HYDROMETALLURGY fundamentals and applications.

462 Pages·2022·10.355 MB·English

by  MICHAEL L. FREE

The Minerals, Metals & Materials Series
Michael L. Free
Hydrometallurgy
Fundamentals and Applications
Second Edition
The Minerals, Metals & Materials Series
The Minerals, Metals & Materials Series publications connect the global minerals,
metals,andmaterialscommunities.Theyprovideanopportunitytolearnaboutthe
latestdevelopmentsinthefieldandengageresearchers,professionals,andstudents
in discussions leading to further discovery. The series covers a full range of topics
from metals to photonics and from material properties and structures to potential
applications.
More information about this series at https://link.springer.com/bookseries/15240
Michael L. Free
Hydrometallurgy
Fundamentals and Applications
Second Edition
123
Michael L. Free
Department ofMaterials Science
andEngineering
University of Utah
Salt Lake City,UT,USA
ISSN 2367-1181 ISSN 2367-1696 (electronic)
TheMinerals, Metals& Materials Series
ISBN978-3-030-88086-6 ISBN978-3-030-88087-3 (eBook)
https://doi.org/10.1007/978-3-030-88087-3
1stedition:©TheMinerals,Metals&MaterialsSociety2013
2ndedition:©TheMinerals,Metals&MaterialsSociety2022
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Preface
This book provides a college-level overview of chemical processing of metals in
water-basedsolutions.Itisanexpandedversionofaprevioustextbook,“Chemical
ProcessingandUtilizationofMetalsinAqueousMedia,”withtwoeditionswritten
by the author. The information in this book is relevant to engineers using, pro-
ducing, or removing metals in water. The metals can take the form of dissolved
ions,mineralparticles,ormetal.Thematerialineachchapterinthistextbookcould
be expanded into individual textbooks. It is clearly not comprehensive in its cov-
erage of relevant information. Other resources, such as the 4 volume series
“Principles of Extractive Metallurgy” by Fathi Habashi, provide more details for
specific metal processing methods. Thus, this text presents a condensed collection
of information and analytical tools. These tools can be used to improve the effi-
ciencyandeffectivenesswithwhichmetalsareextracted,recovered,manufactured,
and utilized in aqueous media in technically viable, reliable, environmentally
responsible, and economically feasible ways.
Theauthorexpressesgratitudetofamily,colleagues,teachers,andstudentswho
have contributed in various ways to the completion of this text.
Theauthorhasusedhisbesteffortstopreparethistext.However,theauthorand
publisher make no warranty of any kind, expressed or implied, with regard to the
material in this book. The author and publisher shall not be liable in any event for
incidental or consequential damages in connection with or arising out of the use
of the material in this book.
Salt Lake City, USA Michael L. Free
v
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.1 The Importance of Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.2 Mineral Deposition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
1.3 Importance of Water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
1.4 Aqueous Processing and Utilization of Metals . . . . . . . . . . . . 13
1.5 Overview of Fundamentals and Applications . . . . . . . . . . . . . 19
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
2 Chemical Fundamentals of Hydrometallurgy . . . . . . . . . . . . . . . . . 23
2.1 General Reactions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
2.2 Chemical Potential . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
2.3 Free Energy and Standard Conditions. . . . . . . . . . . . . . . . . . . 31
2.4 Free Energy and Nonstandard Activities. . . . . . . . . . . . . . . . . 33
2.5 Equilibrium. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
2.6 Solubility Product . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
2.7 Relationships Amongst K, pK, pK , and pH. . . . . . . . . . . . . . 37
a
2.8 Free Energy and Nonstandard Temperatures. . . . . . . . . . . . . . 39
2.8.1 Effect of Temperature on Gas Solubility. . . . . . . . . . 42
2.9 Heat Generation Due to Reactions . . . . . . . . . . . . . . . . . . . . . 42
2.10 Free Energy and Nonstandard Pressures . . . . . . . . . . . . . . . . . 44
2.11 Equilibrium Concentration Determinations . . . . . . . . . . . . . . . 44
2.12 Activities and Activity Coefficients . . . . . . . . . . . . . . . . . . . . 45
2.13 Practical Equilibrium Problem Solving. . . . . . . . . . . . . . . . . . 51
2.14 Electrochemical Reaction Principles . . . . . . . . . . . . . . . . . . . . 56
2.15 Equilibrium and Electrochemical Equations . . . . . . . . . . . . . . 59
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
vii
viii Contents
3 Speciation and Phase Diagrams . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
3.1 Speciation (or Ion Distribution) Diagrams. . . . . . . . . . . . . . . . 69
3.2 Metal–Ligand Speciation Diagrams . . . . . . . . . . . . . . . . . . . . 73
3.3 Phase Stability Diagrams. . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
3.3.1 Steps to Making Stability Diagrams. . . . . . . . . . . . . 78
3.3.2 Precipitation Diagrams . . . . . . . . . . . . . . . . . . . . . . 86
Reference. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
4 Rate Processes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
4.1 Chemical Reaction Kinetics. . . . . . . . . . . . . . . . . . . . . . . . . . 89
4.1.1 Reaction Rate Concepts . . . . . . . . . . . . . . . . . . . . . 89
4.1.2 Determination of the Reaction Order and the
Forward Reaction Rate Constant . . . . . . . . . . . . . . . 90
4.1.3 Equilibrium and Reversibility . . . . . . . . . . . . . . . . . 92
4.1.4 Effect of Temperature on Chemical Reaction
Kinetics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
4.1.5 Determine the Activation Energy for the
Adsorption Process. . . . . . . . . . . . . . . . . . . . . . . . . 96
4.2 Biochemical Reaction Kinetics. . . . . . . . . . . . . . . . . . . . . . . . 97
4.3 Electrochemical Reaction Kinetics . . . . . . . . . . . . . . . . . . . . . 99
4.3.1 Electrochemical Reaction Rate Theory (Butler-
Volmer Kinetics) . . . . . . . . . . . . . . . . . . . . . . . . . . 99
4.3.2 Electrochemical Rate Measurements. . . . . . . . . . . . . 103
4.4 Mass Transport. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111
4.4.1 Ion Mass Transport. . . . . . . . . . . . . . . . . . . . . . . . . 111
4.4.2 Diffusion for Fast Moving, Thin Reaction Zones . . . 113
4.4.3 Diffusion for Slow Moving or Stationary Reaction
Zones. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114
4.4.4 Identifying Mass Transport Control . . . . . . . . . . . . . 119
4.5 Combined Mass Transport and Reaction Kinetics . . . . . . . . . . 119
4.5.1 ApplicationofMassBalancingtoDifferentReactor
Types. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 120
4.6 Models for Reactions Involving Particles . . . . . . . . . . . . . . . . 123
4.6.1 Mixed-Control Kinetic Models Involving Particles
or Surfaces. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123
4.6.2 Shrinking-Core Particle Kinetic Model (Inner
Diffusion and Reaction Control) . . . . . . . . . . . . . . . 124
4.6.3 Inner Diffusion Controlled Rate Model . . . . . . . . . . 129
4.6.4 Outer (Boundary Layer) Diffusion Controlled Rate
Model for Small Particles . . . . . . . . . . . . . . . . . . . . 130
4.6.5 Outer (Boundary Layer) Diffusion Controlled Rate
Model for Large Particles . . . . . . . . . . . . . . . . . . . . 130
4.6.6 Outer (Boundary Layer) Diffusion Controlled Rate
Model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 130
Contents ix
4.6.7 Inner Diffusion with Pore Properties Variations . . . . 131
4.6.8 Surface Reaction Controlled Rates Involving
Particles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 131
4.6.9 Simple Diffusion of Solute from a Porous Sphere. . . 131
4.6.10 Combined Model Weighting for Ore Leaching
Applications. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 132
4.7 Electrochemical Kinetics . . . . . . . . . . . . . . . . . . . . . . . . . . . . 135
4.8 Crystallization Kinetics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 137
4.9 Overview of Surface Reaction Kinetics . . . . . . . . . . . . . . . . . 139
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 142
Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 143
5 Metal Extraction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 145
5.1 General Principles and Terminology. . . . . . . . . . . . . . . . . . . . 145
5.1.1 Permeability and Fluid Flow Through Particle
Beds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149
5.1.2 In-Situ Leaching. . . . . . . . . . . . . . . . . . . . . . . . . . . 154
5.1.3 Dump Leaching . . . . . . . . . . . . . . . . . . . . . . . . . . . 155
5.1.4 Heap Leaching . . . . . . . . . . . . . . . . . . . . . . . . . . . . 156
5.1.5 Modeling Heap and Dump Leaching
Performance. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 162
5.1.6 Solution Application Techniques . . . . . . . . . . . . . . . 165
5.1.7 Commercial Heap Leaching Applications. . . . . . . . . 165
5.2 Bioleaching/Biooxidation. . . . . . . . . . . . . . . . . . . . . . . . . . . . 169
5.2.1 Commercial Bioleaching Applications . . . . . . . . . . . 175
5.3 Precious Metal Leaching Applications . . . . . . . . . . . . . . . . . . 175
5.3.1 Cyanide Leaching. . . . . . . . . . . . . . . . . . . . . . . . . . 176
5.3.2 Other Precious Metal Extractants. . . . . . . . . . . . . . . 179
5.4 Extraction from Concentrates. . . . . . . . . . . . . . . . . . . . . . . . . 182
5.4.1 Concentrate Leaching . . . . . . . . . . . . . . . . . . . . . . . 182
5.4.2 Ambient Pressure Concentrate Leaching. . . . . . . . . . 183
5.4.3 Agitated Leaching of Gold Ores
and Concentrates . . . . . . . . . . . . . . . . . . . . . . . . . . 183
5.4.4 Miscellaneous Atmospheric Pressure Leaching
Methods. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 184
5.4.5 Pressure Leaching of High Grade Ores
and Concentrates . . . . . . . . . . . . . . . . . . . . . . . . . . 187
5.4.6 Elevated Pressure Commercial Aluminum
Ore Leaching . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 188
5.4.7 Sulfide Mineral Concentrate Pressure Oxidation . . . . 190
5.4.8 Commercial Scale Nickel Concentrate Leaching. . . . 191
5.4.9 Uranium Ore Pressure Leaching . . . . . . . . . . . . . . . 191
5.4.10 Opportunities for Hydrometallurgical Recycling
of Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 191
x Contents
5.4.11 Extraction of By-Products . . . . . . . . . . . . . . . . . . . . 192
5.4.12 Rare Earth Elements (REEs) Leaching. . . . . . . . . . . 192
5.4.13 Acid Baking. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 193
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 193
Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 195
6 Separation of Dissolved Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . 197
6.1 Liquid–Liquid or Solvent Extraction . . . . . . . . . . . . . . . . . . . 197
6.1.1 Types of Liquid–Liquid or Solvent Extractants. . . . . 199
6.1.2 General Principles of Solvent Extraction . . . . . . . . . 200
6.2 Ion Exchange . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 215
6.2.1 General Ion Exchange Information. . . . . . . . . . . . . . 215
6.2.2 Equilibrium Ion Exchange Adsorption Models . . . . . 218
6.2.3 Ion Exchange Adsorption Kinetics Models. . . . . . . . 220
6.3 Activated Carbon Adsorption. . . . . . . . . . . . . . . . . . . . . . . . . 222
6.4 Ultrafiltration or Reverse Osmosis . . . . . . . . . . . . . . . . . . . . . 227
6.5 Precipitation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 228
6.5.1 Process and Waste Water Treatment . . . . . . . . . . . . 229
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 230
Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 231
7 Metal Recovery Processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 233
7.1 Electrowinning . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 233
7.2 Electrorefining . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 246
7.3 Cementation or Contact Reduction. . . . . . . . . . . . . . . . . . . . . 249
7.4 Recovery Using Dissolved Reducing Reagents . . . . . . . . . . . . 250
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 252
Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 253
8 Metal Utilization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 255
8.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 255
8.2 Batteries. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 255
8.2.1 Primary Batteries (Non-rechargeable). . . . . . . . . . . . 256
8.2.2 Secondary Batteries (Rechargeable Batteries) . . . . . . 257
8.2.3 General Battery Information . . . . . . . . . . . . . . . . . . 260
8.3 Fuel Cells. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 260
8.4 Electroless Plating. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 264
8.5 Electrodeposited Coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . 266
8.6 Electroforming . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 267
8.7 Electrochemical Machining . . . . . . . . . . . . . . . . . . . . . . . . . . 268
8.8 Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 269
8.8.1 Uniform Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . 270
8.8.2 Pitting Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . 270
8.8.3 Crevice Corrosion. . . . . . . . . . . . . . . . . . . . . . . . . . 272
8.8.4 Galvanic Corrosion. . . . . . . . . . . . . . . . . . . . . . . . . 272