Copper metallurgical slags : mineralogy, bio/weathering processes and metal bioleaching Anna Potysz To cite this version: Anna Potysz. Copper metallurgical slags : mineralogy, bio/weathering processes and metal bioleach- ing. Material chemistry. Université Paris-Est, 2015. English. NNT : 2015PESC1201. tel-01407256 HAL Id: tel-01407256 https://tel.archives-ouvertes.fr/tel-01407256 Submitted on 8 Dec 2016 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. Copper metallurgical slags: mineralogy, bio/weathering processes and metal bioleaching PhD Thesis Committee Reviewers Prof. Emmanuel GUILLON University of Reims Reims (France) Prof. Vojtěch ETTLER Charles University Prague (Czech Republic) Examiners Prof. Gilles GUIBAUD University of Limoges Limoges (France) Hab. Dr. Giovanni ESPOSITO University of Cassino and Southern Lazio Cassino (Italy) Dr. Jakub KIERCZAK University of Wroclaw Wrocław (Poland) Promotor Hab. Dr. Eric van HULLEBUSCH University of Paris-Est Marne la Vallée Paris (France) Co-Promotor Prof. Dr. Ir. Piet N. L. LENS UNESCO-IHE Institute for Water Education Delft (The Netherlands) Co-Supervisor Dr. Malgorzata GRYBOS University of Limoges Limoges (France) Joint PhD degree in Environmental Technology Docteur de l’Université Paris-Est Spécialité : Science et Technique de l’Environnement Dottore di Ricerca in Tecnologie Ambientali Degree of Doctor in Environmental Technology Thèse – Tesi di Dottorato – PhD thesis Anna POTYSZ COPPER METALLURGICAL SLAGS: MINERALOGY, BIO/WEATHERING PROCESSES AND METAL BIOLEACHING Defended on December 10th 2015 In front of the PhD committee Prof. Emmanuel GUILLON Reviewer Prof. Vojtěch ETTLER Reviewer Hab. Dr. Giovanni ESPOSITO Examiner Prof. Gilles GUIBAUD Examiner Dr. Jakub KIERCZAK Examiner Hab. Dr. Eric van HULLEBUSCH Promotor Prof. Dr. Ir. Piet LENS Co-Promotor Dr. Malgorzata GRYBOS Co-Supervisor Erasmus Joint doctorate programme in Environmental Technology for Contaminated Solids, Soils and Sediments (ETeCoS3) viii Table of content Table of content ......................................................................................................................... ix List of tables ............................................................................................................................. xv List of figures ......................................................................................................................... xvii List of abbreviations ................................................................................................................ xxi Acknowledgements ............................................................................................................... xxiii Abstract ........................................................................................................................... xxv Résumé ......................................................................................................................... xxvii Sintesi .......................................................................................................................... xxix Samenvatting ......................................................................................................................... xxxi CHAPTER 1: INTRODUCTION ........................................................................................... 1 1.1 INTRODUCTION ............................................................................................................ 2 1.1.1 General introduction ................................................................................................ 2 1.1.2 Problem statement .................................................................................................... 2 1.1.3 Objectives ................................................................................................................ 4 1.2 STRUCTURE OF THE PhD THESIS .............................................................................. 5 CHAPTER 2: COPPER METALLURGICAL SLAGS - CURRENT KNOWLEDGE AND FATE: A REVIEW ............................................................................................. 10 2.1 INTRODUCTION .......................................................................................................... 12 2.2 MINING AND SMELTING OF COPPER .................................................................... 14 2.3 Cu-METALLURGICAL SLAGS ................................................................................... 15 2.3.1 Chemical and phase composition of copper slags ................................................. 17 2.3.1.1 Primary phases ................................................................................................ 23 2.3.1.2 Secondary phases ............................................................................................ 24 2.3.2 Environmental impact ............................................................................................ 25 2.3.3 Slags weathering .................................................................................................... 26 2.3.3.1 Primary phases: susceptibility to alteration .................................................... 27 2.3.3.2 Secondary phases: formation, metal sequestration and solubility .................. 28 2.3.3.3 Weathering factors .......................................................................................... 30 2.3.3.3.1 Physico-chemical factors ............................................................................ 30 2.3.3.3.1.1 Slag porosity and structure .................................................................... 30 2.3.3.3.1.2 pH conditions ........................................................................................ 30 2.3.3.3.1.3 Redox potential ..................................................................................... 31 2.3.3.3.1.4 Organic components ............................................................................. 31 2.3.3.3.2 Biological factors ........................................................................................ 32 2.3.3.3.2.1 Microbial actions .................................................................................. 32 2.3.3.3.2.2 Biofilm formation ................................................................................. 33 ix 2.3.3.3.2.3 Extracellular polymeric substances ....................................................... 33 2.3.3.3.2.4 Siderophores production ....................................................................... 34 2.3.3.3.2.5 Intracellular metal immobilization ........................................................ 35 2.3.4 Environmental risk assessment .............................................................................. 36 2.4 FATE OF COPPER SLAGS ........................................................................................... 39 2.4.1 Metal leaching ........................................................................................................ 40 2.4.1.1 Influence of extractant .................................................................................... 50 2.4.1.2 Influence of agitation ...................................................................................... 53 2.4.1.3 Influence of temperature ................................................................................. 53 2.4.1.4 Influence of liquid to solid ratio and particle size .......................................... 55 2.4.1.5 Influence of leaching time .............................................................................. 55 2.4.1.6 Slag structure .................................................................................................. 55 2.4.1.7 Optimal parameters ......................................................................................... 56 2.4.2 Copper recovery ..................................................................................................... 57 2.4.3 Metal bioleaching and biorecovery ........................................................................ 58 2.5 CONCLUDING REMARKS .......................................................................................... 66 CHAPTER 3: MATERIALS AND METHODS .................................................................. 76 3.1 MATERIALS AND METHODS .................................................................................... 78 3.1.1 Materials ................................................................................................................ 78 3.1.1.1 Historical slags ............................................................................................... 78 3.1.1.2 Modern slags ................................................................................................... 80 3.1.2 Methods .................................................................................................................. 82 3.1.2.1 Sample preparation ......................................................................................... 82