Index 261 Subject Index 263 vii more short time compared to no argon injection as shown Figure In this case, it was found that the applied current was maintained with approximate 120A And also it was observed that applied current was fluctuated within a certain range during all the time 0 5 2 30 4 Timeihr ) Figure Chronoamperemetry for electrowinning in LiF-NdF3-Nd203 system at 1150°C to inject argon gas in electrolyte It seems that in the LiF-NdF -Nd 03 system the neodymium metal is cathodically produced by the electroreduction of neodymium fluorides while at the anode the oxidation of neodymium oxyfluorides generates oxygen according to the following equations: 2[NdF6]3~ + 6e = 2Nd(s) + 12F 3[NdOF5]4 - 6e" = 3/20 (g) + 3Nd3+ - 15F" (1) (2) It has been reported in Ref [9] that oxygen is generated at the anode during the electrolytic production of neodymium from oxide-fluoride melts The produced oxygen subsequently reacts with the carbon anode and CO and C0 gases are produced Anode efficiency was decreased that CO and C0 on anode prevent contact between anode and electrolyte called as bubble curtain effect Cell performance was improved because of these gases on the anode surface were easily removed by electrolyte flow by argon gas injection In the future, the study will focus on the mechanism of bubble curtain, and its effect during neodymium electrolysis Conclusion Electrolysis of neodymium was carried out using LiF-NdF3-Nd203 electrolyte at 1150°C Cell performance was improved by convection effect of electrolyte of argon gas injection resulting in easy flotation of CO and C0 gases formed on the near surface at anode Acknowledgement This work was supported by the "Energy Efficiency & Resources Core Technology Program" of the Korea Institute of Energy Technology Evaluation and Planning (KETEP), granted financial 251 resource from the Ministry of Trade, Industry & Energy, Republic of Korea.(No 20122010300041) References R A Sharma and R N Seefurth, "Metallothermic Reduction of Nd203 with Ca in CaCI2NaCI Melts," Journal Electrochemical society, 135 (1988), 66-71 P T Velu and R.G Reddy, "Calciothermic reduction of neodymium fluoride," The Minerals, Metals & Materials Society, (2005), 1155-1159 G J Kipouros and R A Sharma, "Electrolytic Regeneration of the Neodymium Oxide Reduction-Spent Salt," Journal Electrochemical society, 137 (1990), 3333-3338 Y Castrillejo et al., "Solubilization of rare earth oxides in the eutectic LiCl-KCl mixture at 450 °C and in the equimolar CaC12-NaCl melt at 550oC," Journal of Electroanalytical Chemistry, 545 (2003), 141-/157 E Stefanidaki, C Hasiotis and C Kontoyannis, "Electrodeposition of neodymium from LiFNdF3-Nd203 melts," Electrochimica Acta 46 (2001), 2665-2670 X W Hu et al., "Electrical conductivity and Nd solubility of NdF3-LiF-Nd203 melts," Metals & Materials Society, (2007) 79-82 S G Chen et al., "Cathodic process of Nd and its dissolution behavior in molten fluoride," Rare Metals, 13 (1994) 46-49 J E Murphy, D K Dysinger and M F Chambers, "Electrowinning neodymium metal from chloride and oxide-fluoride electrolytes," Metals & Materials Society, (1995), 1313-1320 A Kaneko, Y Yamamoto, C Okada "Electrochemistry of rare earth fluoride molten salts," Journal of Alloys and Compounds, 193(1993) 44 - 46 252 Edited by: Neale R Neelameggham, ShafiqAlam, Rare Metal Technology 2015 Harald Oosterhof, Animesh Jha David Dreisinger, and Shijie Wang TMS (The Minerals, Metals & Materials Society), 2015 EXPERIMENTAL INVESTIGATION OF RECYCLING RARE EARTH METALS FROM WASTE FLUORESCENT LAMP PHOSPHORS Patrick M Eduafo1, Mark L Strauss1, Brajendra Mishra1 Colorado School of Mines (Kroll Institute of Extractive Metallurgy); 1500 Illinois Street; Golden, CO, 80401, USA Waste fluorescent lamp, phosphor powder, rare earth metals, recycle, leaching Abstract Direct acid leaching of rare earth metals (REMs) from waste lamp phosphors is non-selective, leading to co-dissolution of impurities mainly calcium, phosphorus, silicon, iron and zinc Calcining the phosphor powder at different temperatures followed by leaching with HC1 isn't efficient for the extraction of all the chief rare earths especially cerium (Ce), lanthanum (La) and terbium (Tb) Therefore, multi-stage leaching operations are required for the separation of the REMs in phosphor dust This paper will outline a new process for extracting Ce, La, Tb, Eu and Y from waste fluorescent lamps using a three-stage leaching and separation process A flowsheet has been developed which shows this process is selective and efficient Introduction Increasing demands for rare earth metals (REMs) due to rapid technological growths in several high-technology applications such as green energy, efficient fuel vehicles, defense related applications, emissive displays and fluorescent lamps, etc coupled with shortage of supply has forced a paradigm shift towards finding alternative routes for rare earth production and supply The concentration of rare-earth oxides in lamps with trichromatic phosphors can be as high as 27.9 wt%, but the actual recycled phosphor fractions contain about 10.0 wt% of rare earths oxides [1], which makes them an important secondary resource A number of processes have been investigated for recovery of REMs present in phosphor powder Takahashi's group carried out a series of studies on the hydrometallurgical separation and recovery of rare earths from phosphors in the fluorescent lamp wastes [2], [3], [4], After optimization of the leaching conditions, 92% of yttrium and 98% of europium were dissolved at sulfuric acid concentration of 1.5 M, temperature of 70°C, leaching time of h, and pulp concentration of 30 g/L Wang et al have conducted leaching experiments on spent trichromatic phosphor mixtures and recovered 96.28% of yttrium with M hydrochloric acid in combination with 4.4 g/L hydrogen peroxide [5], Rabah proposed a process for the recovery of europium, yttrium and some valuable salts from spent fluorescent lamps by pressure leaching with a H2SO4/HNO3 mixture at 125 °C and MPa for hours and dissolved 92.8% of the europium and 96.4% of the yttrium present in the mixture [6], De Michelis and his co-workers produced yttrium oxalate of 99% purity from synthetic sulphuric acid leach solution by oxalic acid precipitation Yang et al [7] developed a two stage leaching process with sulphuric acid in the first stage and nitric acid in the second stage and recovered 99% yttrium and 95% europium from phosphor powder A lot of emphasis on recovery of REMs from spent fluorescent lamps has been on Y and Eu This paper proposes a method for extraction of all chief REEs - Ce, La, Tb, Y and Eu 253 Experimental A Materials Phosphor powder from the spent fluorescent lamps was provided by Veolia ES Technical Solutions, (IL, USA) All the chemicals used were of analytical grade reagents (Sigma Aldrich, USA) Deionized water was used for preparation of solutions of known concentration and 2% HNO3 was used for dilution before chemical analysis B Analysis Elemental composition in the collected phosphor powder was determined by chemical analysis Concentration of metal ions present in the leach liquor was determined by lithium fusion and inductively coupled plasma-optical emission spectrometer (ICP-OES, Optima 5300 DV Perkin Elmer Co., MA, USA) for quantification C Procedure Phosphor powder coating of the fluorescent lamps obtained was sieved with a sieve of 325 Tyler mesh to separate any broken glass particles present Leaching of the powder was carried out with different acid reagents on a hot plate with a magnetic stirring facility in a Pyrex glass beaker Samples were taken at the end of each leaching experiment and analyzed for REE and impurities in the leachate Results and Discussion A Phosphor Dust Characterization Size based separation was done to determine which size fraction will eliminate the most impurities and retain the bulk of the REE Dry sieving the powder to 44 (im results in an upgrade of the REE content by 95.56% and removal of significant impurities (61.92%) The chemical content of the phosphor powder used for the experiments show some variations, which stems from how the powders were generated by the lamp recycling company As can be seen in Table 1, the chief rare earths are Y, Eu, Ce, La and Tb, which are constituents of trichromatic lamp phosphors The main impurities include Ca and P from calcium halophosphate phosphor, Al and Si from alumina (A1203) and silica (Si0 ) used in the barrier layer between the phosphor layer and the glass tube Iron is possibly from the crushing and grinding equipment used in processing the end-of-life lamps Table : Elemental composition of the phosphor powders used in this study Elements (wt%) Y Eu Ce La Tb Ca P Fe Al Si Powder 9.50 0.64 1.48 2.09 0.65 18.50 9.54 0.31 2.72 4.33 Powder 9.65 0.67 1.66 2.15 0.69 17.50 8.35 0.32 2.50 6.33 Powder 5.46 0.37 1.05 1.27 0.41 21.34 9.95 0.38 2.13 6.61 Particle size and QEMSCAN analysis were also performed for physical characterization of the phosphor powder The results (data not shown) show that the sieved powders have a size distribution mainly from [...]... Shijie Wang Rare Earth Metals Neale R Neelameggham Joon Soo Kim Vanadium-Molybdenum-Tungsten Harald Oosterhof Bing Li \v ii Rare Metal Technology 2015 Rare Metal Processes Editedby: Neale R Neelameggham, Rare Metal Technology 2015 Shafiq Alam, Harald Oosterhofi AnimeshJha David Dreisinger, and Shijie Wang TMS (The Minerals, Metals & Materials Society), 2015 INDUSTRIAL PRACTICE OF BIOHYDROMETALLURGY...PREFACE Rare Metal Technology 2015 is the second proceedings of the symposium on Rare Metal Extraction & Processing initiated in 2014 and sponsoredby the Hy drometallurgy and Electrometallurgy Committee of the TMS Extraction and Processing Division The symposium has been organized to encompass the extraction of rare metals as well as rare extraction processing techniques used in metal production... non-ferrous metals', precious metals', rare metals', and rare earth metals' resourcefulness and recovery He is a copper, gold, silver, selenium and tellurium refining subject matter expert Dr Wang has been a TMS member since 1991 and is former chair of the Hydrometallurgy and Electrometallurgy Committee of TMS from 2011 to 2013 xv SESSION CHAIRS Rare Metal Processes Shafiq Alam Takashi Nakamura Precious Metals... cold crucible synthesis of the rare metals and the design of extraction equipment used in these processes as well as laboratory and pilot plant studies This proceedings volume covers about 15 rare metal elements and 15 rare earth elements in 29 papers The symposium is organized into four sessions encompassing (1) rare metal process, (2) precious metals, (3) rare earth metals, and (4) V-Mo-W (vanadium-molybdenum-tungsten)... extraction of rare metals, that is, less common metals or minor metals not covered by other TMS symposia The elements considered include antimony, bismuth, barium, beryllium, boron, calcium, chromium, gallium, germanium, hafnium, indium, manganese, molybdenum, platinum group metals, rare earth metals, rhenium, scandium, selenium, sodium, strontium, tantalum, tellurium, tungsten, etc These are rare metals... been a co-organizer of the Energy Technology symposium each year since 2008 Dr Neelameggham is currently the chair ofthe Hy drometallurgy andElectrometallurgy Committee, and he organized the Rare Metal Technology 2014 and 2015 symposia He is the co-editor of the Essential Readings in Magnesium Technology compendium of TMS papers published in 2014 He is a co-editor of 2015 symposium on Drying, Roasting... low-tonnage sales compared to high-tonnage metals such as iron, copper, nickel, lead, tin, zinc, or light metals such as aluminum, magnesium, or titanium and electronic metalloid silicon Rare processing included biometallurgy, hy drometallurgy, electrometallurgy, as well as extraction of values from EAF dusts, and less common waste streams not discussed in recycling symposia Rare high temperature processes to... technologies in China, Minerals Engineering, 15 (2002) 361-363 10 Editedby: Neale R Neelameggham, Rare Metal Technology 2015 Shafiq Alam, Harald Oosterhofi Animesh Jha David Dreisinger, and Shijie Wang TMS (The Minerals, Metals & Materials Society), 2015 INDUSTRIAL OXYGEN AND ITS ADVANCED APPLICATION TECHNOLOGY FOR HYDROMETALLURGY PROCESS Wei Zhongling1 Zhang Deliang2, Liu Yongguo2, Tang Le2, Yin Qing2 Thomas... Corporation, Rambler Metals, and Anaconda Mining He is an Executive Committee Member of the Hydrometallurgy Section of the Metallurgy and Materials Society (MetSoc) of CIM and currently he holds the office of secretary with MetSoc (201 32015) Dr Alam is also the Vice-Chair of the Hydrometallurgy and Electrometallurgy Committee of the Extraction and Processing Division (EPD) of TMS (2013 -2015) He is actively... technology group that is based in Belgium During his first assignment as Project Leader - Hydrometallurgy, he focused on the refining of cobalt, nickel, and germanium Since 2011, Dr Oosterhof has worked as scientist in the Recycling and Extraction Technology group at Umicore's Central R&D department His main competence areas are special metals hydrometallurgy, recycling and refining of rare earth metals, ... Earth Metals Neale R Neelameggham Joon Soo Kim Vanadium-Molybdenum-Tungsten Harald Oosterhof Bing Li v ii Rare Metal Technology 2015 Rare Metal Processes Editedby: Neale R Neelameggham, Rare Metal. .. about 15 rare metal elements and 15 rare earth elements in 29 papers The symposium is organized into four sessions encompassing (1) rare metal process, (2) precious metals, (3) rare earth metals,... V J Rare Metal Technology 2015 Proceedings of a symposium sponsored by The Minerals, Metals & Materials Society (TMS) held during TIMIS2015 144th Annual Meeting & Exhibition March 15-19, 2015