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 Edited by
SAMUEL WAGSTAFF
The Minerals, Metals & Materials Series
Samuel Wagstaff
Editor

Light Metals 2024

123
Editor
Samuel Wagstaff
Oculatus Consulting
Marietta, GA, USA

ISSN 2367-1181 ISSN 2367-1696 (electronic)

The Minerals, Metals & Materials Series
ISBN 978-3-031-50307-8 ISBN 978-3-031-50308-5 (eBook)
https://doi.org/10.1007/978-3-031-50308-5
© The Minerals, Metals & Materials Society 2024

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Preface

It is with great pleasure and honor that I present to you the Light Metals 2024 proceedings.
This collection of manuscripts serves as a time capsule for later researchers to not only see
how we approach technical problems but also what we value and esteem as an industry. The
challenges the industry faces today around energy efficiency and sustainability represent
difficult obstacles not unlike those faced by our forefathers previously. By contributing to
these proceedings, authors have committed themselves to advancing the collective whole
of the industry over any individual gain. The problems we face today are more than any one of
us can handle individually. The key does not lie in a single technological breakthrough,
derivation, or calculation. Instead, as we look at the exciting breakthroughs happening around
us today, we can see that it is through cross-industry collaboration that the greatest strides are
made. This is largely the magic of TMS. Each year we gather as an industry to discuss
contributions we have all made to making things better than they were the year before.
The Light Metals 2024 proceedings embody countless hours of work supplied by the
volunteer Symposium Organizers, Session Chairs, Reviewers, and TMS staff who labor
tirelessly to bring this tome into fruition each year. Of course, this collection of articles would
be empty without the contribution of the individual authors, whose work brings us together
this year. Special thanks and acknowledgment also go out to the symposium chairs of the five
technical symposia assembled for 2024. I would like to offer my personal thanks to Michael
Coley, Nabeel Aljallabi, Julien Lauzon-Gauthier, Anne Kvithyld, Tao Wang, Christopher
Hutchinson, Sazol Das, and Timothy Langan. Without their invaluable help, none of this
would have happened. The consistent guiding efforts of TMS staff have been integral as
always this year. Patricia Warren and Trudi Dunlap were there every step of the way making
sure that neither deadlines nor quality were allowed to slip.
There are exciting times ahead. With unprecedented expansion projects, bold sustainability
targets, and expanding markets, I cannot wait to see the new developments about to touch off.
I invite you all to read these proceedings with a spirit of growth and collaboration in your
heart. As you seek to create partnerships and discuss these proceedings with colleagues, I hope
we will continue to see great leaps in science and innovation.

Samuel Wagstaff

v
Contents

Part I Alumina & Bauxite

Chemical Thermodynamics and Reaction Kinetics of Bayer Process
Desilication . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
Hong Peng, James Vaughan, Sicheng Wang, John Vogrin,
and Dilini Seneviratne
Challenges with Characterizing and Processing Goethite-Rich Jamaican
Bauxites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
Michael Coley, Anthony Greenaway, Alicia Buckley, Khadeen Henry,
Jheanell James, and Jason Brown
Sugar-Derived Causticization Additives for the Bayer Process . . . . . . . . . . . . . . . 24
Amit Desai, Jun Su An, and LoongYi Tan
Unveiling the Potential: A Paradigm Shift in Energy Reduction at Hindalco
Renukoot Alumina Refinery . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
Paul Gupta and Nitya Nand Roy
An Innovative Approach to Smelter-Grade Alumina Calcination Using
Renewable Energy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
M. Wheatland, J. Fu, Y. Xia, M. E. Boot-Handford, and M. Sceats
Numerical Simulations for Performance Optimization of Circulating
Fluidized Bed Calciner . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
Bharathesh Kumar, Abhishek Seth, Chandrakala Kari, Vilas Tathavadkar,
Ashish Mishra, and Prasanta Bose
Improving the Operational Availability of Hydro Alunorte Calciners
by Proper Refractories Maintenance Management . . . . . . . . . . . . . . . . . . . . . . . . 54
Mariana A. L. Braulio, Thais A. Novais, Thiago Macedo, Veridiano Gomes,
Jessika Silva, Thiago Iwanaga, and Victor C. Pandolfelli
Bauxite Processing Via Sulfide Chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
Caspar Stinn, Lucas Marden, Ethan Benderly-Kremen, William Gilstrap,
and Antoine Allanore
Study on a New Method of Clean Production of Alumina by Calcification
Transformation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
Ting-an Zhang, Guozhi Lyu, Yan Liu, and Yiyong Wang
Comparative Economic Efficiency of Processing High-Potassium
Aluminosilicate Raw Materials into Alumina and Related Products . . . . . . . . . . . 82
R. A. Seitenov, V. A. Lipin, S. N. Akhmedov, and V. V. Medvedev

vii
viii Contents

Development of a Hydrometallurgical Process to Obtain High-Purity

Alumina Using Bauxite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
Bárbara da Rocha Pereira, Morgana Rosset, Amilton Barbosa Botelho Junior,
and Jorge Alberto Soares Tenório
Research of Cleaner Production of Alumina and Harmless Utilization
of Red Mud . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99
He Xin, Lv Guo-zhi, Zhang Ting-an, Wang Song, and Wang Long
Sustainable Valorization of Bauxite Residue (“Red Mud”): Exploring
the Potential of H2 Reduction for Multi-metal Recovery . . . . . . . . . . . . . . . . . . . . 110
Ganesh Pilla, Tobias Hertel, and Yiannis Pontikes
Dealkalinization Effect of Carbon Dioxide in Flue Gas on Bayer Red Mud . . . . . 118
Chaojun Fang, Yihong Jia, Ruixue Lou, Yongping Wang, Xiaowei Deng, and Bo Lv
Pilot Study on the Recovery of Iron from High-Iron Red Mud by Vortex
Smelting Reduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123
Xiaofei Li, Ting-an Zhang, Guozhi Lv, and Kun Wang

Part II Aluminum Alloys: Development and Manufacturing

New 6xxx Al–Mg–Si Alloy with High Electric Conductivity and Great
Bendability for EV Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 131
Gregor Michael, Josef Berneder, and Roland Lorenz
Effects of Alloying Elements Content on Microstructural Properties
of AlMgSiCu Alloy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 137
Osman Halil Çelik, Onuralp Yücel, Senem İsçioğlu,
and Mustafa Demirkazık
Influence of Feedrate on Microstructure and Hardness of Conventionally
Spin-Formed 6061-O Plate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149
Andrew Boddorff, Cecilia Mulvaney, and Wesley Tayon
Influence of Copper Addition on the Thermal Stability and Corrosion
Behavior of Aluminum 6082 Alloy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 159
İlyas Artunç Sarı, Görkem Özçelik, İbrahim Bat, Alptug Tanses,
and Zeynep Tutku Özen
Corrosion Effect on Mechanical Properties of Stamped Al Alloy 6451
for Auto Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 165
M. Abdul, W. Shen, Lance Ying, and H. Hu
Effect of Shot Peening and High-Temperature Shot Peening
on the High Cycle Fatigue of 7010-T7452 Aluminum Alloy . . . . . . . . . . . . . . . . . . 171
Abouthaina Sadallah, Hong-Yan Miao, Benoit Changeux, Elie Bitar-Nehme,
Apratim Chakraborty, Sylvain Turenne, and Etienne Martin
X-Ray Computed Tomography of Fracture Paths in AA7075-T6 Sheet
Torn at 200 °C . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 177
Danny Nikolai, Philip Noell, and Eric Taleff
Utilizing Magnetic Field Annealing to Enhance the Microstructure
and Mechanical Properties of 7075 Aluminum Alloy . . . . . . . . . . . . . . . . . . . . . . . 185
Damilola Alewi, Kirk Lemmen, Haluk Karaca, and Paul F. Rottmann
Contents ix

Investigating the Potential of Secondary Aluminum Cast Alloys Used

as Wrought Alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 191
Patrick Krall and Stefan Pogatscher
Creative Approaches to Long-Term Recycling of Aluminium Scrap Forming
AlSiMgMnCu Alloy with Excellent Mechanical and Microstructural
Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 196
Safaa El-Nahas, Ahmed S. Aadli, and Hassan M. Salman
High-Throughput Compositional Study of 3xxx Al Alloy Using Laser
Synthesis and Small-Scale Rolling: A Case Study . . . . . . . . . . . . . . . . . . . . . . . . . 206
Qingyu Pan, Monica Kapoor, John Carsley, and Xiaoyuan Lou
Enhancing Recycling Efficiency and Critical Raw Material Substitution
in 6xxx Alloys’ Production with Respect to Their Extrusion Feasibility
and Mechanical Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 215
Zeynep Tutku Özen, İlyas Artunç Sarı, İrem Yaren Siyah, Alptuğ Tanses,
Görkem Özçelik, Ali Hakan Nurten, Baris Özdemir, and Melih Caylak
Influence of Solidification Rate and Impurity Content on 5/7-Crossover
Alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 226
Sebastian Samberger, Lukas Stemper, Peter J. Uggowitzer, Ramona Tosone,
and Stefan Pogatscher
Influence of Increased Fe, Cu, and Zn Concentrations on Phase Formation
in Aluminum A356 (AlSi7Mg0.3) Alloy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 234
T. Beyer, R. Kleinhans, M. Rosefort, S. Klan, A. Siemund, P. Decker, and W. Volk
AMAG CrossAlloy®—Lightweighting the Future by Unconstraint Alloy
Design: A Case Study . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 241
Lukas Stemper, Florian Schmid, and Ramona Tosone
Correlation of Thermodynamic Calculations and Mechanical Properties
of an Al-Si Cast Alloy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 248
A. Siemund, P. Decker, T. Beyer, and M. Rosefort
Design and Characterization of Hierarchically-Strengthened, Cast
Al-Ce-Ni-Mn-Sc-Zr Alloys for High-Temperature Applications . . . . . . . . . . . . . . . 255
Clement N. Ekaputra, Jovid U. Rakhmonov, Ekin Senvardarli, David Weiss,
Jon-Erik Mogonye, and David C. Dunand
Investigation Effect of In-Situ Grain Refiners on the 1XXX and 3XXX Twin
Roll Casted Aluminum Products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 263
Tuğçe Sezen, Sergen Belit, Fatmanur Özel, Altay Başaran, Bilal Demir,
and Sadık Kaan İpek
Developing Banding Microstructures in Directional Solidification
of Aluminum Metal Matrix Composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 268
Jaime Perez Coronado, Shanmukha Kiran Aramanda, Jonathan Goettsch,
Ashwin J. Shahani, and Alan Taub
Investigation of Ripple Formation in Aluminum Flat Products Produced
by Different Types of Twin Roll Casters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 273
Fatmanur Özel, Altay Başaran, Sergen Belit, Sadık Kaan İpek, and Bilal Demir
Effect of Shot Peening on Fatigue Properties of A20X Fabricated by Laser
Powder Bed Fusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 278
Heidar Karimialavijeh, Apratim Chakraborty, Martin Proebstle, and Etienne Martin
x Contents

Investigations on the Solid-State Additive Manufacturing of Al Alloy: Process,

Microstructure, and Crystallographic Texture . . . . . . . . . . . . . . . . . . . . . . . . . . . . 285
Abhishek Pariyar, Evren Yasa, Adrian Sharman, and Dikai Guan
Evaluating Three-Point Bending Behavior of Aluminum Extruded Thin
Walled Structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 293
Melih Çaylak, Görkem Özçelik, Berat Bayramoğlu, and Tolgahan Çalı
Meshfree Process Modeling and Experimental Validation of Friction Riveting
of Aluminum 5052 to Aluminum 6061 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 298
Lei Li, Mayur Pole, Hrishikesh Das, Sridhar Niverty, Md Reza-E-Rabby,
Jorge F. Dos Santos, and Ayoub Soulami
Influence of Welding Tool Material and Type of Joint on the Formability
of Friction Stir Welded Tailored Blanks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 306
M. Bachmann, R. Göbel, K. R. Riedmüller, and M. Liewald
Parameters Controlling Drilling and Tapping Characteristics of Aluminum
Based Alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 313
H. Barakat, Y. Zedan, A. M. Samuel, V. Songmene, and F. H. Samuel
Determining the Corrosion Speed of Welded AA 5005 Alloy with AA5356
Filler Metals According to Weld Rate Using the MIG Welding Technique . . . . . . 326
Hüseyin Müştak, Yusuf Özçetin, and Günhan Bayrak
Investigating the Corrosion Performance of EN-AW-8006 Alloy with Mn
and Cu Additions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 335
Ece Harputlu, Cemil Işıksaçan, Mert Günyüz, and Erdem Atar
Annealing Behavior of Cold Rolling Sheets of a Continuous Cast Al-1.5Cu
Alloy with Potential Application to Low-Cost Auto Forming Parts or Sheets . . . . 341
Xiyu Wen, Yan Jin, and Wei Li
Effect of Annealing Process on Recrystallization Structure, Texture,
and Precipitates of 1235D Aluminum Sheets . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 350
Wei Tang, Junpeng Pan, Zhisheng Guo, Hongpo Wang, and Zizong Zhu
Comparison of Heating Systems for Aluminum Forging . . . . . . . . . . . . . . . . . . . . 356
Nurcan Akduran, Ahmet Asım Eser, Ahmet Umit Cakal, and Mustafa Acarer
Effect of Cold Rolling Prior to Homogenization Heat Treatment
on the Microstructural Evolution and Mechanical Properties of Twin-Roll
Cast 8026 Aluminum Alloy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 362
Ahmet Kabil, Hatice Mollaoğlu Altuner, and Onur Meydanoglu
Influence of T6 and T7 Heat Treatments on the Mechanical Properties
of Rheocast Secondary AlSi7Cu3Mg Alloy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 369
Giulio Timelli, Stefano Capuzzi, and Giulia Scampone
Heat Treatment of A20X Alloy Manufactured Using Laser Powder Bed
Fusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 376
Heidar Karimialavijeh, Apratim Chakraborty, Martin Proebstle, Kentaro Oishi,
Jean-Philippe Harvey, and Etienne Martin
Thermomechanical and Metallographic Comparison of Twin-Roll CAST 1235,
3003, 8006, and 8079 Alloy Series Used in the Production of Foil
Manufacturing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 383
Sergen Belit, Tuğçe Sezen, Altay Başaran, Fatmanur Özel, and Sadık Kaan İpek
Contents xi

The Effect of Cold Rolling Strain Degree in Corrosion Resistance of Fully

Soft Temper Automotive 5182 Alloy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 391
Dionysios Spathis, John Tsiros, Andreas Mavroudis,
and Athanasios Vazdirvanidis
Effect of Silicon Content on Solidification Parameters and Microhardness
of Al–Si Alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 399
Edgar R. Ibañez, Carlos D. Rodríguez, Paula R. Alonso, and Alicia E. Ares

Part III Aluminum Reduction Technology

Aluminium Carbide and Carbon Dust in Aluminium Electrolysis
Cells—A Conceptual Model for Loss in Current Efficiency . . . . . . . . . . . . . . . . . . 411
Asbjørn Solheim
A Method of Cell Heat Balance Control to Enable Variable Power Usage
by Aluminium Smelters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 419
Nick B. Depree, Yashuang Gao, Mark P. Taylor, and John J. J. Chen
Computational Simulation of Electromagnetic Fields in an Aluminum
Electrolysis Cell . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 427
Ryan M. Soncini
A Method for Anode Effect Prediction in Aluminum Electrolysis Cells Based
on Multi-scale Time Series Modeling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 436
Kejia Qiang, Jie Li, Jinghong Zhang, Jiaqi Li, Ling Ran, and Hongliang Zhang
Predicting Electrolyte and Liquidus Temperatures of Aluminium Smelting
Cells for Power Modulation Using Dynamic Model . . . . . . . . . . . . . . . . . . . . . . . . 445
Choon-Jie Wong, Jie Bao, Maria Skyllas-Kazacos, Barry Welch, Jing Shi,
Nadia Ahli, Amal Aljasmi, Mohamed Mahmoud, and Mustafa Mustafa
Construction and Application of Digital Twin in Aluminum Electrolysis . . . . . . . 453
Jiaqi Li, Kejia Qiang, Chunhua Yang, Xiaofang Chen, Jie Li, and Hongliang Zhang
Estimation of the Spatial Alumina Concentration of an Aluminium Smelting
Cell Using a Huber Function-Based Kalman Filter . . . . . . . . . . . . . . . . . . . . . . . . 464
Luning Ma, Choon-Jie Wong, Jie Bao, Maria Skyllas-Kazacos, Jing Shi,
Nadia Ahli, Amal Aljasmi, and Mohamed Mahmoud
Limits for the Current Efficiency in Hall-Héroult Cells . . . . . . . . . . . . . . . . . . . . . 474
Asbjørn Solheim
Numerical Modeling of Anode Changes and Their Effect on Current
Distribution and Magnetohydrodynamic Behavior of an Aluminium
Reduction Cell . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 481
Jinsong Hua, Pascal Beckstein, Eirik Manger, Steinar Kolås, Øyvind Jensen,
and Sigvald Marholm
Specific Energy Reduction Through Design Modifications at Aditya
Aluminium Smelter . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 493
Venkannababu Thalagani, Rajeev Kumar Yadav, Shanmukh Rajgire, Amit Jha,
Amit Gupta, Sai Mahati Bottla, Sanjay Pal, Sarthak Mohapatra, Anshu Mangal,
Deepak Dash, Anish Das, Madhusmita Sahoo, Kamal Kant Pandey,
and Vilas Tathavadkar
Thermo-Electrical Analysis of Lying-Bed Patterns During Preheating Phase . . . . 499
Rohini-Nandan Tripathy, Daniel Marceau, Simon-Olivier Tremblay, Duygu Kocaefe,
Antoine Godefroy, and Sébastien Charest
xii Contents

New 32-H Metal Tapping Cycle Implementation at ALBRAS . . . . . . . . . . . . . . . . 508

Camila R. Silva, Franciny Lobato, Benedito Z. Silva, Valfredo C. Filho,
Michel V. Pena, João P. F. Souza, Marcio N. Souza, Pierre Reny, and Kurt J. Nilsson
Re-Usage of Big Butts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 514
Andresa O. Menezes, Camila R. Silva, Marcio N. Souza, Valfredo C. Filho,
Michel V. Pena, João P. F. Souza, Paulo N. Júnior, Nayary P. Monteiro,
and Marcus Brasiliense
Amperage Increase Program and Enablers in EGA Al Taweelah DX Technology
Potlines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 520
Vishal Ahmad, Ishaq Alkharusi, Shaikha Al Shehhi,
and Almero Austin Eybers
Cell Startup and Early Operational Improvements in Albras . . . . . . . . . . . . . . . . 526
Ana Renata M. Nunes, Michel V. Pena, Pierre Reny, George Cardoso, Márcio Souza,
and Ana Carolina Guedes
Metal Tapping Yoke and Platform Modification for Improved Locking
and Unlocking . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 532
Yousuf Al Bastaki, Hassan Al Raqabani, Sajjad Hussain, Adnan Jafar, Sandeep Naik,
Shibu Joseph, Sohail Akram, Zamad Hassan, and Muhammad Saleem
Restart of AP30 Cells at Boyne Smelters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 537
Daniel Whitfield, Murray Ure, Rashmi Jena, Evan Andrews,
and Shashidhar Ghatnatti
Technology of Reducing Carbon Dust Amount in Aluminum Electrolysis
Production with High Lithium Potassium Electrolyte System . . . . . . . . . . . . . . . . 545
Shengzhong Bao, Kaibin Chen, Guanghui Hou, Huaijiang Wang, Yingtao Luo,
Xu Shi, Jing Li, Lifen Luo, Fangfang Zhang, and Changlin Li
Application of SAMI Energy-Saving and Current-Intensifying Technology
in a 330 kA Potline . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 553
Jinlong Hou, Yafeng Liu, Hongwu Hu, Wei Liu, Xuan Wang, Xi Cao,
and Michael Ren
Pot Failure Prediction in EGA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 562
Shaikha Al Shehhi, Satheesh Mani, Jose Blasques, and Yusuf Ahli
SMARTCrane, a Fives’ Digital Solution for Aluminium Production
Optimization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 568
Vincent Delcourt, Clement Pessemesse, Vianney Boyer, Jean-Paul Leroy,
and Frederic Moreira Pereira
A Review of Challenges and Solutions in Ledge Control and Measurement
in Aluminium Electrolysis Cell . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 577
Bazoumana Sanogo, Lukas Dion, Sébastien Gaboury, László Kiss, Thomas Roger,
Sébastien Guérard, and Jean-François Bilodeau
Accurate Measurement of Anode Current in Aluminum Electrolysis:
From Ideal to Reality . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 586
Yi Meng, Jun Tie, Chun Li, Rentao Zhao, Hongwei Jiang, Xingzu Peng,
Hao Xiao, Dongwei Liu, and Jun Lei
Contents xiii

Correlation Between Corrosion Rate and Electrochemical Parameters

of Anode Process on the Metallic Electrode in Molten Oxyfluorides . . . . . . . . . . . 596
Andrey Yasinskiy, Thomas Jamieson, Kamaljeet Singh, Guðmundur Gunnarsson,
Jon Magnússon, Dominic Feldhaus, Roman Düssel, Isabella Gallino,
and Bernd Friedrich
Direct Production of Al-Mn Alloys During the Electrodeposition of Aluminum
in a Laboratory Cell . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 602
Omar Awayssa, Geir Martin Haarberg, Gudrun Saevarsdottir,
and Rauan Meirbekova
Electrowinning of Al-Sc Master Alloys in the LiF-AlF3-Sc2O3 Melts . . . . . . . . . . . 608
Andrey Yasinskiy, Ilya Moiseenko, Dmitriy Varyukhin, Anastasia Saparova,
Aleksandr Samoilo, Pavel Yuryev, Youjian Yang, Zhongning Shi, Zhaowen Wang,
Peter Polyakov, and Bernd Friedrich
Factors Affecting the Performance of Oxygen-Evolving Ni–Fe–Cu Anodes
in Low-Temperature Molten Fluoride Electrolyte for Aluminium
Electrowinning . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 614
Gudrun Saevarsdottir, Geir Martin Haarberg, and Sai Krishna Padamata
Dimensional Analysis Applied to the Dissolution and Disintegration
of Alumina Rafts: The Riddle of Dissolving Alumina Rafts Solved . . . . . . . . . . . . 621
Jonathan Alarie, László I. Kiss, Lukas Dion, Martin Truchon, Sébastien Guérard,
and Jean-François Bilodeau
Fundamental Loss of Current Efficiency During Aluminium Electrolysis
and Its Correlation with Sodium Content Dissolved in the Aluminium . . . . . . . . . 630
Lukas Dion and Paul Desclaux
Novel Developments for Inert Anodes and Wettable Cathodes in Aluminium
Electrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 639
David J. Jarvis, Rosanna E. van den Blik-Jarvis, Rosie F. L. Mellor, and Alf Bjørseth
Online Monitoring of Metal Oxides in Molten Fluoride Electrolytes . . . . . . . . . . . 648
Wojciech Gebarowski, Samuel Senanu, Arne Petter Ratvik, Ole Kjos,
Henrik Gudbrandsen, and Egil Skybakmoen
Smelting 4.0: Digital Strategy for Aluminum Production . . . . . . . . . . . . . . . . . . . 655
Ved Prakash Rai and Datta Raju D
Study of the Degradation of Ordinary Refractory Bricks in an Aluminum
Reduction Cell . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 664
Mohamed Hassen Ben Salem, Gervais Soucy, Daniel Marceau, Antoine Godefroy,
and Sébastien Charest
Cradle-to-Gate Carbon Footprint Assessment of Graphite Cathode
for Aluminium Electrolysis Pots . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 671
T. Carrère, B. Allard, and T. Reek
Influence of Low Temperature on the Surface and Morphological
Properties of Hydrated Lime in SO2 Desulfurization Reaction . . . . . . . . . . . . . . . 680
Karthikeyan Rajan, Duygu Kocaefe, Yasar Kocaefe, Julie Bureau, Jonathan Bernier,
Yoann Robert, and Yves Dargis
xiv Contents

Preliminary Testing and Simulations of Pot Integrated Abart (PIA)

at Alcoa Mosjøen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 688
Asbjørn Solheim, Anders Sørhuus, Ole S. Kjos, Håvard Olsen,
and Helene M. E. Granlund
Sustainability of Different Aluminium Production Technologies . . . . . . . . . . . . . . 696
Samuel Senanu, Mona Hassel, Asbjørn Solheim, and Egil Skybakmoen
Thermal Analysis of Operational Events Affecting Electrolysis Cells
and Their Local Alumina Dissolution Conditions . . . . . . . . . . . . . . . . . . . . . . . . . 703
Ali Kodfard, Lukas Dion, Thomas Roger, Sébastien Guérard,
and Jean-François Bilodeau
Industrial Experimental Study on High Efficiency Recovery Technology
of Side Waste Heat in Aluminum Electrolytic Cells . . . . . . . . . . . . . . . . . . . . . . . . 714
Yanan Zhang, Yang Zhang, Qiang Yu, Guisheng Liang, Guanghui Hou,
Yuechao Guan, and Junqing Wang
Regeneration of Aluminum Fluoride From Pure Bath . . . . . . . . . . . . . . . . . . . . . . 723
Brian Zukas and Xiangwen Wang
Low Carbon Emission Technology Upgrading Industrial Pilot of 350kA Pots . . . . 730
Tiejun Wang, Yafeng Liu, Guijun Ge, Shimin Qu, Mingzhu Zhou, Hailong Liu,
Wei Zhu, Yuanbing Zhu, Hongwu Hu, Xi Cao, and Michael Ren
MHD Stability of Aluminium Cells—Cathode Design Effects . . . . . . . . . . . . . . . . 746
Valdis Bojarevics and Marc Dupuis
Modelling and Design of the Cathode Block Assembly Using Different
Types of Models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 754
Marc Dupuis, Xianan Liao, and Nyah Ren
Cathode Inspection and Repair Procedure Improvements in ALBRAS . . . . . . . . . 766
Ana Carolina A. Guedes, Marvin Bugge, Michel V. Pena, Marcio N. Souza,
Ana Renata N. Monteiro, and Adalberto Pastana
Combining New and Old Cathode Block Assembly to Increase
the Lifetime of Pot at INALUM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 773
Kukuh Yudiarto, Rainaldy Harahap, Ade Buandra, Ari Purwanto,
and Ferdy Rahadian
Design and Trial of Electrical Collector Plate in Cathode Assemblies . . . . . . . . . . 779
Guorong Cao and Hao Zhang
Determination of the Air-Gap Distribution at the Cast Iron to Carbon
Cathode Interface Using a 3D Scanning Approach . . . . . . . . . . . . . . . . . . . . . . . . 786
Omolbanin Saeidi, Simon-Olivier Tremblay, Daniel Marceau, Antoine Godefroy,
and Sébastien Charest

Part IV Electrode Technology for Aluminum Production

Alternative Binder for Carbon Anode . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 797
Sheetal Gupta, Dibyendu Ghosh, Bibhuti Sahu, Amit Gupta,
and Vilas Tathavadkar
Contents xv

Effect of Mixing and Pressing Parameters on the Properties of Biopitch-Based

Lab-Scale Carbon Anodes for Use in the Hall-Héroult Electrolytic Cell . . . . . . . . 804
Nooshin Baastani, Simon Laliberté-Riverin, Marie-Aimee Tuyizere-Flora,
Guillaume Gauvin, Julien Lauzon-Gauthier, Thierry Ollevier,
and Houshang Alamdari
CFD Modelling of Air Injection Nozzles in Coke Calcination Kilns, Identification
of the Best Compromise Between Carbonaceous Deposit Formation
and Kiln Performance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 815
Marie-Josée Dion, Hans Darmstadt, Louis-Michel Malouin, Eric Duplain,
Debbie Soriano, and Sunny Huang
Estimation of the Coke Calcination Yield by Granulometry Analysis . . . . . . . . . . 822
Hans Darmstadt, Marie-Josée Dion, André Bouchard, and Luc Coté
Comparing Handling Degradation of Shaft and Rotary Cokes . . . . . . . . . . . . . . . 828
Howard Childs, Austin Andrian, Barbara Chu, and Barry Sadler
Influence of Selective Crushing and Particle Shape of Shaft and Hearth
Calcined Anode Coke Components on Blend Bulk Density . . . . . . . . . . . . . . . . . . 834
Howard S. Childs, Barry Sadler, and Barbara Chu
Effect of Boron on the Evolution of Petroleum Coke Active Pore Size
Under Air Oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 841
Ramzi Ishak, Francois Chevarin, Gaétan Laroche, Donald Ziegler,
and Houshang Alamdari
Measurement of SO3 in Flue Gas from Anode Baking Furnace . . . . . . . . . . . . . . 850
Ole S. Kjos, Thomas Park Simonsen, and Thor Aarhaug
Performance Improvement of the Anode Baking Process in Horizontal
Furnaces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 856
Emmily Fonseca, Marcus Brasiliense, Paulo Teixeira, Leonardo Campos,
Fernando Von Schaffelw, Paulo Nogueira, Alexandre Aquino, and Douglas Almeida
Study on the Protection Technology Against Aluminized Surface of Anode
Stub for Aluminum Electrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 865
Shengzhong Bao, Dongsheng Li, Guanghui Hou, Kaibin Chen, Huaijiang Wang,
Jing Li, Xu Shi, Dan Liu, Junyi Ma, and Huiyao Wang

Part V Melt Processing, Casting and Recycling

Reverberatory Furnaces Decarbonization—The Case of Hydrogen Combustion:
Proof of Concept and First Experimental Results on Borel Furnace . . . . . . . . . . . 873
Louis Piquard, Emilien Clément, Martin Adendorff, Esin Iplik, and Tomas Ekman
Decarbonization of Aluminum Reverberatory Furnaces: The Case of Plasma
Melting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 881
Juan E. Salazar, Louis Piquard, Simon Vecten, and Emilien Clement
Influence of Water Vapor on the Oxidation Behavior of Molten Aluminum
Magnesium Alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 890
Stefan Tichy, Simon Doppermann, Philip Pucher, Bernd Prillhofer, Stefan Wibner,
and Helmut Antrekowitsch
Dissolution Rates of Various Manganese Alloying Elements in Aluminium . . . . . . 897
Anne Kvithyld, Sarina Bao, Martin Syvertsen, Arne Petter Ratvik, Kjerstin Ellingsen,
Mehdi Maghsoudi, and Kristján Leósson
xvi Contents

Results Achieved with the Application of Optifine High Efficiency Grain

Refiner in the Production of AA5182 Can Lid Stock . . . . . . . . . . . . . . . . . . . . . . . 905
John Courtenay, Lei Shi, JunJun Xia, and Zhao Weitiao
Efficient Molten Metal Transfer in the Cast House: Introducing a New Thermal
Insulation Solution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 912
Alireza Hekmat, Alain Simard, Bo Jin, and Michael Mastor
An Estimation of Scrap Melting Rates by an Inverted Chvorinov Method . . . . . . 922
S. R. Wagstaff, R. B. Wagstaff, and A. Anestis
Recovery Considerations in the Pyrometallurgical Recycling of Used Beverage
Cans . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 929
Theofani Tzevelekou, Malamatenia Koklioti, Athanasia FIampouri,
Nikolaos Chamakos, Ioannis Contopoulos, Alexandros Anestis, Grigorios Galeros,
Epameinondas Xenos, and Andreas Mavroudis
Optimization of Boron Treatment for Production of 1370 Electrically
Conductive Grade Aluminum Alloy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 941
Shahid Akhtar, Massoud Hassanabadi, and Ragnhild E. Aune
LAlum—Standardization of Launder Systems for Aluminum Casting . . . . . . . . . 952
Michel J. Quintiano and José G. Hernandez
Silicon Depletion in Ceramic Foam Filters (CFFs) during Aluminium Melt
Filtration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 962
Are Bergin, Robert Fritzsch, Shahid Akhtar, Lars Arnberg, and Ragnhild E. Aune
A PoDFA Benchmarking Study Between Manual and AI-supervised
Machine Learning Methods to Evaluate Inclusions in Wrought
and Foundry Aluminum Alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 970
Pascal Gauthier, Vincent Bilodeau, and John Sosa
Automated Metal Cleanliness Analyzer (AMCA): Improving Digital Image
Analysis of PoDFA Micrographs by Combining Deterministic Image
Segmentation and Unsupervised Machine Learning . . . . . . . . . . . . . . . . . . . . . . . 977
Hannes Zedel, Eystein Vada, Robert Fritzsch, Shahid Akhtar, and Ragnhild E. Aune
Elemental Analysis and Classification of Molten Aluminum Alloys by LIBS . . . . . 984
A. Demir, D. K. Ürk, K. Akben, M. Doğan, E. Pehlivan, Ö. Yalçın, M. A. Kıştan,
G. Gökçe, and A. Obalı
Enhancing Quantification of Inclusions in PoDFA Micrographs Through
Integration of Deterministic and Deep Learning Image Analysis Algorithms . . . . 991
Anish K. Nayak, Hannes Zedel, Shahid Akhtar, Robert Fritzsch,
and Ragnhild E. Aune
Formation Kinetics of TiB2 in Aluminum Melt Studied Using Laser-Induced
Breakdown Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 996
Antonio Vazquez Prudencio, Mehdi Maghsoudi, Kristbjorg Anna Thorarinsdottir,
and Kristjan Leosson
On the Importance of Measurement and Process Uncertainty in Certifying
the Quality of Aluminium-Based Products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1002
Varuzan M. Kevorkijan, Sandi Žist, and Lucija Skledar
Characterization of Aluminum Dross Compositions Using Rietveld XRD
Technique, Standardless XRF Method and Carbon Analyzer . . . . . . . . . . . . . . . . 1009
Hussain Al Halwachi
Contents xvii

Thermomechanical Modeling on AirSlip® Billet DC Casting of High-Strength

Crack-Prone Aluminum Alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1015
Bin Zhang and Gary P. Grealy
A Passive Approach to Butt Swell Management . . . . . . . . . . . . . . . . . . . . . . . . . . 1026
S. R. Wagstaff, R. B. Wagstaff, B. Opdendries, A. Anestis, S. Pinis, G. Pashos,
E. Xenos, and A. Mavroudis
Characterization of Cr-Bearing Intermetallics Causing Pinhole Formation
in Twin Roll Cast 8079 Aluminum Alloy Thin Foils . . . . . . . . . . . . . . . . . . . . . . . 1033
Yusuf Özçetin, Ali Ulus, Onur Birbaşar, and Feyza Denizli
Corrosion of EN-AW 3105 Aluminum Strip Produced via Twin-Roll Casting
with a Steel/Copper Roll Pair . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1039
Seval Aksoy Aydın, Ece Harputlu, Hikmet Kayaçetin, Cemil Işıksaçan,
and Erdem Atar
In Situ Experimental Study of the Nucleation and Growth of Fe-Al Based
Intermetallics: An Insight for Designing Next-Generation Recycling
Friendly Aluminium Alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1048
G. Salloum-Abou-Jaoude, K.-H. Cheong, S. Akamatsu, Ph. Jarry,
and S. Bottin-Rousseau
Measurement of the Heat Transfer in the Primary Cooling Area
of a Laboratory Direct Chill Casting Plant for Alloy Design . . . . . . . . . . . . . . . . . 1055
Andreas Weidinger, Sebastian Samberger, Florian Schmid,
and Stefan Pogatscher
Influence of Chemistry and Direct Chill (DC) Casting Parameters
on the Formation of Altenpohl Zone in 5xxx Alloys . . . . . . . . . . . . . . . . . . . . . . . 1062
Akash Pakanati, Snorre Rist, Thomas Hartmut Ludwig, Eystein Vada,
Shiva Talatori, and Jan-Erik Ødegård
Mechanisms of Twin-Roll Caster Tips Degradation . . . . . . . . . . . . . . . . . . . . . . . . 1069
Guillaume Girard, François Veillette, and William Roy
Revolutionizing Slab Casting: Unveiling the Power of AI and Computer
Vision . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1078
Loïc Fracheboud, Julien Valloton, and Frederik Rummens
Study of Vertical Fold Formation on Al–Mg Alloys During Direct Chill
Casting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1085
Marianthi Bouzouni, Theofani Tzevelekou, Spyridon Pinis, Sofia Papadopoulou,
and Andreas Mavroudis
Liquid Alloy Atomistic Modelling Perspective to Al Alloy Design . . . . . . . . . . . . . 1098
Philippe Jarry, Alaa Fahs, and Noel Jakse

Part VI Scandium Extraction and Use in Aluminum Alloys

The Role of New Aluminium-Scandium Alloys for Emission Reduction
in Various Sectors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1105
Thomas Dorin and Timothy Langan
Sc-Containing Al–Si–Mg (6xxx) Alloys for Automotive Extrusions . . . . . . . . . . . . 1111
Avishan Shomali, Timothy Langan, Thomas Wood, and Paul Sanders
xviii Contents

Investigation of the Mechanical Properties of Flat Rolled Products of Aluminium

Alloy Al-Mg-Sc Under Various Deformation Processing Modes . . . . . . . . . . . . . . 1120
Alexander Alabin, Sergey Valchuk, Alexander Krokhin, and Dror Shaked
Effect of Sc and Zr Microalloying on Grain Structure After Hot Deformation
and Brazing in Al–Mn 3xxx Alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1125
Alyaa Bakr, Paul Rometsch, and X.-Grant Chen
Hot Deformation Behavior and Post-brazing Grain Structure of Dilute
Al–(Sc–Zr) Alloys for Brazed Heat Exchangers . . . . . . . . . . . . . . . . . . . . . . . . . . . 1133
Alyaa Bakr, Paul Rometsch, and X.-Grant Chen
Investigating the Influence of Iron Content on the Microstructure
and Mechanical Properties of a High Strength Al-Alloy for Additive
Manufacturing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1141
Matteo Turani, Walter Jannic, Paulo Davi Borges Esteves, Enrico Tosoratti,
Adriaan Spierings, and Markus Bambach
How Can Europe Reduce Offshore Dependence of Its Supply Chain
for Critical Metals like Scandium, Niobium, Strontium, Magnesium,
and Titanium? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1148
Beate Orberger, Henk van der Laan, Carsten Dittrich, Robin Scharfenberg,
Edward Peters, Georges Croisé, Pierre Feydi, Carolin Maier, Richard Schneider,
Bernd Friedrich, Yashvi Baria, Konstantinos Sakkas,
and Christos Georgopoulos
Behavior of Yttrium and Other Impurities in the Production of Scandium
Oxide from Bauxite Residue . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1154
Alexander Suss, Alexander Kozyrev, Natalia Kuznetsova, Alexander Damaskin,
Sergey Pishchalnikov, Andrey Panov, Sergey Ordon, and Oleg Milshin

Author Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1167

Subject Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1173

About the Editor

Samuel Wagstaff is currently a partner at Oculatus Consult-

ing, specializing in aluminum processing and product devel-
opment. He holds degrees in Mechanical Engineering from
Cornell University (B.S.) and Materials Science from MIT
(M.S., Sc.D.). Previously as the Lead Scientist at Novelis, he
led new product and process development for the entire R&D
ecosystem across three continents. Currently, Dr. Wagstaff
focuses on increasing profitability and productivities of non-
ferrous products by process improvement and fundamental
research. He has helped to design over 1 million tons of
recycle capacity in the aluminum sector and is the author of
over 35 patents. Dr. Wagstaff is currently serving as the
principal investigator on a $1M ReMADE grant to develop
technology to improve the recyclability of organic laden alu-
minum scrap and is involved in much of the industrial
expansion of the aluminum sector in North America. In his
private life Sam enjoys being with his wife, hunting, fishing,
and scuba diving.

xix
Program Organizers

Alumina & Bauxite

Michael Coley is a Lecturer and Section Head of the Applied
Chemistry Division, Department of Chemistry, The University
of the West Indies, Mona, Jamaica. He has a Ph.D. in
Chemistry and teaches Industrial, Analytical and Environ-
mental Chemistry. Dr. Coley’s research interests include Air
Quality and Renewable Energy however he is especially
involved in Bayer Process Technology research. His areas of
focus include alumina precipitation, the management of pro-
cess impurities, and the development of strategies for pro-
cessing marginal bauxites. Over the last 20 years, he has
worked on several major projects that involve study of
Jamaican bauxites and has reported on his work at major
conferences and in academic journals. Dr. Coley enjoys
mentoring and is the senior Undergraduate Coordinator for his
Department. He is married and has two daughters.

Aluminum Alloys: Development and Manufacturing

Christopher Hutchinson is a Professor in the Department of
Materials Science and Engineering at Monash University in
Melbourne, Australia, and co-Chair of the Woodside Energy
FutureLab at Monash University. He received his Ph.D. from
the University of Virginia in the USA, and after several
post-doc years at Grenoble Institute of Technology in France,
joined the faculty at Monash. His work covers both the rela-
tionship between processing and structure, and structure and
properties of engineering alloys with a large fraction of his
activities on steels, stainless steels, aluminum, and copper and
brasses. The coupling of modelling and experiment, wherever
possible, is a priority for his approach to problems. Approxi-
mately half of his research is funded in association with
industry and half from fundamental agencies such as the
Australian Research Council. He is an Editor of Acta Mate-
rialia and Scripta Materialia.

xxi
xxii Program Organizers

Sazol Das is an R&D Leader at Novelis Global Research and

Technology Center, Kennesaw, GA, USA. He has over 16
years of experience in Product & Process Development, Dif-
fusion Kinetics, Thermodynamic Modeling, Electronic
Materials Packaging, and Thin Film Coating. Dr. Das grad-
uated from McGill University, Montreal, QC, Canada with a
Doctoral Degree in Materials Engineering. He is a certified
agile Scrum Master and Product Owner who enjoys mentor-
ing, empowering, and inspiring young professionals in their
career advancement.

Aluminum Reduction Technology

Nabeel Al Jallabi has been a Sr. Manager in Process Control
and Development for 30 years with Alba. He has worked in
different disciplines including Reduction Lines, Process Con-
trol and Development, and Operation Support Services. Al
Jallabi has played instrumental roles in many projects including
Reduction Lines 1–3 conversion from side break to point feed
system, Reduction Lines 3 expansion, Reduction Line 5
commissioning, KA increase across Reduction Lines, lean
manufacturing along with the McKinsey team, SPL detoxifi-
cation and recycling project, Reduction Line 6 commissioning,
and Reduction Line 5 restart. Al Jallabi has participated in
many conferences as an author and delegate including TMS,
ICSOBA, and Australasian. Al Jallabi’s educational back-
ground includes a BSc in Mechanical Engineering, MCs in
Aluminum Smelting Technology, and an MBA.

Electrode Technology for Aluminum Production

Julien Lauzon-Gauthier is a Sr. research engineer at Alcoa,
within the Operational Excellence smelting technology
development group. He is responsible for the development
and deployment of new technology and process optimization
linked to anode manufacturing for Alcoa’s carbon plants. He
is a chemical engineer and holds an M.Sc. and Ph.D. from
Université Laval in Canada. His postgraduate work focused
on multivariate statistics and machine vision applied to the
anode manufacturing process. Dr. Lauzon-Gauthier also held
different process engineer roles at Alcoa smelters in Canada
before joining the technology development team. He has
published his work in scientific journals and at the TMS
annual meeting and received the TMS Light Metals Division
Young Leaders Professional Development Award in 2020 as
well as the Electrode Technology best paper award in 2021.
Program Organizers xxiii

Melt Processing, Casting and Recycling

Anne Kvithyld is a senior research scientist at SINTEF,
Norway, where she has been since 2007. Her research interests
are centered around refining and recycling of metals. She
earned her Ph.D. entitled “Thermal Decoating of Aluminium
Scrap” in 2003. She has been a Visiting Post.Doc at the
Colorado School of Mines, USA, and was the winner of the
2011 Vittorio de Nora Award for Environmental Improve-
ments in Metallurgical Industries. She is the co-author and
co-editor of the book Principles of Metal Refining and Recy-
cling published in 2021 and an active member of The Min-
erals, Metals & Materials Society (TMS).

Tao Wang currently holds the position of Technical Mar-

keting Manager-Atlantic at Rio Tinto focusing on aluminum
product development and customer technical support. Before
joining Rio Tinto, he served as a chief metallurgist in the steel
industry. He has over 10 years of experience in product/
market development and has published more than 20 journal
papers and 8 patents related to metal casting, rolling, and heat
treatment. Tao holds a Ph.D. degree in metallurgical engi-
neering from The University of Alabama, and a bachelor’s
degree in materials science and engineering from Jiao Tong
University in China.

Scandium Extraction and Use in Aluminum Alloys

Timothy Langan began his career at Martin Marietta
developing advanced aluminum alloys for space and Marine
applications. He received his Ph.D. in Materials Science from
Johns Hopkins University. Dr. Langan is currently working
with Sunrise Energy Metals to develop applications for
scandium that will be produced from its Sunrise Project in
New South Wales, Australia. In this role, Dr. Langan is
working with industrial partners to guide, develop, and focus
research efforts on aluminum-scandium alloys at universities
including Deakin University, Michigan Technological
University, Monash University, and Chongqing University.
xxiv Program Organizers

Frank Palm is a Senior Expert (1990–present) in metallic

materials and processes focusing on welding and additive
manufacturing for Airbus Central Research & Technology
(CR&T). He is a dedicated and passionate specialist in the
aerospace technology field, including failure analyzes with a
strong current focus on metallic additive manufacturing (laser
powder bed fusion material and process fundamentals), elab-
orating the prospects of Sc in Al-alloy applications for more
than 25 years. Over the past 30 years, he has initiated, written,
contributed, and published nearly 100 presentations and sci-
entific papers. His background includes mentoring, teaching,
and accompanying 12 Airbus in-house Ph.D. theses and about
50 diplomas, masters, and bachelor’s theses. He caused more
than 30 invention filings and Airbus-related patent applica-
tions and, together with Airbus, currently holds more than 15
patents in the field of additive manufacturing, metallic mate-
rials technology, and integral aircraft fuselage constructions
(e.g., Scalmalloy®—AlMgSc alloy concept for Additive
Manufacturing (brand and patent)).
He is a member of the German Engineering Community
(VDI), the American Society of Materials (ASM), and of the
German Welding Society (DVS). In the frame of the publicly
hosted German Research Community (IGF) he has served for
more than 10 years voluntarily as an appointed project con-
sultant and assessor.

Thomas Dorin is a Senior Research Fellow at Deakin

University and the leader of the aluminum research group. Dr.
Dorin has a distinct specialization in the incorporation of
scandium in aluminum alloys.
After gaining his Ph.D. from the University of Grenoble in
2013, Dr. Dorin has been instrumental in the development of
innovative aluminum alloys, with his work leading to multiple
patents and influential research papers. Among his many
accolades, he was awarded the esteemed ICAA16 Early
Career Researcher award in 2018. Additionally, he was rec-
ognized with the Discovery Early Career Researcher Award
by the Australian Research Council in 2019. Dr. Dorin was an
organizer and co-chair of the TMS symposium titled “Scan-
dium Extraction and Use in Aluminum Alloys” in both
TMS2023 and TMS2024. Dr. Dorin has co-authored 47
journal papers, 21 conference papers, 3 book chapters, and
holds 4 patents. Furthermore, his work has been cited over
1800 times, with an h-factor of 22.
Program Organizers xxv

Paul Rometsch obtained his Ph.D. in Materials Engineering

at the University of Queensland, Australia, and has published
widely in the field of aluminum metallurgy. He has held
various academic and industrial positions focused on R&D
within the global aluminum industry, including appointments
at Comalco Aluminium (Australia); the University of
Southampton and the Luxfer Group (UK); Hydro Aluminium
Precision Tubing (Europe and China); and Monash University
(Australia). Since 2018, Paul is has been a Principal Research
Scientist with Rio Tinto Aluminium, where he currently
works on aluminum product metallurgy at the Arvida
Research and Development Centre in Saguenay, Québec
(Canada).

Henk van der Laan is a senior consultant and owner of Van

der Laan International Consultancy BV (V.I.C.). Henk was
born in 1954 in Rotterdam, The Netherlands. Henk has
worked 44 years in the aluminum industry of which 34 years
at KBM Affilips BV as an international sales manager for
specialty alloys and master alloys in the non-ferro industry.
The last 15 years he has been active as specialist for critical
metals like magnesium, titanium, and scandium. Henk studied
Metallurgy in Utrecht and Business Economics in Rotterdam
and Industrial Marketing in Arnhem, all in The Netherlands.
As a metallurgist he specializes in the grain refining mecha-
nism of aluminum titanium boron, which is the main product
of KBM. Besides his passion for aerospace, astronomy, alu-
minum, and scandium, Henk is an active mountain biker,
golfer, and a fan of all kinds of sports like soccer, cycling, and
formula 1.

Efthymios Balomenos studied Mining and Metallurgical

engineering at National Technical University of Athens and
received his Ph.D. degree in Thermodynamics in the same
school in 2006. Since 2008 he has been working in the Lab-
oratory of Metallurgy as a postdoc researcher focusing on
sustainable process development, CO2 mitigation strategies,
exergy analysis, and resource utilization efficiency. He is
involved in the research management and coordination of
several collaborative large scale research projects (ENEXAL,
EURARE, SCALE, ENSUREAL, RemovAl, BIORECOVER,
AlSiCaL, SISAL PILOT, HARARE, and ReActiv) most of
which focus on Bauxite Residue valorization or alumina
production. He has more than 80 research publications in
journals and conference proceedings with more than 1,000
citations and an h-index of 19. Since 2015, he has cooperated
with MYTILINEOS—Metals as a senior consultant on R&D
projects. He was a recipient of the TMS Light Metals Subject
Award – Alumina & Bauxite in 2017 and since 2022 he has
been on ICSOBA’s board of directors.
xxvi Program Organizers

Muhammad Akbar Rhamdhani is currently the Director of

Fluid and Process Dynamics (FPD) Group; and Program
Leader of Net Zero Carbon Materials and Processes (Manu-
facturing Future Research Platform) at Swinburne University
of Technology, Australia. Dr. Rhamdhani is a Professor in
Extractive Metallurgy and Metals Recycling and obtained his
Ph.D. from McMaster University, Canada, in Materials Sci-
ence and Engineering. He was a teaching-research academic
at the Institute of Technology Bandung (ITB) and the
University of Queensland, before joining Swinburne. Dr.
Rhamdhani was a Visiting Professor at Katholieke Univer-
siteit Leuven Belgium and a Visiting Scientist at CSIRO. He
is also currently an Adjunct Professor at the Faculty of
Engineering, Universitas Indonesia.
Dr. Rhamdhani’s research expertise is on advanced
metal/material refining and impurities removal (e.g., in steel,
aluminium, magnesium, silicon, nickel, and minerals);
development of new processes for metal production; ther-
modynamics and kinetics of high temperature metal and
chemical processes; and physical chemistry of interface. Dr.
Rhamdhani’s current research directions include: (1) recycling
and recovery of metals from urban resources (e-waste,
end-of-life alkaline and lithium ion batteries, solar panel,
permanent magnet; (2) decarbonization and hydrogenation of
metallurgical processes; (3) pyrometallurgical processes of
rare earth elements (REE) minerals; (4) solar metallurgy (the
use of concentrated solar thermal energy for minerals and
metals processing); and (5) astro metallurgy (extra-terrestrial
minerals and metals processing; e.g., metals extraction on
Mars and Lunar).
Aluminum Committee 2023–2027

Executive Committee 2023–2024

Chairperson
Stephen Broek, Kensington Technology Inc., Ontario, Canada
Vice Chairperson
Samuel Wagstaff, Oculatus Consulting, Georgia, United States
Past Chairperson
Dmitry Eskin, Brunel University, Middlesex, United Kingdom
Secretary
Kristian Etienne Einarsrud, Norwegian University of Science & Technology, Trondheim,
Norway
JOM Advisor
Anne Kvithyld, SINTEF, Trondheim, Norway
Light Metals Division Chair
Eddie McRae Williams, Arconic, Pennsylvania, United States

Members-At-Large Through 2024

Stephan Broek, Kensington Technology Inc., Ontario, Canada

Kristian Etienne Einarsrud, Norwegian University of Science & Technology, Trondheim,
Norway
Duygu Kocaefe, University of Quebec, Quebec, Canada
Johannes Morscheiser, Novelis Koblenz GmbH, Koblenz, Germany
Alan Tomsett, Rio Tinto Pacific Operations, Queensland, Australia

Members-At-Large Through 2025

Dmitry Eskin, Brunel University, Middlesex, United Kingdom

Linus Perander, Yara International, Sandefjord, Norway
Derek Santangelo, Hatch, Quebec, Canada
Jason Tessier, Alcoa Corporation, Quebec, Canada

xxvii
xxviii Aluminum Committee 2023–2027

Members-At-Large Through 2026

Kristian Etienne Einarsrud, Norwegian University of Science & Technology, Trondheim,

Norway
Mertol Gökelma, Izmir Institute of Technology, Urla, Turkey
Martin Iraizoz, Aluar Aluminum, Puerto Madryn, Argentina
Julien Lauzon-Gauthier, Alcoa Corporation, Quebec, Canada
Pascal Lavoie, Alcoa Corporation, Quebec, Canada
Olivier Martin, Rio Tinto, Saint Jean, France
Ray Peterson, Real Alloy, Tennessee, United States
Andre Phillion, McMaster University, Ontario, Canada
Andre-Felipe Schneider, Hatch, Quebec, Canada
Eddie McRae Williams, Arconic, Pennsylvania, United States

Members-At-Large Through 2027

Houshang Alamdari, Laval University, Quebec, Canada

Evan Andrews, Boyne Smelters Ltd, Queensland, Australia
Samuel Awe, Automotive Components Floby AB, Falköping, Sweden
Sumit Bahl, Oak Ridge National Laboratory, Tennessee, United States
Roy Cahill, Rio Tinto, Australia
Mark Dorreen, CSIRO, Victoria, Australia
Marc Dupuis, GeniSim Inc., Quebec, Canada
Les Edwards, Rain Carbon Inc., Louisiana, United States
John Griffin, ACT LLC, New Jersey, United States
Halldor Gudmundsson, Nordural—Century Aluminum Company, Iceland
Errol Jaeger, The Business Consultants FZ LLC, Florida, United States
Keerti Kappagantula, Pacific Northwest National Laboratory, Washington, United States
Anne Kvithyld, SINTEF, Trondheim, Norway
Julie Levesque, Quebec Metallurgy Center, Quebec, Canada
Xinghua Liu, Alcoa Corporation, Pennsylvania, United States
Lorentz Petter Lossius, Hydro Aluminium AS, Norway
Pierre Marcellin, Rio Tinto, France
Aditya Nittala, Pacific Northwest National Laboratory, Washington, United States
Eric Nyberg, Kaiser Aluminum, Washington, United States
Jitendra Odhrani, Sunpowergen, United Arab Emirates
Hong Peng, University of Queensland, Queensland, Australia
Katherine Rader, Pacific Northwest National Laboratory, Washington, United States
Arne Ratvik, SINTEF, Trondheim, Norway
Herve Yves Roustan, Rio Tinto Aluminium Pechiney, France
Barry Sadler, Net Carbon Consulting Pty Ltd, Victoria, Australia
Gudrun Saevarsdottir, Reykjavik University, Reykjavik, Iceland
Benjamin Schuessler, Pacific Northwest National Laboratory, Washington, United States
Samuel Wagstaff, Oculatus Consulting, Georgia, United States
Tao Wang, Rio Tinto, Illinois, United States
David Sydney Wong, Atmolite Consulting Pty Ltd, Queensland, Australia
 Part I
Alumina & Bauxite
 Chemical Thermodynamics and Reaction
Kinetics of Bayer Process Desilication

Hong Peng, James Vaughan, Sicheng Wang, John Vogrin,

and Dilini Seneviratne

Abstract residue/red mud), and precipitation of gibbsite and calcina-

tion of the gibbsite to alumina.
With increasing amount of high silica bauxites used as
Bauxite is also comprised of iron phases such as goethite
Bayer refinery feed, the re-precipitation of dissolved
and hematite, titanium oxides, clay minerals comprised of
silicates results in greater volumes of desilication product
quartz (SiO2), and kaolinite (Al2O3⋅2SiO2⋅2H2O) as well as
(commonly known as DSP) which corresponds to
other impurities such as organics [1, 3, 4]. During bauxite
elevated caustic consumption and issues with bauxite
digestion, in addition to extraction of aluminium from bauxite
residue neutralisation and storage. Furthermore, incom-
ores (Eqs. 1 and 2), there is also the desilication products
plete desilication of pregnant Bayer liquor also results in
(DSP) from clay minerals in solution as shown by Eqs. 3 and 4.
silicate reactor and piping scaling as well as the
possibility of contamination of the alumina product.
Alumina-Bearing Minerals Digestion
Optimization of silicate management in the Bayer process
is therefore a high priority. Understanding the chemistry
of silicate leaching and precipitation of silicate in Bayer AlðOHÞ3 ðsÞ
þ NaOHðaÞ , NaAlðOHÞ4 ðaÞ ð1Þ
process underpins potential process improvements. This gibbsite
literature review summarises the chemistry of DSPs, with
AlOOHðsÞ
a focus on chemical-thermodynamics and reaction þ NaOHðaÞ þ H2 OðaÞ
kinetics. diaspore/Boehmite
, NaAlðOHÞ4 ðaÞ ð2Þ
Keywords The reactive silica in the bauxite, mainly kaolinite, reacts

Desilication products
Solubility Bauxite

Bayer process
Sodalite
with the sodium hydroxide to form the sodium metasilicate
solution. Once sufficiently supersaturated, the silicates then
re-precipitate as insoluble sodium aluminosilicate
DSP. Based on the different types of X anions and solution
temperature, DSP could be hydroxysodalite, Cl-sodalite and
Introduction cancrinite [1, 5, 6]. While DSP is costly, it plays a beneficial
role in the Bayer process in terms of purifying the liquor of
Since the Bayer process was patented in 1888 by Australian impurities such as sulphate, carbonate, and chloride, and
chemist Karl Bayer, this technology has been the major therefore a certain amount of DSP is helpful to ensure a high
industrial process for the producing of alumina from bauxite degree of recyclability of the Bayer liquor.
ores [1, 2]. Even after 135 years, this process remains
unchanged for four major key sections: digestion of alumina- Reactive Silica Dissolution
rich minerals (gibbsite, boehmite, and diaspore) into hot
caustic solution, clarification of the insoluble phases (bauxite Al2 O3
2SiO2
2H2 O
þ 6NaOH
kaolinite
H. Peng (&)
J. Vaughan
S. Wang
J. Vogrin
D. Seneviratne , 2Na2 SiO3 þ 2NaAlO2 þ 5H2 O ð3Þ
School of Chemical Engineering, The University of Queensland,
Brisbane, QLD 4072, Australia
e-mail: [email protected]

© The Minerals, Metals & Materials Society 2024 3

S. Wagstaff (ed.), Light Metals 2024, The Minerals, Metals & Materials Series,
https://doi.org/10.1007/978-3-031-50308-5_1
4 H. Peng et al.

Dissolved Silica Precipitation uncertainty ±10.4 with 95% confidence level. The major
contribution in the uncertainties was due to the uncertainty in
6Na2 SiO3 þ 6NaAlO2 þ Na2 X þ 12H2 O the Gibbs energy of formation of the DSP phase. Later,
Moloy et al. [20] reported the formation and hydration
DT 3ðNa2 O
Al2 O3
2SiO2
nH2 OÞNa2 X
, þ 12NaOH enthalpies of the hydroxysodalite family by hydrothermally
Bayer  sodalite synthesising the material from a zeolite phase. More
ð4Þ recently, Zeng and Li [21] determined the solubility of so-
X = OH−, Cl−, SO42− and CO32−. dalite in NaOH-NaAl(OH)4 solutions at temperatures
The principles of Bayer desilication have been described between 30 and 75 °C by dissolving synthetic sodalite into
in many studies [7, 8]. Impurities in bauxite dissolve and solution. By data regression, they reported sodalite enthal-
accumulate in the Bayer circuit, contributing to an array of pies and Gibbs energies of formation at standard conditions.
process issues thus making it difficult to operate and control For cancrinite, Kurdakova et al. [22] estimated the thermo-
[9] with silicate phases being a primary contributor. Silicates dynamic properties of synthetic sodium carbonate cancrinite
such as kaolinite, halloysite, chamosite, and quartz exhibit at 27 °C using the reported thermodynamic data for calcium
different solubilities and reaction kinetics [1, 10]. Quartz cancrinite by Liu et al. [23] and Ogorodova et al. [24]. In this
typically does not significantly dissolve during the extraction section, the solid (synthesised under hydrothermal condi-
of alumina from bauxite, unless the grain structure is fine tions) is different from the phases that would be formed
and the digestion temperature and residence time are high. during the Bayer process. No reports have been identified
However, if quartz does dissolve it is especially costly as it that include the enthalpies and Gibbs energies of formation
leads to additional loss of dissolved aluminium. Halloysite is for sodalite and cancrinite at Bayer process conditions.
reactive but tends to be a minor component if present at all. Furthermore, there is no reliable report of the heat capacity–
Kaolinite is the most commonly found reactive silica and temperature relationship for the high-alumina, semi-
dissolves readily in caustic soda [5, 11, 12]. In the absence crystalline DSPs forming in the Bayer process.
of crystallization seed, most of the reactive silica forms
soluble sodium silicate which then precipitates as DSP
during the predesilication and digestion stages of the Bayer Empirical Solubility Models
process [13].
This review summarises the factors that influence ther- The equilibrium concentration of sodium aluminosilicate in
modynamics solubility and kinetic DSP crystallisation, and sodium aluminate solutions has been the subject of a number
mineral phase transformation during Bayer processes. The of studies. There is a considerable amount of evidence in
objective is to bring together the relevant fundamental literature to suggest that the desilication kinetics are directly
information about reaction equilibrium and kinetics to proportional to the liquor SiO2 supersaturation ratio.
enable the optimisation or improvement of predesilication Therefore, in order to optimise desilication it is important to
and digestion in terms of economic and environmental accurately predict equilibrium SiO2 values. The supersatu-
outcomes ration ratio is defined in Eq. 5 [25]:

½SiO2 t  ½SiO2 eq

r¼ ð5Þ
Thermodynamic Research of Desilication ½SiO2 eq
Products
where [SiO2]t is the silicate concentration (expressed as SiO2
Despite several empirical solubility correlations proposed for equivalent) at time t and [SiO2]eq is the equilibrium silicate
silicates [14, 15], there is a lack of reliable chemical- concentration. Previous research has led to development of
thermodynamic data relevant to the Bayer process. This data models predicting equilibrium silicate concentration. How-
is essential for predictive solubility modelling of DSPs. Only ever, most of these models are empirical in nature and not
a single report has been found on the measurement of based on any experimentally determined thermodynamic
thermodynamic data for anhydrous sodalite (Na6(Al- parameters, which strictly limits their application to a set
SiO4)6*NaCl2) by Komada et al. [16]. Using the group range of factors such as temperature, solution ionic strength,
contribution method for calculating properties such as caustic concentration, and liquor impurities [26]. Models
enthalpies, free energies of formation, and heat capacities used in industry (which are confidential and therefore not
proposed by Mostafa et al. [17, 18], Park and Englezos [19] published) are also limited to their specific refinery due to
estimated the equilibrium constant for sodalite solubility as it the empirically determined nature [27]. When conditions fall
was not available in the literature. The results showed that outside their parameterisation, the model predictions become
the equilibrium constant ln(K) was 88.7 with large almost meaningless [28]. Fundamental understanding of
Chemical Thermodynamics and Reaction Kinetics of Bayer Process Desilication 5

silicate precipitation behaviour and accurate prediction of the A later study by Park and Englezos modelled silicate
products could enable novel, efficient methods of desilica- solubility from a chemical-thermodynamics perspective at
tion to be realised. Table 1 outlines the correlations for SiO2 conditions applicable to Kraft pulp mills. In their model, a
solubility in open literature and their range of applicability. slightly different precipitation reaction was used to give the
As these are empirical models, they have expressed the corresponding equilibrium constant in Eq. 7 [19]:
equilibrium concentration of silicate as [SiO2]eq.
a4H2 O ðm12
OH cOH Þ
12
K c ðT Þ ¼ ð7Þ
ðm8Na þ c8Na þ Þðm6AlðOHÞ c6AlðOHÞ Þðm6SiO2 c6SiO2 Þ
4 4 3 3
Thermodynamics Solubility Models
Although both models were reported to have good pre-
Outside of empirical correlations, only a few studies have dictions, they consistently predicted higher values than the
attempted to construct a silica solubility model from a measured data, especially at higher temperatures. When
thermodynamics perspective. The earliest thermodynamic- considering solubility from thermodynamic first principles,
based model found in literature was created by Jamialahmadi the equilibrium product Kp is dependent exactly on the
and Müller-Steinhagen [10]. They used the equilibrium nature of the chemical species. Given newly understood
constant for the precipitation reaction in Eq. 6 to provide a speciation, the equilibrium constant Kc can be written as
fit to experimental data. Eq. 8 which considers silicate species in terms of H2SiO42−
molality—the predominant silicon ion in Bayer process
½NaOH2 conditions [36]:
K c ðT Þ ¼ ð6Þ
½Na2 SiO3 ½NaAlO2 ½H2 O

Table 1 Correlations for silicate equilibrium solubility

Author Correlation Range of
applicability
Adamson et al. SiO2 = 2.6  10–5 [Na2O][Al2O3] Not stated
[29]
Smirnov [30] SiO2 = 2 + 6.6  10–4 [Al2O3]2 – 3.3  10–2 [Al2O3] T = 298–368 K
[NaOH] = 12–378
g/L
[Al(OH)3] = 13–
431 g/L
Leiteizen [31] SiO2 = 1.28  10–5 [Na2CO3][Al2O3] Not stated
–4 –3 –6
Cresswell [32] SiO2 = 0.1587 – 6.058  10 T(°C) – 2.078  10 [Na2CO3] + 9.156  10 T = 373–513 K
[Na2CO3]2 + 9.509  10–6 [Na2CO3]T(°C) [NaOH] = 136 g/L
[Al
(OH)3] = unknown
Hewett et al. [33] SiO2 = 1.44  10–5 [Al2O3]2 + 1.85  10–4 T(°C) + 2.97  10–4 [NaOH] T = 328–460 K
[NaOH] = 50–190
g/L
[Al(OH)3] = 69–
275 g/L
Smith et al. [34] Below 180 °C: SiO2 = 2.67  10–3 [Al2O3] + 1.18  10–4 [Na2CO3] T = 373–523 K
Above 180 °C: SiO2 = 2.67  10–3 [Al2O3] + 1.18  10–4 [Na2CO3] + 2.5  10–3 (T − 100) [NaOH] = 113–226
g/L
[Al(OH)3] = 69–
321 g/L
Sizgek and SiO2 = 1.82  10–6 [Na2CO3]2 + 3.37  10–13 [Na2CO3]2T3(°C) + 2.08  10–5 [Na2CO3]2(A/ T = 373–523 K
Aguila [35] C)3 [NaOH] = 121–196
g/L
[Al(OH)3] = 97–
302 g/L
Barnes et al. [14] SiO2 = −2.26  10–3 [Al(OH)3]0.5 + 2.42  10–4 [NaOH] + 6.66  10–4 [Al(OH)3] T = 363–493 K
[NaOH] + 1.47  10–5 T(°C) − 1.77  10–3 [NaOH] = 155–217
(All concentrations in mol/L) g/L
[Al(OH)3] = 108–
174 g/L
Where all the concentrations are in g/L of that compound unless otherwise stated
6 H. Peng et al.

12 12 
a10
H2 O mOH cOH decrease in silicate solubility is inevitable as aluminate
K c ðT Þ ¼
  

m6Na þ c6Na þ m6H SiO2 c6H SiO2 m6AlðOHÞ c6AlðOHÞ mNa2 X cNa2 X concentration decreases [40]. As plant liquors typically do
2 4 2 4 4 4
not fall below 100 g/L Al2O3, the empirical correlations do
ð8Þ not parameterise a U-shaped curve and instead show only a
where a is the activity, m is the molality, and c is the activity positive relationship as shown in Fig. 2 Region III.
coefficient of the species. Problems arise when considering both Al and Si species
Considerable attention must be paid to speciation in in highly alkaline solution as neither Fig. 1 nor 2 adequately
Bayer liquors, especially at high ionic strength and temper- describe their co-existence. Pokrovski et al. were among the
ature. When considering Eq. 8 as the equilibrium constant first group to investigate Al-Si speciation in basic solutions
equation for DSP, good agreement has been observed with [41]. It found that the species AlSiO(OH)6− and its forma-
reported solubility values at extremely dilute conditions and tion through Eq. 9 accounted for at least 80% of the total
low temperature, however fails when increasing either of dissolved aluminium in the presence of silicate through 27Al
these conditions. Equally and perhaps more important to nuclear magnetic resonance measurements.
DSP modelling than the aluminium speciation is the speci-
H4 SiO04ðaqÞ þ AlðOHÞ 
4 ðaqÞ $ AlSiOðOHÞ6 ðaqÞ þ H2 OðlÞ
ation of silicon. Problems associated with Si speciation
modelling can be traced back to its origins in geochemical ð9Þ
modelling [37]. It is generally accepted that the predominant
Gout et al. later conducted comprehensive Raman spec-
silicate species at high pH such as in the Bayer process is the
troscopic investigations on Al-Si complexation in ultrabasic
monomeric H2SiO42− although other polymeric and alumi-
solutions at 20 °C with higher OH− molality than previous
nosilicate species may exist. According to the speciation
studies [38]. Through measuring band intensities, they
diagram in Fig. 1, the H2SiO42− ion accounts for at least
derived the amounts of complexed Al and Si in solution
90% of the total silicate species in solution and is a gener-
shown in Fig. 3. The dimer species AlSiO3(OH)43− was
alised form of silicate ion shown in the equations as it is the
suggested to be the dominant complex formed through
dominant species [38, 39].
Eq. 10:
A systematic study undertaken by Smirnov [30] into
aluminate solutions that revealed three distinguishable  3
4 ðaqÞ þ AlðOHÞ4 ðaqÞ $ AlSiO3 ðOHÞ4 ðaqÞ þ H2 OðlÞ
H2 SiO2
regions in a characteristic ‘U’-shaped solubility curve as
shown in Fig. 2: (I) at low Al(OH)3 concentrations where a ð10Þ
decrease in the alumina concentration leads to a considerable Zeng and Li modelled silicate speciation using OLI’s
increase in solubility of DSP (higher SiO2); (II) an inter- mixed solvent electrolyte (MSE) [42] and the AlSiO3(OH)43−
mediate zone where the solubility is practically independent species proposed by Gout et al. [43]. Their model appeared to
of Al(OH)3 concentration; and (III) at high Al(OH)3 con- fit their low-temperature data well and suggested it to be the
centrations the equilibrium silica concentration increases predominant anion at Bayer conditions. However, even
with increasing alumina concentration. Note that at gibbsite sophisticated electrolyte solubility calculations such as that
precipitation conditions (3.3–3.8 M Al(OH)3), a sharp often do not always predict the unusually high Al and SiO2

Fig. 1 Distribution of solution silicate species in a 0.001 M Si solution at T = 25 °C a by Raman spectra [38]; b by geochemical modelling
software using IUPAC data (solid line) and HSC data (dashed line) [39]
Chemical Thermodynamics and Reaction Kinetics of Bayer Process Desilication 7

6 Crystallization Mechanisms and Kinetics

I Boundary III of DSPs
5

4 The mechanisms of crystallization during Bayer process,

SiO2 (g/L)

including nucleation, growth, DSP metastable phase trans-

3 II formations, and agglomeration, are complicated. Under-
standing these mechanisms is crucial for increasing the
2
particle size of DSP and enable adequate recycling of
1 otherwise lost sodium and aluminium.
As shown in Eq. 11, mass deposition is split into a dif-
0
0 50 100 150 200 250 300 350
fusion step and a first-order reaction step. Here m = mass
deposited in time t; A = crystal surface area; c = solute
Al(OH)3 (g/L)
concentrations in the bulk solution; ci = at the interface and
Fig. 2 The solubility of silicate (as g/L SiO2) in sodium aluminate c* = equilibrium saturation; kd and kr = deposition/reaction
solution as a function of aluminate concentration (as g/L Al(OH)3). mass transfer coefficients; and g = exponent g, the order of
Graph was taken and modified from [38] the overall crystal growth process [45, 46]. These reactions
can be combined by approximating the overall driving force
or concentration difference and introducing an overall crystal
growth coefficient KG.

dm dm
¼ k d Að c  c i Þ ¼ k r Að c i  c  Þ ! ¼ K G Aðc  c Þg
dt dt
ð11Þ
The nucleation and crystal growth of DSP can be deter-
mined from the desilication rate and the supersaturation
order. Smith et al. proposed that the order of the reaction
(n) depends on the supersaturation ratio, with n equal to 1 at
lower ratios and 2 or 3 at higher ratios [34]. However, even
when the initial silicate concentration is the same, the seed
mass or surface area can also affect the order of the reaction.
Ruan et al. suggest that desilication with a third-order or
Fig. 3 Complexed Al and Si concentration as a function of the product
of concentrations of the free silicate and aluminate [38] greater dependence on Si supersaturation is due to nucle-
ation, either primary heterogeneous or secondary, while less
than third-order dependence is predominantly due to alu-
concentrations of Bayer liquors and nuclear waste tank con- minosilicate crystal growth [47, 48]. The nucleation and
centrates [44]. With the abundance of conflicting species, crystal growth rates of DSP during Bayer process vary with
further studies into the system at elevated temperature are kaolinite dissolution in caustic solutions [11, 12]. As shown
required for accurate modelling. in Fig. 4, kaolinite from bauxite completely dissolves into
The chemical-thermodynamic approach for estimating caustic solutions within hours, which is coupled with an
solubility can be a powerful predictive tool, provided the early increase of SiO2 concentration in the solutions. The
model is based on a complete and accurate data set. There is SiO2 concentration starts to decrease after complete disso-
limited data available for certain aqueous species such as lution of kaolinite due to precipitation of DSP which con-
aluminate-silicate polyanions and the heat capacity–tem- sumes the SiO2 component in the solution [49]. Nucleation
perature relationships have not been established for some and growth rate for DSP have historically been studied in
important components, including sodalite. Reliably relating terms of changes in silicate supersaturation, but not in terms
the thermodynamic predictions to practical solution phase of fundamental parameters. Furthermore, evidence of growth
concentrations requires an estimate of the activity coefficient rate dispersion and growth as a function of particle size has
for the aqueous species which is also currently lacking for not been investigated for DSP.
aqueous silicates. The systems are further complicated when The reactivity of kaolinite on the precipitation step to
considering the wide range of other solution components and form DSP has also been studied. Kotte states that experi-
ion substitutions in the DSP. ments have shown that kaolinite from most bauxites will
8 H. Peng et al.

Fig. 4 Kaolin dissolution and

DSP precipitation. Adapted from
[49] with data from the model
described in [11]

dissolve rapidly (less than 15 min) provided the temperature dependent on temperature and conversion rates. This phase
is kept close to the atmospheric boiling point [49]. However, transformation sequence has received support from several
this is dependent on the particle size and kaolinite form research groups [1, 62, 63] and is regarded as the ‘correct’
present. Smith et al. similarly found that DSP precipitation phase transformation sequence in synthetic Bayer liquor.
rate is limited by the dissolution of kaolin [50]. Kaolinite can Radomirovic et al. [64] and Peng et al. [60] also observed
also be heat treated to form meta-kaolin, which reacts rapidly DSP formation beginning with an amorphous phase under
forming DSP phases seen under similar conditions using a Bayer conditions. In most of the studies investigating phase
soluble silicate source [11, 12, 51, 52]. transformation, a soluble silicate source such as sodium
metasilicate pentahydrate or waterglass was used. Some
studies have concluded that the starting silicate source
Desilication Products Phase Transformation influences the precipitating phase, implying that the true
phase transformation pathway originating from kaolin is still
The DSPs have much lower solubility than the kaolinite in unknown. It is suggested that DSP is initially heteroge-
Bayer liquor. Many researchers have investigated the neously nucleated on the kaolin and as kaolin further dis-
structure of DSP [6, 13, 50, 53–56]. Depending on the solves, these nuclei are released, allowing for secondary
solution chemistry and plant operating conditions, various nucleation. Vogrin et al. recently concluded that the DSP
types of DSP can be formed. The silicon-oxygen tetrahedron formed at alumina digestion concentrations directly precip-
is a basic structural element of most DSPs. Based on the itates as a high-alumina cancrinite-type structure that can
different types of anion incorporation and solution temper- remain stable at equilibrium [65]. This was the proposed
ature, the structure of DSP could be either that of a sodalite phase of DSP in bauxite residues compared to heat
(Na6(AlSiO4)6*2NaOH*2H2O) or cancrinite (Na6(Al- exchangers. Generally, in the Bayer liquor, truncated octa-
SiO4)6*Na2CO3*2H2O) [1, 5, 6] with molar soda to a sili- hedral cages (toc units) are formed by crosslinking AlO4 and
cate ratio (Na2O/SiO2) of 2/3. These two types of DSPs, on SiO4 tetrahedral blocks [66] and these are the fundamental
the other hand, are known to form as a result of a series of building blocks of the different DSP phases after kaolinite
solution-mediated silica-rich phase transformations (e.g., dissolution at temperature less than 100 °C [11, 67, 68].
kaolinite) [45, 57–59]. This sequence was explained by Peng
et al. in the context of thermodynamic driving forces and the
observed crystallization pathway occurs via the Ostwald Anion Effects on the Formation of DSPs
successive transformation step rule, which was proposed as
amorphous sodium aluminosilicate ! zeolite Linde Type A Anion impurities present in Bayer liquors are known to have
(LTA) ! sodalite ! cancrinite [39, 60, 61]. It suggests that a detrimental effect on the efficiency of the Bayer process.
Bayer process heat exchanger scale is in fact possibly made These anions originate from partial dissolution of sulphur- or
up of all phases including amorphous material, zeolite A, carbonate-containing minerals, organic material, process
sodalite, and cancrinite, but their proportions will be additives, as well as the diffusion of atmospheric carbon
Chemical Thermodynamics and Reaction Kinetics of Bayer Process Desilication 9

dioxide [69]. The presence of different anions can impact the sequence. For example, Seimiya et al. discovered DSP in
phase transformation rates [50, 52, 61, 70, 71] and trace bauxite residue transformed from zeolite A to sodalite after
amounts of impurities (*10–3 M) can cause significant desilication with the addition of NaCl, Na2CO3, and Na2SO4
effects on the crystal formation process. As Bayer liquor is [80]. Breuer et al. demonstrated that the addition of sodium
recirculated in the process there is a tendency for impurity salt such as sodium oxalate, carbonate, and sulphate pro-
levels to build up, reducing liquor productivity by affecting moted formation of cancrinite over sodalite at 200 °C [7].
alumina solubility, yield, liquor density, and viscosity [72]. However, other studies have found that specific salts might
As a result, they require purging to maintain reasonable inhibit the transformation of zeolite A to other phases [62].
steady-state concentration in the process. Although generally In summary, it is critical to understand the behaviour of each
considered undesirable, the precipitation of sodium alumi- anion influencing secondary nucleation rates, crystal growth,
nosilicate shows that various anions can become enclath- and agglomeration processes under Bayer DSP precipitation
rated within the framework, including Cl−, CO32−, SO42−, conditions.
etc. DSP is both paradoxically problematic and useful as the
inclusion can actually remove significant amounts of impu-
rities from Bayer liquors [73]. It has been reported that in- Conclusions and Outlook
clusions in DSP may account for up to 75% of Na2SO4
exiting the Bayer circuit, while chloride and carbonate are This review summarizes both chemical and physical prop-
seemingly lower at about 25% [72]. As anions are able to erties of DSPs and reviewed key issues relating to current
replace the hydroxide ion, the potential to reduce caustic challenges faced by the alumina industries for silica con-
losses by charging sodium salts after digestion has been tamination in the Bayer liquor, thermodynamics and solu-
suggested and patented in the literature [74, 75]. bility of DSPs, phase transformation, and crystallization
Only a few studies have been conducted into anion enlargement of DSPs during Bayer process that may affect
incorporation in DSP that are relevant to Bayer process the refinery aluminium grade or subsequent separation of
temperatures, caustic and sodium aluminate concentrations DSP with other minerals in bauxite residue.
[7, 76, 77]. Fundamental studies by Seimiya et al. into The concentration of NaOH and NaAl(OH)4 is a primary
desilication in the presence of impurities revealed that the factor that affects the concentration of silicate in Bayer
percentage of anions enclathrated in DSP increases with liquor. The solubility of silicate in aluminate-free solutions is
higher synthesis temperatures and longer times [78–80]. higher than in aluminate-bearing solutions under Bayer
Sodalite synthesised with added Na2CO3 contained up to liquor conditions, and the relationship between silicate
300% more CO32− than control tests without impurity concentration and caustic concentration is positively corre-
addition. The results also suggested that there is some lated while the equilibrium silicate concentration decreases
preference to incorporate not only CO32−, but also Cl− and with decreasing aluminate concentration. The temperature
SO42− into the crystal lattice over OH− and Al(OH)4− [80]. has minimal impact on solubility within a range of 30–75 °C
Comprehensive studies on anion impurities and their but has been shown to intensify at Bayer digestion temper-
effects on DSP were conducted over two decades [13, 52, atures. The crystalline phase also affects silica levels in the
54, 61, 71, 81]. The composition of sodalite formed after Bayer liquor, with the early amorphous phase formed during
predesilication and digestion in liquors containing added the Bayer process contributing to higher silica concentration.
sodium salts such as NaCl, Na2CO3, or Na2SO4 salts was For mineral phase transformation during the Bayer pro-
investigated, which shows that the magnitude of anion cess, sodalite and cancrinite are common types of DSPs
incorporation into sodalite under pseudo-Bayer conditions (digestion-soluble products) formed during the process from
follows the trend: OH− < Al(OH)4− < Cl− < CO32− < SO42 kaolinite. These DSPs are known to form because of
−
. The incorporation of chloride (Cl−) and sulphate (SO42−) solution-mediated silica-rich phase transformations, and the
was also observed to follow a Langmuir-type isotherm with crystallization pathway occurs via the Ostwald successive
increasing anion concentration, which was later supported transformation step rule. Anion impurities present in Bayer
by Whittington et al., Smith et al., and Vogrin et al. [13, 81, liquors can impact the phase transformation rates and trace
82]. These studies were beneficial as they modelled quanti- amounts of impurities can cause significant effects on the
tative anion incorporation into DSP, although they did not crystal formation process. Future studies need to be done to
relate to other fundamental factors such as reaction kinetics. clarify the chemical composition and mineral structures of
In addition to being incorporated into the DSP structure, DSPs formed during Bayer process in the presence of anion
anions can promote or suppress the phase transformation impurities.
10 H. Peng et al.

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79. Seimiya, S. and S. Mori, Study on sodalite compounds in the bayer 81. Smith, P.G., et al., The composition of DSP formed under
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80. Seimiya, S., Some properties of sodalite in red mud, in Extractive aluminosilicate solubility in Bayer liquor aiding the desilication
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1963, Interscience: NY. p. 115–132.
 Challenges with Characterizing
and Processing Goethite-Rich Jamaican
Bauxites

Michael Coley, Anthony Greenaway, Alicia Buckley, Khadeen Henry,

Jheanell James, and Jason Brown

Abstract Introduction
Low-temperature alumina plants in Jamaica traditionally
process hematite-rich ores with manageable concentra- The Bayer process uses high-pressure digestion conditions
tions of mineral impurities. As these ores become scarce, to extract alumina minerals from bauxite [1]. During the
the new bauxite mines have lower available alumina, process, a variety of impurities often dissolve and eventually
higher goethite, and higher concentrations of phosphorus, impact the liquor characteristics, alumina yield, and quality,
chromium, and manganese contaminants. Since the often making the alumina unsuitable for smelter operations
minerals associated with some of the minor impurities [2]. Traditionally mined Jamaican bauxites are gibbsitic, red
have not been identified, this paper explores whether the in colour, and contain hematite as the main iron mineral.
contaminants accumulate in the coarse or fine bauxite These ores, generally found at low altitudes, contain low
fractions. Samples of hematite-rich bauxite from the concentrations of phosphorus and metal impurities. As
traditional mining areas and also goethitic ores from the supplies of these ores decline, new mining areas with goe-
new mines were wet-sieved into three size fractions thitic bauxite having lower available alumina and higher
(+200, −200/+325, and −325 mesh). Each fraction was concentrations of chromium, zinc, and phosphorus are being
investigated using X-ray fluorescence (XRF) and X-ray explored [3]. These yellow bauxites are mainly found in
diffraction (XRD) spectroscopies. Following digestion, hillside locations that are dominated by pocket deposits with
their caustic soluble concentrations of phosphorus, highly variable mineral compositions [4, 5].
chromium, and zinc were also determined. The traditional The local Bayer plants have well-established methods for
bauxites had no correlation between size fraction and the processing hematite-rich ores containing 0.1–0.4% P2O5.
alumina, iron, calcium, or phosphorus concentrations in However, as the use of goethitic bauxites becomes immi-
the ore, however larger particles had slightly more nent, plants require new strategies to manage bauxite blends
manganese impurities. In contrast, larger particles from with higher concentrations of phosphorus (1–2.5% P2O5),
the new mines had higher concentrations of iron and zinc (0.02–0.06% ZnO), and chromium (0.06–0.20%
chromium impurities while smaller particles contained Cr2O3). High P2O5 concentrations in bauxite have significant
marginally more alumina. During digestion, the new implications for soluble phosphorus control and lime
bauxites gave higher caustic soluble P, Zn, and Cr and requirements; liquor viscosity and alumina yield and purity
will be more challenging and costly to process into may also be impacted [3]. Poorly controlled soluble phos-
alumina that meet the required specifications. phorus may reduce mud settling rates, lower filtration effi-
ciency, cause scale formation, and increase fines production
Keywords during precipitation [6].

Jamaican bauxite Hematite
Caustic soluble phosphorus

Goethite
Size fraction
The main phosphorus mineral in goethitic bauxite is cran-
dallite (CaAl3(PO4)2(OH)5
H2O), however apatite (Ca5(PO4,
CO3)3 (F, OH, Cl), wavellite (Al3(PO4)2(OH)3(H2O)5, and
variscite (AlPO4
2H2O) may also be present. These minerals
M. Coley (&)
A. Greenaway
A. Buckley
K. Henry
J. James
dissolve differently in caustic, for example, apatites are spar-
J. Brown ingly soluble while crandallite dissolves quite readily. Hence,
Department of Chemistry, The University of the West Indies, unless the phosphorus mineralogy is known, it is difficult to
Mona, Kingston, 7, Jamaica establish the lime requirements needed for phosphorus control
e-mail: [email protected]

© The Minerals, Metals & Materials Society 2024 13

S. Wagstaff (ed.), Light Metals 2024, The Minerals, Metals & Materials Series,
https://doi.org/10.1007/978-3-031-50308-5_2
14 M. Coley et al.

during predesilication and digestion [7, 8]. Managing the metal concentration ranges of P2O5 (0.11–0.95%), ZnO (0.003–
impurities (Cr2O3, ZnO, and MnO) is also challenging as their 0.140%), and Cr2O3 (0.09–0.19%) within the traditional
low concentrations in the ore make it difficult to identify their mining area. In selecting samples from the new mining area,
source minerals using traditional X-ray diffraction (XRD) the concentrations of impurities within the different ore
techniques. It is also difficult to predict their caustic soluble bodies (P2O5, 0.32–24.6%; ZnO, 0.018–0.308%; and Cr2O3,
concentrations and to design protocols for their control [7, 9]. 0.06–0.37%) were also taken into consideration [11]. The
Jamaican bauxites are mainly fine particles but these may samples selected included processable bauxites and also a
aggregate to form larger units. The presence of sand, lime- few with unusually high or low impurity concentrations. The
stone, and a variety of other minerals often results in crushed extreme samples were included to enhance detection of
bauxites having a fairly wide range of particle size. differences in the mineral concentrations of each bauxite
This paper compares the characteristics of traditionally fraction.
mined, red, hematite-rich Jamaican bauxite with samples of Six bauxite samples were selected from the traditional
yellow, goethitic ores that are slated for mining in the near mining area and six from the new mines. The metal oxide
future. These new bauxites have high phosphate and metal concentrations of exploration samples from each mining area
impurity concentrations. Crushed exploration samples from are shown in Tables 1 and 2. These XRF concentrations
both mines were wet-sieved and fractioned into three typical were not confirmed in this study and were only used as
categories: >75 lm (+200 mesh), 45–75 lm (−200/+325 guides for sample selection. Data in the tables are organized
mesh), and <45 lm (−352 mesh). Selected fractions from based on the % P2O5 concentrations.
each mining area were analysed using XRF to investigate
metal oxide concentrations. XRD was used to explore
potential differences in mineralogy and following digestion, Bauxite Analysis
caustic soluble P2O5, Cr2O3, and ZnO were measured to
assess dissolved impurity concentrations in the process Bauxite samples (100 g) were spread out over the surface of
liquors. The study seeks to determine whether there are a #200 mesh sieve (Fisher Scientific). The mesh and sample
distinct differences in the concentrations of bauxite impuri- were then partially submerged in distilled water and the
ties in the different fractions of bauxite samples taken from sieve shaken for four minutes to allow particles capable of
the current and future mining areas. Since the processing of exiting the mesh to escape. Particles retained on the sieve
goethitic bauxites has been associated with slow mud set- were transferred, dried at 100 °C, weighed, and subsequently
tling and low alumina productivity, the study will also analysed. The filtrate suspension was further wet-sieved
explore process challenges that might impact use of the new using a #325 mesh and particles retained on this sieve were
bauxites to produce smelter-grade alumina [3, 10]. treated as described above. The fine bauxite particles that
exited the #325 sieve were allowed to settle overnight and
were then filtered using Whatman #1, #40, and #42 filter
Materials and Methods papers. The #42 filter paper (2.5 µm pore size) was fitted in
the Büchner funnel first, followed by the #40 (8 µm pore
Sample Selection size) while the #1 filter paper (24 cm) was cupped within the
filter funnel to ensure that all the −325 fraction particles
Composite exploration samples of traditionally mined were captured. After filtration, the sample was dried as
bauxites were studied alongside the ore samples that domi- previously described.
nate the future mining area. Samples having comparable Pressed pellets were produced from each bauxite fraction
Al2O3, Fe2O3, SiO2, and TiO2 concentrations were selected and elemental concentrations were determined using a
from both mines. Samples were selected to span the PANalytical Magix Pro XRF operating at 40 kV and 60 mA.

Table 1 XRF data of unsieved Sample % % % % % % % % %

exploration samples from the Al2O3 Fe2O3 SiO2 TiO2 CaO P2O5 Cr2O3 ZnO MnO
traditional mining area
DCS11A 50.8 19.8 0.71 2.30 0.04 0.11 0.182 0.003 0.16
DCS10B 49.5 19.6 2.73 2.20 0.29 0.16 0.136 0.011 0.29
DCS21B 49.6 21.2 0.42 2.85 0.04 0.18 0.119 0.029 1.31
DCS08B 50.6 19.3 2.67 2.57 0.08 0.20 0.085 0.018 0.62
DCS14B 49.8 16.2 2.80 2.25 0.12 0.25 0.121 0.106 2.63
DCS16A 46.4 19.5 4.40 2.35 0.18 0.95 0.131 0.079 0.41
Challenges with Characterizing and Processing Goethite-Rich Jamaican Bauxites 15

Table 2 XRF data of unsieved Sample % % % % % % % % %

exploration samples from the new Al2O3 Fe2O3 SiO2 TiO2 CaO P2O5 Cr2O3 ZnO MnO
mining area
DCN30A 48.3 22.4 0.07 2.12 0.09 1.10 0.251 0.101 2.10
DCN47A 57.5 7.60 0.08 2.06 0.33 1.40 0.150 0.018 0.03
DCN10A 46.1 21.3 0.21 2.04 1.26 2.04 0.227 0.126 1.18
DCN16A 47.2 22.9 1.42 2.71 0.39 2.10 0.374 0.025 0.03
DCN21 47.9 15.0 2.07 1.98 3.05 5.35 0.144 0.094 0.36
DCN29 47.9 17.1 0.42 1.76 3.06 9.75 0.252 0.052 0.23

Mineralogy of selected samples was examined using a standard solutions via flame atomic absorption spectropho-
Bruker Analytical D5005 X-ray diffractometer operated at tometry (FAAS) at 231.9 nm for Zn and 357.9 nm for Cr.
45 kV and 40 mA. Scans were collected between 4 and 75°
2h [11].
The XRF elemental data and the measured loss of mass Results and Discussion
(LOM) values were combined with data on peak intensities
from the XRD scans using the X-ray database programme Bauxite samples from a currently mined hematite-rich area
(XDB Powder Diffraction Phase Analytical System version and from a new potential replacement mine were studied to
3.107) [12, 13]. The XDB software creates a full-profile fit compare their characteristics and to evaluate their
of the XRD and quantifies the minerals identified based on low-temperature processabilities. Bauxites were compared in
the XRF and LOM measurements. Minerals that are unde- terms of their bulk particle size, elemental concentrations,
tected in the XRD scans are sometimes identified using the mineralogy, and the caustic solubilities of key contaminants
XDB software and their concentrations are estimated [14]. (P2O5, Cr2O3, and ZnO).
The available alumina concentrations were determined on
each bauxite fraction using a proprietary FTIR analytical
method. Size Fraction

Table 3 compares the size fractions and % available alumina

Caustic Soluble Phosphorus in the two types of bauxite samples. A reproducibility check
on the sieving procedure showed agreement to within ±1.2%
Separate fractions of three of the bauxites samples from the while the error associated with the % available alumina was
new mining area were digested in 102 g/L NaOH (ACS ±1.3%. The samples in the table are arranged based on the
grade; BDH Chemicals) at 145 °C for 30 min. Slurries were P2O5 concentrations in the original exploration samples.
centrifuged, filtered, diluted, and were then acidified to pH 2 Four of the six bauxites from the traditional mining area
with 5 M H2SO4. Soluble phosphorus was measured at 880 had >60% of bulk particles in the +200 fraction. The
nm using the molybdenum blue ascorbic acid procedure remaining two bauxites (DCS10B and DCS14B) were
[11]. Fractions of currently mined ores were not studied dominated by fines (*50% −325 fraction). For the new
similarly as they generally have low % P2O5 (typically 0.10– mining area, only two bauxites had >50% of particles in the
0.20) and there are established plant protocols for managing +200 fraction. On average, 45.8% of particles from the new
soluble P in these bauxites. mines were in the −325 fraction in comparison to only 32%
of particles from the traditional mines. For both bauxite
mines, less than 10% of particles were of intermediate size
Caustic Soluble Zn and Cr (−200/+325 fraction).
Data in Table 3 shows that the % available alumina was
Bauxite samples were digested, and the slurries cooled, slightly higher for samples from the traditional mines.
centrifuged, filtered, and then 1.0 mL portions of the clari- Across both mining areas, the larger sized fractions of each
fied liquors were separately combined with 2.5 mL bauxite sample (+200 and −200/+325 fractions) had similar
ultra-pure concentrated HNO3 and diluted quantitatively. % available alumina; these were consistently higher than the
The dilute samples were analyzed alongside suitable alumina content of the −325 bauxite fractions.
16 M. Coley et al.

Table 3 Size fraction and % available alumina of bauxite samples from the traditional and new mining areas
Traditional hematite-rich mining area New goethitic mining area
Goethitic bauxites Sample % % available Goethitic bauxites Sample % % available
fractions mass alumina fractions mass alumina
DCS11A +200 68.7 47.9 DCN30A +200 38.6 40.3
−200/+325 8.6 47.0 −200/+325 11.8 40.5
−325 22.7 44.7 −325 49.5 37.6
DCS10B +200 39.8 42.6 DCN47A +200 47.1 47
−200/+325 9.3 41.3 −200/+325 8.0 47.1
−325 51.0 40.2 −325 44.9 44.2
DCS21B +200 67.6 46.7 DCN10A +200 38.7 43.6
−200/+325 9.7 46.0 −200/+325 6.4 41.2
−325 22.7 43.1 −325 55.0 39.2
DCS08B +200 61.1 40.1 DCN16A +200 34.4 40.9
−200/+325 11.5 41.1 −200/+325 6.0 41
−325 27.4 37.4 −325 59.5 37.7
DCS14B +200 39.9 43.0 DCN21 +200 56.1 40.4
−200/+325 9.6 43.4 −200/+325 11.9 40.2
−325 50.5 41.5 −325 32.0 36.9
DCS16A +200 73.1 38.6 DCN29 +200 58.6 39.1
−200/+325 7.5 39.1 −200/+325 7.8 41
−325 19.4 37.5 −325 33.7 37.8
Average size +200 58.4 43.2 Average size +200 45.6 41.9
fractions −200/+325 9.4 43.0 fractions −200/+325 8.6 41.8
−325 32.3 40.7 −325 45.8 38.9

XRD Analysis of Al2O3, SiO2, CaO, P2O5, and ZnO are roughly similar
within the three size fractions for each bauxite (Table 4).
Figure 1 shows the overlaid diffractograms of the unsieved Figure 2 shows that the MnO concentrations increase with
DCN21A bauxite sample and its +325 and −325 fractions. particle size for all but one sample (DCS11A). Significant
DCN21A is from the new mining area. Scans of the sieved differences in MnO concentrations are observed for the
and unsieved samples are similar which suggests that their fractions of samples DCS21B and DCS14 and it would be
mineralogies are also similar. The broad peak at values >15° worthwhile to probe these fractions to explore whether there
2h concealed the boehmite peaks. This broad peak was is improved opportunity to identify the Mn minerals in each.
characteristic of all the scans recorded on the instrument Similar differentiation was not observed for any other element
during the time and resulted from interferences due to the within the traditional bauxite mines.
sample holder. Fractions of the traditionally mined bauxites
were not examined via XRD. The New Bauxite Mines
The % Fe2O3 and % Cr2O3 in goethitic bauxites from the
new mining area occur in higher concentrations in the +200
XRF Analysis bauxite fractions (Table 5). The % Fe2O3 were lowest in the
−325 bauxite fractions except maybe for sample DCN21A.
Traditional Bauxite Mines The fine fractions tended to have higher % P2O5, however
The XRF data for bauxites from the traditional mines are in the trends were not always consistent (Fig. 3). The % P2O5
Table 4 and those for the new mining area are in Table 5. As in fractions of DCN29 from the new mining area (Fig. 3) are
with previous tables, samples are organized based on the XRF well differentiated and are potentially useful for identifying
concentrations of P2O5 in the original unsieved samples. Data the phosphorus minerals in each. Studies of their caustic
for the traditionally mined ores show that the concentrations soluble concentrations could also be pursued. No defined
Challenges with Characterizing and Processing Goethite-Rich Jamaican Bauxites 17

4 10 20 30 40 50 60 70

2-Theta - Scale

DCN21A DCN21A DCN21A

Dunsieved +325 fraction D -325 fraction
Fig. 1 Overlaid X-ray diffractograms of DCN21A, a bauxite from the new mining area: scans are of unsieved DCN21A and the +325 and −325
fractions

Table 4 XRF data for fractions of bauxite samples from the traditional mining area
Sample % Al2O3 % Fe2O3 % SiO2 % CaO % P2O5 % Cr2O3 % ZnO % MnO
DCS 11A +200 47.2 18.2 0.8 0.03 0.11 0.164 0.014 0.16
DCS 11A +325 47.3 17.7 0.8 0.04 0.09 0.137 0.014 0.16
DCS 11A −325 47.9 18.2 0.82 0.04 0.1 0.139 0.016 0.16
DCS 10B +200 47.3 19.5 2.49 0.27 0.15 0.147 0.023 0.34
DCS 10B +325 47.0 18.4 2.38 0.21 0.14 0.110 0.023 0.21
DCS 10B −325 47.1 18.4 2.4 0.19 0.15 0.105 0.024 0.17
DCS 21B +200 46.6 19.6 0.58 0.04 0.15 0.113 0.028 1.11
DCS 21B +325 46.2 19.1 0.57 0.04 0.15 0.108 0.021 0.76
DCS 21B −325 46.7 19.6 0.61 0.04 0.15 0.110 0.022 0.71
DCS 8B +200 47.1 18.3 2.34 0.08 0.16 0.079 0.027 0.53
DCS 8B +325 47.1 18.5 2.34 0.06 0.16 0.078 0.024 0.37
DCS 8B −325 47.7 19.2 2.44 0.06 0.17 0.082 0.025 0.34
DCS 14 +200 47.9 16.0 2.6 0.11 0.18 0.121 0.102 2.53
DCS 14 +325 47.8 16.4 2.59 0.10 0.19 0.120 0.071 1.64
DCS 14 −325 47.9 16.6 2.61 0.10 0.19 0.121 0.045 0.90
DCS 16A +200 46.0 18.0 3.48 0.15 0.77 0.121 0.089 0.38
DCS 16A −325 46.5 18.5 3.44 0.19 0.81 0.114 0.093 0.36

trends were observed between the % Al2O3, SiO2, CaO, It is probable that the characteristics of bauxite fractions of
MnO, and ZnO in relation to the particle size of samples each sample are mainly determined by small constituent
from the new mining area. bauxite particles that aggregate together. The data so far are
An assessment of the XRF data for bauxite samples from not conclusive however they suggest that fractioning bauxite
both mining areas shows that some metal species concentrate samples followed by use of conventional XRF, XRD or other
in the coarse or fine bauxite particles but this is not widespread. traditional techniques will not concentrate mineral species
18 M. Coley et al.

3.0

2.5

2.0
% MnO

1.5

1.0

0.5

0.0
11A 11A 11A - 10 B 10B 10B - 21B 21B 21B - 8B 8B 8B - 14 14 14 - 16A 16A -
+200 +325 325 +200 +325 325 +200 +325 325 +200 +325 325 +200 +325 325 +200 325

Sample Names - Traditional Mines

Fig. 2 % MnO in fractions of bauxite samples from the traditional hematite-rich mining area. (DCS precedes the name of each sample in the chart)

Table 5 XRF data for fractions of bauxite samples from the new mining area
Sample % Al2O3 % Fe2O3 % SiO2 % CaO % P2O5 % Cr2O3 % ZnO % MnO
DCN 30A +200 46.2 22.9 0.34 0.09 0.85 0.316 0.080 2.19
DCN 30A +325 48.0 17.4 0.32 0.09 0.8 0.169 0.100 2.35
DCN 30A −325 48.4 16.1 0.32 0.10 0.81 0.141 0.105 2.32
DCN 10A (+200) 46.0 18.6 0.45 1.02 3.08 0.241 0.106 1.17
DCN10A (−325) 46.1 16.8 0.47 1.16 3.15 0.139 0.090 0.75
DCN 16A +200 42.9 25.8 1.17 0.24 1.62 0.711 0.041 0.06
DCN 16A −325 47.9 16.4 1.4 0.40 1.98 0.198 0.033 0.04
DCN 21 +200 46.0 14.8 1.83 3.21 5.12 0.169 0.097 0.29
DCN 21 +325 46.6 14.7 1.89 3.03 5.28 0.128 0.098 0.34
DCN 21 −325 46.3 14.2 1.98 2.95 4.85 0.113 0.100 0.33
DCN 29 +200 44.8 21.8 0.36 1.87 6.03 0.391 0.053 0.24
DCN 29 +325 47.0 16.0 0.36 2.58 7.63 0.208 0.053 0.22
DCN 29 −325 47.0 12.2 0.36 3.65 10.20 0.135 0.054 0.16

12

10

8
% P2O5

0
30A 30A 30A 10A 10A 16A 16A 21 21 21 29 29 29
(+200) (+325) (-325) (+200) (-325) (+200) (-325) (+200) (+325) (-325) (+200) (+325) (-325)
Samples Names - New goethite-rich mine
Fig. 3 % P2O5 in fractions of bauxite samples from the new mining area (DCN precedes the name of each sample in the chart)
Challenges with Characterizing and Processing Goethite-Rich Jamaican Bauxites 19

enough to provide improved mineralogy information. The The plots below are for fractions of the bauxite samples
approach seems promising for samples with unusually high from each mining area. Figures 4a, c, and e are for currently
impurity concentrations such as DCN29 however. mined bauxites while Figs. 4b, d, and f are for the new ores.
A plot of % MnO versus % ZnO for bauxite fractions from the
Elemental Correlations traditional mine (Fig. 4a) shows a strong correlation with only
The mineral impurities in bauxites are typically at low one bauxite (DCS16A) deviating significantly from the line.
concentrations and are difficult to identify using traditional Feret and See identified lithiophorite ((Al,Li)(Mn4+,Mn3+)
XRD. Simple plots of the elemental concentrations of spe- O2(OH)2) as the main manganese mineral in Jamaican bauxite.
cies in the ore may give clues about their mineral associa- They proposed that Zn2+ substitutes for Li+ and results in a
tions [15]. This approach is useful where distinct minerals of strong correlation between the Zn and Mn [16]. They proposed
the low-concentration species do not exist or where the that zinchophorite, a zinc-enriched lithiophorite, is the
mineral concentrations are extremely low. zinc-contaminating mineral in Jamaican bauxite.

3.0 2.5
% MnO % MnO - DCS 16A y = 19.34x - 0.71
2.0
2.0 y = 26.05x - 0.16 R² = 0.34
% MnO

R² = 0.88

% MnO
1.5
1.0 1.0
0.5
0.0
0.0
0.00 0.03 0.06 0.09 0.12
0.00 0.05 0.10 0.15
a % ZnO b % ZnO

1.0 12
y = 1.09x + 0.11 10 y = 1.93x + 1.07
0.8 R² = 0.777
R² = 0.14
8
% P2O5

0.6
% P 2O 5

6
0.4
4
0.2 2
0.0 0
0.00 0.10 0.20 0.30 0.0 1.0 2.0 3.0 4.0
c % CaO d % CaO

0.20
0.8
0.15 y = 0.037x - 0.41
0.6
R² = 0.824
% Cr2O3

% Cr2O3

0.10 0.4

0.05 y = -0.0038x + 0.19 0.2

R² = 0.031
0.00 0.0
0.0 10.0 20.0 30.0 0.0 10.0 20.0 30.0
e % Fe2O3 f % Fe2O3

Fig. 4 Correlation of selected elemental oxides in bauxites from the traditional (a, c and e) and new goethitic mining areas (b, d and f)
20 M. Coley et al.

Although the number of samples in this study is small, the samples and has an extensive database on the minerals found in
strong correlation observed between % MnO and % ZnO in bauxites across the world. For a given bauxite, the programme
the hematitic bauxites suggests occurrence of a single mineral apportions the metal species to their natural host minerals such
that contains both metals. A plot of % MnO versus % ZnO for that they are distributed to match the XRD profile while
the goethitic bauxites suggests that the mineral associations of achieving a balance with the XRF concentrations [14].
zinc and manganese are much more complex. Zinc concen- Only one bauxite sample was studied via XDB in this pre-
trations in these ores are also consistently higher and more liminary work. Fractions of the unsieved and sieved portions of
than one mineral sources might be present. The higher zinc sample DCN21A (+200, −200/+325, and −325) were exam-
concentrations and possibly the presence of uncharacteristic ined. The XDB output (Table 6) predicts the distribution of the
zinc-bearing contaminants might have implications for the metal oxides among the various bauxite minerals in the sieved
management of soluble Zn in the new bauxite. and unsieved fractions of DCN21A. The programme identified
Figure 4c shows a very weak correlation between % P2O5 gibbsite as the main alumina mineral in all the samples. All
and % CaO. This contrasts with the fairly strong relationship samples had additional alumina in boehmite, crandallite, and
observed in Fig. 4d which shows the plot for the new aluminous goethite; however, nordstrandite was only detected
bauxite mine. Previous work has identified crandallite as the in the −325 fraction. Based on the XDB analysis, crandallite
main P mineral in the new mine [6, 11]. Bauxites from both was the only P mineral detected in the unsieved DCN21A.
mines will likely have very different caustic soluble P2O5 Analysis of the +200 mesh DCN21A fraction identified both
concentrations. crandallite and hydroxyapatite however.
Figure 4e plots % Cr2O3 against % Fe2O3 for the cur- While the predictive ability of XDB relies heavily on the
rently mined ore while Fig. 4f gives a similar plot for the quality of the XRD scans and the accuracy of the XRF data,
new mine. Clear differences in the mineral associations are the results obtained for DCN21A demonstrate the potential
again observed. This suggests need for careful study of of using XDB to study fractions of bauxite samples, espe-
caustic soluble chromium in the new bauxites. Based on the cially those with unusually high concentrations of mineral
strong correlation in Fig. 4f, the chromium impurity is impurities. Further work is required to determine whether
probably associated with the iron mineral in the new mine. these approaches can eventually identify the presence of
low-concentration mineral species, especially those associ-
ated with Cr or Zn.
XDB Analysis

The XDB software was applied to fractions of the bauxite Caustic Soluble Concentrations
samples to predict their mineral constituents by relating their
measured XRF and LOM data with the XRD scan obtained in The concentrations of caustic soluble P2O5, Cr2O3, and ZnO
each case. The programme was specially developed for bauxite were studied for three bauxite samples from the new mining

Table 6 XDB predictions of the mineral species in the unsieved and sieved fractions of sample DCN21A (new mining area)

Crandalite Alumino-goethite Gibbsite Boehmite

Unsieved (+200) (+325) (-325) Unsieved (+200) (+325) (-325) Unsieved (+200) (+325) (-325) Unsieved (+200) (+325) (-325)
Fe2O3 (%)
TiO2 (%)
CaO (%) 2.44 2.32 2.35 2.18 15 15.26 14.7 14.3
P2O5 (%) 6.16 5.86 5.95 5.53
SiO2 (%)
Al2O3 (%) 6.64 6.32 6.41 5.95 1.69 1.72 1.66 1.61 38.78 33.47 34.78 33.8 not observed 4.14 4.43 4.51

Anatase Quartz Hydroxyapatite Norstrandite

Unsieved (+200) (+325) (-325) Unsieved (+200) (+325) (-325) Unsieved (+200) (+325) (-325) Unsieved (+200) (+325) (-325)
Fe2O3 (%)
TiO2 (%) 1.98 1.91 2.02 1.99
CaO (%) 0.67
P2O5 (%) 0.51
SiO2 (%) 1.89 1.98
Al2O3 (%) 0.86
Challenges with Characterizing and Processing Goethite-Rich Jamaican Bauxites 21

Table 7 % caustic soluble P2O5, Cr2O3, and ZnO in different size fractions of bauxite samples from the new mining area
Sample % P2O5 % caustic soluble % Cr2O3 % caustic soluble % ZnO % caustic soluble
(XRF) P2O5 (XRF) Cr2O3 (XRF) ZnO
DCN21 (+200) 5.12 55.0 0.169 14.8 0.097 12.1
DCN21 (+325) 5.28 52.5 0.128 17.2 0.098 10.6
DCN21 (−325) 4.85 55.0 0.113 15.5 0.100 11.0
DCN16A(+200) 1.62 88.0 0.711 10.0 0.041 1.2
DCN16A (−325) 1.98 80.5 0.198 21.8 0.033 1.7
DCN30A (+200) 0.85 99.5 0.316 25.0 0.080 6.2
DCN30A (+325) 0.80 100.5 0.169 35.0 0.100 6.35
DCN30A (−325) 0.81 101 0.141 38.5 0.105 5.05

area (Table 7). DCN30A is a typical low P bauxite but its Management of Caustic Soluble P2O5, ZnO,
low % CaO suggests presence of a non-crandallite P mineral, and Cr2O3 from the New Mining Area
possibly variscite (Table 5). DCN21A has excess % CaO
beyond that due to crandallite alone; however, for sample Of the three impurities studied in this work, the management
DCN16A, the %CaO:%P2O5 ratio suggests that crandallite is of P2O5 will likely require the most significant effort and
likely the only P mineral that is present (Table 5) [11]. The possibly will incur the greatest cost. The solubilities of the
caustic soluble concentrations of bauxite fractions from the P2O5 minerals in this work (52.5–100%) are much higher
currently mined areas were not studied as their soluble than those observed for the Zn (1.2–12.1%) and Cr impu-
concentrations in plant liquors are typically low and are well rities (10.0–38.5%) (see Table 7). Bauxite blending has long
known. Strategies to manage their build-up in the traditional been used as an option for managing high concentrations of
low-temperature process are well established. On the other bauxite impurities, hence this section explores the use of
hand, the solubility characteristics of P2O5, Cr2O3, and ZnO blending to manage the high % P2O5 in the new bauxite.
from the new bauxite mines are unclear and the extent to Samples of currently mined bauxites were digested by
which they dissolve from each bauxite fraction has not been themselves and in blends with the goethitic ores. The mg/L
reported. caustic soluble P2O5 was measured in each case and is
Based on data from the three bauxites, there are no major reported in Table 8.
differences in the extraction of phosphorus from the fractions When bauxite from the traditional mines (0.22% P2O5)
of each ore (Table 7). There were major differences however was digested under low-temperature conditions, the average
between each sample. Several factors could be responsible P2O5 concentration was 169 mg/L. In contrast, separate
for the differences, for example, the nature of the P mineral digestions of unsieved ores from the new mines containing
(e.g., in DCN30A) or the presence of excess CaO in the 1.0%, 2.0%, and 3.0% P2O5 gave soluble P2O5 concentra-
bauxite (e.g., in DCN21A), among others [11]. On average, tions of 981 g/L (75% caustic soluble P2O5), 2287 mg/L
about 70% of the P2O5 that enters with the bauxite is (85.5% caustic soluble P2O5), and 3019 mg/L P2O5 (74.9%
expected to end up in the liquor [11]. The results in this caustic soluble P2O5), respectively (Table 8). Separate
study, however, show a much wider range and illustrate the blends comprising 25, 50, and 75% ore from the new mines
difficulties that will be encountered in managing process (1, 2, and 3% P2O5) were combined with the matching
impurities from these ores. proportions of the traditionally processed ore (i.e., 75, 50,
As seen for soluble phosphorus (Table 7), there is no and 25% of traditional ore; 0.22% P2O5).
significant differentiation in the soluble Zn concentrations The soluble phosphorus concentrations (mg/L P2O5) of
among the different bauxite fractions. Cr2O3 was more digest liquors from each goethitic bauxite sample and its
extractable from the finer fractions of DCN16A and blends with the low P ore (from current mines) were plotted
DCN30A, however there is insufficient data from which to against the % P2O5 in the bauxite. The plots gave linear
draw conclusions. relationships with R2 > 0.995 (Table 8). As the total % P2O5
22 M. Coley et al.

Table 8 Caustic soluble P2O5 based on digests of a traditional hematite-rich bauxite, digests of a goethitic bauxite, and digests of blends from
both ores
Blends 1% P2O5 (new bauxite) with 2% P2O5 new bauxite) with 3% P2O5 new bauxite) with
0.2% P2O5 (traditional bauxite) 0.2% P2O5 (traditional bauxite) 0.2% P2O5 (traditional bauxite)
Total mg/L % caustic Total mg/L % caustic Total mg/L % caustic
P2O5 P2O5 soluble P2O5 P2O5 P2O5 soluble P2O5 P2O5 P2O5 soluble P2O5
(%) (%) (%)
100% 0.22 165 57.5 0.22 186 64.8 0.22 157 54.9
traditional bxt
(TB)
75% TB, 25% 0.42 387 70.9 0.68 592 67 0.94 836 68.4
NB
50% TB, 50% 0.63 615 75.1 1.13 1150 78.3 1.66 1527 70.8
NB
25% TB, 75% 0.83 914 84.7 1.59 1697 82.1 2.37 2245 72.9
NB
100% new 1.03 981 75.2 2.04 2227 85.5 3.09 3019 74.9
bauxite (NB)
Equation and y = 1005.9x − 49.4; R2 = 0.999 y = 1139.8x − 120; R2 = 0.997 y = 994.7x − 90.4; R2 = 0.999
R2

in the blends increased, higher soluble P2O5 concentrations

were observed. This means that blends of the new bauxites Conclusions
and the traditional ores can be successfully processed and the
resulting soluble P2O5 concentrations can be predicted On average, bauxite from the traditional mining areas had
(Table 8). Lime requirements for phosphorus control can larger +200 fractions while the new bauxites had larger −325
therefore be estimated. Accuracy of the estimates will be fractions. For the traditional mines, concentrations of Al2O3,
impacted by the phosphorus mineralogy of the ores and the SiO2, CaO, P2O5, and ZnO were similar for all three frac-
calcite concentrations. When goethitic bauxite with 1.0% tions of each bauxite; however, the % MnO values were
P2O5 was blended 50/50 with traditional bauxite containing higher in the +200 size fractions. In the new mining areas,
0.22% P2O5, the resulting soluble P2O5 in the digestion there were higher % Fe2O3 and Cr2O3 in the +200 fractions
liquor was 615 mg/L. This is almost four times higher than but Al2O3, SiO2, CaO, MnO, and ZnO were similar for the
the 165 mg/L P2O5 that the plant would be accustomed to if three fractions of each bauxite sample. Nevertheless, baux-
the traditional ore (0.22 % P2O5) was processed. Much ites with high mineral concentrations (MnO, Cr2O3, or P2O5)
higher soluble P2O5 concentrations occur with bauxite tended to show enrichment in one of the fractions. Study of
blends that contain higher proportions of the new bauxite. these fractions using XDB or other sophisticated techniques
Blending bauxite from the new mines with low P2O5 ores may show enhanced potential to identify minerals that were
is the best option currently available for managing the high not observed during analysis of the bulk, unsieved bauxites.
phosphorus concentrations in the new bauxite mines. Even The total impurity concentrations (% P2O5, % Cr2O3, %
with blending, higher soluble P2O5 concentrations will ZnO, and % MnO) in the new bauxites are sometimes more
occur. This will require more CaO to precipitate the impurity than five times higher than in the traditionally processed
and will result in a higher mud load. New processes for ores. Processing these ores will therefore require strategies to
managing soluble P2O5 are therefore required if these high manage these impurities. There are options to manage sol-
phosphorus bauxites are to be economically processed to uble zinc impurities but these are traditionally associated
yield high-quality smelter-grade alumina [17]. with high-temperature bauxite plants. Pilot-scale recirculat-
The processing of goethitic bauxites is usually associated ing experiments are probably needed to assess their rele-
with slow mud settling and lower alumina yields. Increased vance for use in low-temperature processing of the new
soda and alumina losses, higher energy costs, and lower quality bauxite feed. Managing soluble Cr2O3 may also be chal-
alumina also occur [3, 18]. The processing of ores from the new lenging and more data are therefore needed to better
bauxite mines will likely experience some of these challenges; understand the behaviour of these impurities.
however, in addition, the management of P2O5, ZnO, and Whether the new bauxites are processed by themselves or
Cr2O3 impurities in the bauxite will further complicate alumina in blends with traditional hematitic ores, much higher caustic
production from these replacement ores [19, 20]. soluble impurities will result. Managing these will likely
Challenges with Characterizing and Processing Goethite-Rich Jamaican Bauxites 23

impact production costs and also alumina yield and purity. If 10. Kirwan L., Lawson D., Rijkeboar A., Hodnett K., Mooney A.,
the process slurries settle slowly, this will further complicate Walker R. (2009) Characterisation of iron mineralogy in Jamaican
Bauxite and associated aspects of alumina and soda losses. Light
the processing operations. Metals, 133–138
11. Henry, K., Coley, M., Greenaway, A., (2018) The dissolution of
Phosphorus from Jamaican bauxites under low temperature Bayer
References conditions, Hydrometallurgy, 179, 132–140.
12. Sajó, I.E. X-Ray diffraction quantitative phase analysis of Bayer
process solids. In Proceedings of the10th International Congress of
1. Ostap, S., Effect of Bauxite Mineralogy on its Processing. In ICSOBA, Bhubaneshwar, India, 28–30 November 2008; pp. 71–
Bauxite Proceedings of 1984 Bauxite Symposium. The Society of 76.
Mining Engineers of the American Institute of Mining, Metallur- 13. Sajó, I.E. XDB Powder Diffraction Phase Analytical System,
gical and Petroleum Engineers Inc.: Los Angeles CA. pp 651–671. version3.107; Software, Copyright Sajó, I.E. 1987–2016; Sajó, I.
2. Teas, E.B. and J.J. Kotte. The effect of impurities on process E.: Budapest, Hungary, 2005.
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Bauxite Symposium IV, Kingston. 1980. of Bidi-koum Bauxites (Guinea). Clays Clay Miner. 45, 418–427.
3. Lawson D., Rijkeboer A., Andermann L.J., Mooney A. Impact of 15. Greenaway, A.M., Bucknor, A.N., Henry K. and Coley, M.D.
Jamaican bauxite mineralogy on plant operations. Light Metals (2013) Identifying possible associations of minor and trace
2008, 113–118. elements with major elements in Jamaican hillside and catchment
4. Libby, S.C., Grubbs, D.K., Rodenburg, J.K., Wefers, K.A. (1980); bauxites using multivariate analysis tools; Minerals Engineering
The Geology, Mineralogy and Clarification Properties of Red and 53, 124–135
Yellow Jamaican Bauxites. Jamaica. Jour. Geol. Soc. Jamaica, 16. Feret, F.; See, J. (2006) Occurrence and Craracterization of Zn and
176–186. Mn in Bauxite. Light Metals 41–45.
5. Grubbs, D.K. (1982) The Iron and Phosphate Mineralogy of the 17. Lindsay, S. J. (2005) SGA requirements in coming years. Light
Bauxites in Harmons Valley and the Mocho Mountains, Jamaica. Metals 2005, 117–122.
Jour. Geol. Soc. Jamaica, 55–61 18. Powell KA, Kirwin LJ, Hodnett, K, Lawson D, Rijkeboer A.
6. Young N, Coley M, Greenaway A (2019) Mineralogical investi- Characterisation of Alumina and soda losses associated with the
gations of Jamaican hematite-rich and goethite-rich bauxites using processing of geothitic rich Jamaican bauxite. Light Metals 2009,
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7. Authier-Martin, M., Forté, G., Ostap, S., See, J. (2001) The H. Approaches to the Processing of Jamaican Bauxite with High
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 Sugar-Derived Causticization Additives
for the Bayer Process

Amit Desai, Jun Su An, and LoongYi Tan

Abstract Introduction
Bauxite digestion in the Bayer process results in a buildup
of sodium carbonate in the caustic liquor, which reduces Bayer process liquors are inevitably contaminated with
the efficiency of alumina production. This effect is carbonate, which arises from base-catalyzed oxidation of
mitigated by lime causticisation, during which carbonate organic compounds and dissolution of inorganic carbonate
is removed, preferably as calcium carbonate. The extent from the bauxite, and absorption of CO2 from the air [1, 2].
and efficiency of causticisation in Bayer liquors are The carbonate content of Bayer liquor is conventionally
limited by the formation of tricalcium aluminate expressed as the caustic to soda ratio, C/S, where
(TCA) and alumino-carbonates, which also reduce overall C = [NaOH] in units of g/L of Na2CO3 and S = C + [
plant productivity due to the consequent loss of alumina Na2CO3] in the same units. C/S = 1 for pure NaOH.
from the liquor. We demonstrate that TCA formation can Lime causticisation is used to limit the carbonate content
be minimized or eliminated by using sugar-derived of the liquor and thus maintain its productivity. Improve-
molecules, specifically gluconic acid, a mixture of ments in the causticization process therefore lead to better
gluconic and glucaric acids, and sodium gluconate. This liquor productivity, and hence higher alumina production, as
reduction in TCA formation improves the efficiency of well as lower lime consumption. The C/S of the main liquor
causticisation by three to four times as determined by the stream in Bayer refineries is generally in the range of 0.80–
rate constants for carbonate consumption or by the 0.95, depending on carbonate inputs and the efficiency of the
relative increase of C/S ratio. This in turn reduces causticisation process. The desired solid product of causti-
alumina and caustic losses in the causticiser, with the cisation (calcium carbonate) is rarely formed directly in
potential to improve the plant liquor C/S and hence the Bayer liquors, but mostly via alumino-carbonate intermedi-
overall productivity of the Bayer circuit. ates, with tricalcium aluminate (TCA) as the undesired
byproduct. TCA formation not only reduces causticisation
Keywords and increases lime usage but also results in alumina loss that

directly reduces the overall alumina yield of the Bayer plant.
Bayer process Causticization Organic acids and salts The relative proportions of calcium carbonate and TCA
Tricalcium aluminate inhibition depend on a range of equilibrium and kinetic factors [3, 4].
Approaches to limiting TCA formation include causticising
at high temperature (e.g., at 145 °C) in a single stage [5] or
multiple stages [6], or at normal temperatures (<105 °C)
using chemical additives such as phosphate [7] or gluconate
[8] as ‘TCA inhibitors’.
In this paper, we describe preliminary results on
A. Desai (&)
J. S. An
L. Tan sugar-derived molecules as TCA inhibitors or causticization
Solugen Inc., 14549 Minetta Street, Houston, TX 77035, USA additives. The inhibitors tested are gluconic acid, a mixture
e-mail: [email protected]
of gluconic and glucaric acid, and sodium gluconate. These
J. S. An molecules were produced by oxidizing sugars using Solu-
e-mail: [email protected]
gen’s proprietary, carbon-negative chemienzymatic process.
L. Tan
e-mail: [email protected]

© The Minerals, Metals & Materials Society 2024 24

S. Wagstaff (ed.), Light Metals 2024, The Minerals, Metals & Materials Series,
https://doi.org/10.1007/978-3-031-50308-5_3
Sugar-Derived Causticization Additives for the Bayer Process 25

Materials and Methods Procedure to Evaluate Causticization Additives

Materials SBGL (0.5 L) was heated to 95 °C with agitation. The

causticization additive was dosed at a molar concentration of
Laboratory-grade hydrated lime and sodium aluminate, and 4.58 mM (equivalent to 1 g/L sodium gluconate, as per prior
analytical-grade sodium hydroxide were purchased from art [3, 5]). Reaction was initiated (t = 0) by adding a 140%
Chem-Supply, Australia. Analytical-grade sodium sulfate, stoichiometric lime charge, and the reaction mixture was
sodium carbonate, aluminium hydroxide, and silica were continuously agitated in a shaking water bath at 95 °C in
purchased from Sigma-Aldrich. A 50 wt% aqueous solution separate bottles according to the number of samples
of gluconic acid, sodium gluconate in powder form, and 45 required. After the desired reaction time, the appropriate
wt% aqueous solution of a proprietary mixture of gluconic sample was filtered (through a 0.45 lm Acrodisc®) and
and glucaric acid (‘Gluconic-Glucaric Mix’) were supplied analyzed for A, C, and S using the Bayer Liquor Analysis by
by Solugen Inc. Infra-red (BLAIR) system [9, 10]. At the end of the
pre-determined reaction time, the bulk slurry was filtered and
the filtrate was analyzed for A, C, and S.
Preparation of Synthetic Bayer Green Liquor
(SBGL)
Results and Discussion
Synthetic Bayer Green Liquor was used to mimic the liquor
during the causticization process in a production setting. The results of an initial test on the effect of gluconate on
Sodium hydroxide, aluminium hydroxide, sodium carbonate, causticisation are shown in Table 2.
silica, sodium sulfate, and quick lime were dissolved in C/S ratio as a function of time is plotted in Fig. 1 along
deionized (DI) water at 70 °C in a stainless-steel vessel with with comparative values for a similar test in a plant liquor
stirring using an OLS Aqua Pro Shaking Water Bath. In from the literature [3]. The current test shows a significantly
accordance with the American Bayer industry convention, greater initial enhancement by gluconate, followed by a
A is the concentration of Al2O3 in g/L, C (caustic) is the decline which is not evident in the presence of gluconate in
concentration of NaOH + NaAlO2 in units of g/L Na2CO3 the previous work. These differences are probably due to
equivalent, and S (soda) = C + Na2CO3 (g/L). The con- differences in testing protocols and/or differences between
centrations of the ingredients were adjusted to achieve the the specific plant liquor and our SBGL. Such drops in C/S
composition shown in Table 1. Batches of SBGL were ratio have been attributed to a change in reaction mechanism
prepared prior to each experimental run and used immedi- favoring the formation of tricalcium aluminate (TCA) over
ately to avoid auto-precipitation of alumina. calcium alumino-carbonate or carbonate solids [3]. Our

Table 1 Target composition of Components A C A/C S SiO2 Na2SO4

SBGL
Conc. (g/L) 75 115 0.65 140 1 6

Table 2 Data for causticization Additive Time (min) A C S C/S

of SBGL with and without
sodium gluconate using 40% Blank 0 74.6 117 141.8 0.83
excess lime, 95 °C 30 70.3 127.2 145.6 0.87
60 70.4 128.3 146.9 0.87
180 69.0 125.7 146.6 0.86
Sodium gluconate 0 75.7 118 142.1 0.83
30 73.3 135.3 145.2 0.93
60 72.8 138.3 145.7 0.95
180 70.7 130.6 146.5 0.89
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Dear Madam:—In answer to your inquiries I would say that Bridget
Ryan has served me in the capacity of chambermaid for two years,
and has given me satisfaction. She is neat and tidy in her work,
and respectful in her deportment.
Mrs. James Brown.

Rekommendationsbref för en tjenarinna.

Pittsburg, Pa., den 1 Mars 1894.

Fru C. B. Brown.
Min Fru! Till svar på edra spörjsmål kan jag säga, att Bridget
Ryan har under två år varit i min tjenst i egenskap af
kammarjungfru och har varit till min fulla belåtenhet. Hon är nätt
och renlig i sitt arbete samt höflig i sitt uppförande.
Fru Jakob Brown.

BJUDNINGSBREF (Invitations).
 Bjudningsbref böra besvaras så skyndsamt som möjligt. Intet svar
erfordras på inbjudning till en “mottagning” (reception) eller till “té.”
Bjudning till en bal bör utsändas omkring tre veckor i förväg, bjudning
till andra festligheter minst en vecka före den för samkvämet bestämda
tiden.
Inbjudningar till dansnöjen och baler utfärdas i värdinnans namn och
böra vara affattade i följande ordalag:

Mrs. Axel Brown requests the pleasure

of your company
on Wednesday evening, December tenth,
at nine o’clock.
Dancing.
Or,
Mrs. Axel Brown,
At Home,
Wednesday evening, December tenth,
at nine o’clock.
Dancing.

Fru Axel Brown anhåller om nöjet

af ert sälskap
Onsdags afton, den tionde December,
klockan 9.
Dans.
Eller:
Fru Axel Brown,
Hemma,
Onsdags afton, den tionde December,
klockan 9.
Dans.
 Bokstäfverna R. S. V. P., som äro en förkortning af det franska
uttrycket “Respondez s’il vous plait” (haf godheten lemna svar) sättas
ofta nedtill på en inbjudning för att fästa uppmärksamhet på, att ett svar
åstundas. Följande formulär kan användas såsom jakande svar på
ofvanstående inbjudning.

“Mr. Smith accepts with pleasure Mrs. Brown’s kind invitation for
Wednesday evening, December tenth.”

“Herr Smith mottager med nöje fru Browns vänliga inbjudning till
Onsdags afton, den tionde December.”

Eller inbjudningen kan afböjas i följande ordalag:

“Mr. Smith regrets his inability to accept Mrs. Brown’s kind

invitation for Wednesday evening, December tenth.”

“Herr Smith är ledsen att icke vara i stånd att mottaga fru Browns
vänliga inbjudning till Onsdags afton, den tionde December.”

Inbjudningar till middagar utfärdas i värdens och värdinnans namn

och formuläret för dem lyder på följande sätt:

Mr. and Mrs. James Brown

request the pleasure of
Mr. and Mrs. Smith’s company at dinner,
October ninth, at seven o’clock.
1125 Arch St.

Herr och Fru Jakob Brown

anhålla om nöjet af
Herr och Fru Smiths sälskap till middag
den nionde Oktober, klockan sju.
1125 Arch St.
 Sådana inbjudningar böra ofördröjligen besvaras och svaret aldrig
affattas i vilkorliga ordalag. Uppgif bestämdt, huruvida Ni ämnar komma
eller icke komma. Om Ni skulle mottaga inbjudningen och senare finna,
att Ni är ur stånd att hålla ert löfte, så skrif genast till värdinnan och
underrätta henne derom.

Amerikas upptäckt 1492. Första åsynen af land.

Form of Acceptance.

Mr. and Mrs. John Smith

accept with pleasure the kind invitation of
Mr. and Mrs. James Brown for dinner
on October ninth, at seven o’clock.

Formulär för ett jakande svar.

Herr och Fru John Smith

mottaga med nöje Herr och Fru Browns
 vänliga inbjudning till middag
den nionde Oktober, klockan sju.

Skulle inbjudningen behöfva afböjas böra orden “äro ledsna att icke
kunna mottaga” (“regret that they cannot accept”) insättas i stället för
orden “mottaga med nöje” (“accept with pleasure”).
Inbjudningar till bröllop böra utsändas minst två veckor före
bröllopsdagen. De böra vara tryckta på papper af mindre format
(“biljett-papper”) samt bära föräldrarnes och brudens namn; de kunna
hafva följande utseende:

Mr. and Mrs. Smith

request the pleasure of your company at the

wedding of their daughter Anna to Henry Jones,
at Trinity Church,
on Thursday evening, June eleventh,
at eight o’clock.

Herr och Fru Smith

anhålla om nöjet af eder närvaro vid

vigselakten mellan deras dotter Anna och Henry Jones,
i Trinity Church,
klockan åtta Torsdagsafton,
den elfte Juni.

Mindre kort till de personer, som inbjudas till mottagningen efter

vigselaktens slut, inneslutas med bröllopsinbjudningen och lyda sålunda:

Reception

at 24 Vernon Place, at half-past eight.

Mottagning
 No. 24 Vernon Place, klockan half nio.

Intet svar erfordras på dessa inbjudningar. Om Ni icke kan öfvervara

mottagningen, bör Ni sända ert kort.
Inbjudning till té och vanliga mottagningar kunna skrifvas på visitkort
sålunda:

Tea

from seven to nine o’clock.

Té

från klockan sju till nio.

Vid besvarandet af inbjudningar bör Ni gifva akt på, huru de äro

affattade. Om de äro i tredje personen, bör svaret vara i tredje
personen; om i den första, böra de vara i första.

Invitation to a Dinner Party.

Mr. and Mrs. George request the pleasure of Mrs. Putnam’s

company at dinner on Thursday, the 19th of December, at six
o’clock.
Riversham Park, December 10.

Inbjudning till middag.

Herr och fru George anhålla om nöjet af Fru Putnams sällskap till
middag Torsdagen, den 19 December, klockan sex.
Riversham Park den 10 December.

Declining the Same.

 Mrs. Putnam regrets extremely that a prior engagement will
prevent her having the pleasure of dining with Mr. and Mrs. George
on the 19th of December.
31, Russell Square, December 11.

Afböjande svar på föregående.

Fru Putnam är särdeles ledsen, att en tidigare öfverenskommelse

hindrar henne från att hafva nöjet att infinna sig till middag hos
Herr och Fru George den 19 December.
31 Russell Square den 11 December.

Accepting.

Mrs. Putnam has much pleasure in accepting Mr. and Mrs.

George’s invitation to dinner on the 19th of December.
391, Russell Square, December 11.

Mottagande svar.

Fru Putnam har det stora nöjet att mottaga Herr och Fru Georges
inbjudning till middag den 19 December.
31 Russell Square den 11 December.

Invitation to a Dinner Party.

My Dear Miss Summer:

Will you favor us with your company at dinner on Tuesday next?
It will be quite a family gathering, but Edward and I should not
consider it complete without your presence. I will take no denial.
Believe me, Yours sincerely,
Hannah Delmar.
Judd Street, June 9.
 En annan middagsinbjudning.

Min Kära Fröken Summer!

Vill Ni hedra oss med ert sällskap till middag nästkommande
Tisdag? Det är ingenting annat än ett familjesälskap, men Edvard
och jag skulle icke anse det fullständigt utan er närvaro. Jag vill
icke veta af något afslag.
Var försäkrad om min uppriktiga vänskap,
Hanna Delmar.
Judd Street den 9 Juni.

The Same.

Dear Louis:
Come and dine with us on Thursday next, to meet a few old and
valued friends, whose names I shall not here mention, but I assure
you it will give you great pleasure to see them. Pray let me have a
favorable reply, and
Believe me, Yours ever sincerely,
Lucy Gordon.
The Elms, Hornsey, June 4.

En liknande inbjudning.

Käre Ludvig!
Kom och ät middag med oss nästkommande Torsdag, då du får
träffa några gamla, värderade vänner, hvilkas namn jag icke nu vill
uppenbara, men hvilka du säkerligen skall finna stort nöje i att
träffa. Var god och låt mig hafva ett gynsamt svar och var försäkrad
om, att jag förblifver
Din alltid uppriktiga vän,
Lucy Gordon.
 The Elms, Hornsey, den 4 Juni.

Invitation to Evening Parties.

Mrs. Falk requests the pleasure of Mr. Catto’s company to-

morrow evening, half-past nine.
Dancing.
Romney Lodge, January 4.

Inbjudning till aftonsälskap.

Fru Falk anhåller om nöjet af Herr Cattos sälskap i morgon afton

klockan half nio.
Dans.
Romney Lodge den 4 Januari.

An Invitation to an Evening Party.

Mrs. Strom requests the pleasure of Captain, Mrs. Frodsham, and

family’s company to a small evening party, on Friday, the 18th
September, 1893. Eight o’clock.
Music and cards.
4, St. Dominic Place, E. C.

Liknande inbjudning.

Fru Ström anhåller om Fru kaptenskan Frodshams och hennes

familjs sälskap vid en mindre aftonbjudning klockan 8 Fredagen
den 18 September 1893.
Musik och kort.
4, St. Dominic Place, E. C.

A Very Friendly Invitation.

 Ashmead, Dec. 22, 1893.
Dear Mrs. Hill:
We propose having a small party for music and cards next
Thursday, and hope that you, your husband, and the dear girls will
join us. If you can favor us with your company, please ask the
young ladies to bring their music, and do not be later than eight
o’clock.
We unite in kindest love to you all.
Believe me, most affectionately yours,
Susan Sharpless.

En särdeles vänlig inbjudning.

Ashmead den 22 December 1893.

Kära Fru Hill!
Vi ämna hafva ett mindre sälskap till musik och kort
nästkommande Torsdag och hoppas, att Ni, er man och era kära
flickor vilja komma till oss. Om Ni kan glädja oss med nöjet af ert
sälskap, så var god och bed de unga damerna att taga med sina
notor och kom icke senare än klockan åtta.
Vi förena oss alla i en kärleksfull helsning.
Er varmt tillgifna
Susanna Sharpless.

Accepting.

The Grove, Dec. 23, 1893.

My Dear Mrs. Sharpless:
We shall have much pleasure in accepting your kind invitation for
Thursday next. Edith desires me to give you her love, and to say
that she is delighted at the prospect of a musical evening; she will
bring all your favorite songs, and do her best to sing them.
 With our united regards, believe me,
Yours affectionately,
Jane Hill.

Mottagande Svar.

The Grove den 23 December 1893.

Min Kära Fru Sharpless!
Det är med stort nöje vi mottaga eder vänliga inbjudning till
nästa Torsdag. Edith beder mig framföra sin kärleksfulla helsning
och säga, att hon är förtjust öfver utsigten af en musik-afton; hon
skall taga med sig alla edra favoritsånger och göra sitt bästa i att
sjunga dem.
Mottag våra kärleksfulla helsningar och var förvissad om
Vår uppriktiga högaktning,
Johanna Hill.

Invitation to a Juvenile Party.

George Street, December 4th.

Dear Mrs. Gibson:
Will you allow your little girls to join a juvenile party at our
house, at five o’clock, on the 7th instant? It is Selina’s birthday, and
I have invited a few of her young friends to keep it with her.
I have named an early hour, as I do not like late hours for little
folks.
With kind regards, believe me, yours sincerely,
Maria Gray.

Inbjudning till ett ungdomssälskap.

George St. den 4 December 1893.

Min Kära Fru Gibson!
Vill Ni tillåta edra små flickor att deltaga i ett ungdomssälskap
hemma hos oss klockan fem den 7 dennes? Det är Selinas
födelsedag, och jag har inbjudit några af hennes unga väninnor att
komma till henne.
Jag har bestämt en tidig timme, emedan jag icke tycker om, att
smått folk är sent uppe.
Mottag min vänliga helsning och var försäkrad om
Min uppriktiga vänskap,
Maria Gray.

Answer Accepting.

John Street, December 4th.

Dear Mrs. Gray:
I feel much pleasure in accepting your kind invitation for my little
girls, particularly as you have named an early hour. I have hitherto
refused all invitations for them, on account of the late hours of
juvenile parties in the present day, which I consider very injurious
to children.
With many thanks, believe me, yours very sincerely,
Maria Gibson.

Mottagande svar.

John Street den 4 December 1893.

Kära Fru Gray!
Det är med stort nöje, jag mottager eder vänliga inbjudning till
mina små flickor, i synnerhet som Ni bestämt en tidig timme. Jag
har hittills afböjt alla inbjudningar till dem, på grund af att
ungdomssälskap i våra dagar hållas så sent, något som jag anser
särdeles skadligt för barn.
 I det jag frambär min hjertliga tacksamhet, förblifver jag
Eder uppriktiga,
Maria Gibson.

Declining.

John Street, December 4, 1893.

My Dear Mrs. Gray:
Thanks for your kind invitation to my little ones. I should not
hesitate to accept it if they were quite well, but Sarah has a very
bad cold and sore throat; and as our doctor has some fear that she
is showing symptoms of measles, I am compelled to decline it.
I hope Selina may enjoy her birthday party. Kiss her for me, and
wish her many happy returns of the day.
Ever yours very truly,
Maria Gibson.

Afböjande svar.

John Street den 4 December 1893.

Min Bästa Fru Gray!
Mottag mina tacksägelser för er vänliga inbjudning till mina små.
Jag skulle icke draga i betänkande att mottaga den, om de voro
riktigt friska, men Sara lider af en mycket svår förkylning och af
ondt i halsen; och som vår läkare hyser farhågor för symptomer till
mässling, ser jag mig nödsakad att lemna ett afböjande svar.
Jag hoppas Selina skall komma att roa sig på sin födelsedag.
Kyss henne från mig och önska henne många lyckliga födelsedagar.
Eder mycket tillgifna,
Maria Gibson.
Karl Von Linné, verldsberömd
svensk naturforskare.
 Om skiljetecknen.
Skiljetecknens ändamål är att främja öfverskådligheten af skriftlig
framställning och, i sammanhang dermed, att angifva hvilopunkter för
rösten vid uppläsning.
Man har indelat skiljetecknen i två klasser: De större skiljetecknen
och de mindre skiljetecknen.
De större skiljetecknen, hvilka sättas vid slutet af fullständiga
meningar och beteckna de längsta uppehållen, äro: punkt,
frågetecken och utropstecken.
De mindre skiljetecknen, hvilka sättas inuti meningar och beteckna
kortare uppehåll äro: komma, semikolon, kolon,
inneslutningstecken och tankstreck.
Andra skriftecken äro; anföringstecken, bindetecken,
uteslutningstecken, likhetstecken, accenttecken, paregraftecken,
hänvisningstecken, omsägningstecken, kvantitetstecken, et-tecken samt
förklaringstecken.
Att på rätt sätt använda skiljetecknen är af den allra största vigt. En
persons sätt att bruka dem är en god gradmätare på hans bildning,
eftertanke och ordentlighet.
Riktig satsbildning är ett nödvändigt vilkor för god interpunktion (bruk
af skiljetecknen). En sådan omöjliggöres eller försvåras genom fel mot
satsläran. Omsorgsfull uppläsning af hvad man skrifvit främjar
skiljetecknens rätta bruk.
Mycket ofta gifva samma ord helt olika mening med olika
interpunktion. Det är t. ex. stor skilnad mellan “ett mindre, vackert rum”
och “ett mindre vackert rum,” mellan “den andra, vackra flickan” och
“den andra vackra flickan.” Ett ganska åskådligt exempel i samma
afseende äro följande verser, som uppgifvas vara ett af en domare
afkunnadt utslag i ett tvistemål:
 “Om nådig fröken det gamla aset,
Den döda hästen, begrafva vill,
Så må hon veta: att det hör rackarn,
Och ej vällofliga rätten till,”

hvilka ord få en ganska olika mening, om man sätter komma efter

“fröken,” men ej efter “hästen.”

Kort anvisning rörande bruket af de olika

skiljetecknen.

Punkt (.) sättes:

1) Efter meningar, som icke utgöra direkta frågor eller äro utrops-,
önske- eller uppmaningssatser. Ex. Alla nya sanningar möta i början
motstånd.
2) Efter ofullständiga satser, t. ex. svar, samt efter vissa enstaka ord
och uttryck, hvilka ej kunna anses såsom fullständiga satser, t. ex. de
flesta öfverskrifter, boktitlar, inskrifter m. m.
3) Stundom i stället för utropstecken, i synnerhet efter längre
meningar, hvilka innehålla en önskan eller en uppmaning.
4) Såsom förkortningstecken: t. ex. (= till exempel), d. v. s. (det vill
säga), o. s. v. (och så vidare), m. m. (med mera), i st. f. (i stället för).
Anm. Fel emot den första af dessa regler äro ytterst vanliga och röja
alltid okunnighet eller tanklöshet. Mången skrifver komma, då
sammanhanget (afslutad mening) nödvändigt kräfver punkt eller annat
större skiljetecken. I ett tidningsnummer står: “Ni bör taga i betraktande
Er ålder, krafterna förminskas och själsförmögenheterna med dem.”
Detta borde vara: Ni bör taga i betraktande Er ålder. (Kropps-) krafterna
förminskas, och själsförmögenheterna med dem.
Den oriktiga föreställningen, att ordet men icke får stå i början af en
mening, framkallar sådana interpunktionsfel som nedanstående:
“Patronen fordrade, att tjenarne skulle slafva från tidigt på morgnarna
till sent på aftnarna, men icke nog dermed. Han gaf dem ej tillräcklig
föda.” I st. f. Patronen … på aftnarna. Men icke nog dermed: Han gaf …
 Stundom får man se punkt, der meningen icke är afslutad. Så t. ex.
var det i synnerhet förr mycket vanligt att sätta punkt i st. f. komma vid
början af relativsatser (satser, som börja med hvilken, som, hvarpå o. s.
v.).

Frågetecken (?) nyttjas:

1) Efter direkta frågor (ord och satser), äfven när de stå inuti en
mening. Ex.: Hvarföre? Hvad har händt? Hvem der? ropade han. Har du
hört nyheten? frågade han.
2) Stundom inuti meningar (ensamt eller jemte utropstecken) för att
antyda tvifvel om en uppgifts sanning o. s. v. Ex.: Modern påstår, att
hennes son är lydig[?] och arbetsam.
Anm. Efter indirekta frågor sättes icke frågetecken, utan punkt. Ex.
Han frågade, hvad som hade händt.

Utropstecken (!) nyttjas:

1) Efter utrops- eller tilltalsord. Ex. Ack! Ve öfver förrädaren! Min
herre!
2) Efter meningar, som innehålla utrop, önskningar, befallningar eller
uppmaningar, äfven om de icke afsluta en mening. Ex. Hvad hör jag!
Gud skydde fosterlandet! Håll ut! Gud sade: “Varde ljus!” och det vardt
ljus.
3) Stundom sättes utropstecken inom parentes inuti meningar för att
påpeka tryck- eller skriffel, besynnerliga påståenden, ovanliga ord o. s.
v. Ex. Karlen skref, att han blifvit bragd [!] i olycka.
Anm. 1. Inuti tal, bref o. d. plägar man omsluta tilltals-uttryck inom
kommata i st. f. att sätta komma före och utropstecken efter dem. Ex.
Det är, mine herrar, ingen lätt fråga, som vi nu dryfta.
Anm. 2. Sätt ej utropstecken efter utropssatser, som till betydelsen äro
vilkorssatser. Ex. Kom (= om du kommer), så skall du få se.
Anm. 3. I allmänhet bör inom en mening ej gerna förekomma mer än
ett utropstecken. Det gäller derför att noga tillse, huruvida,
utropstecknet tillhör ett enskildt ord eller hela satsen. Ex. Hörpå, gosse!
Ack, hvad lyckan är flyktig! Drottning, Björn! du fåfängt jagar. (Tegnér).
Verka, menniska, medan tiden varar!
Anm. 4. Man bör ej använda utropstecken ofta och ej gerna sätta två
eller flere tillsammans.

Kommats (,) användning är i flere fall ganska svår. Brist på utrymme

hindrar oss att här gifva fullständiga regler derför, men följande korta
anvisningar torde dock, om också icke uttömmande, tjena till någon
ledning. Vi rekommendera härvid exemplen till noggrant begrundande,
ty genom dem torde mer kunna läras än genom de korta regler, vi här
kunna gifva.
Detta skiljetecken bör utsättas i följande fall:
1) Mellan samordnade hufvudsatser, i de flesta fall. Ex. Gossen läser,
och flickan skrifver. Hon sjunger, och hon dansar. (Om det hade stått:
Hon sjunger och dansar, så borde icke sats komma framför och). Fröken
B. spelar bra, men hennes mor spelar bättre. Antingen läser Hjalmar,
eller är han ute i skogen. Ju mer han arbetade, desto friskare blef han.
Han är lycklig, ty han är nöjd. Nordanvindarna komma från kalla nejder,
derför (eller och derför) medföra de köld. I sistnämnda exempel kan—i
fall och ej utsättes—i stället semikolon nyttjas.
Anm. Framför men och utan, när de stå i början af bisatser, sättes
komma, äfven om dessa satser äro sammandragna. Ex. Han är klok,
men icke rik. Karl reser icke i dag, utan i morgon.
2) För att från hufvudsatser skilja fullständiga relativbisatser (vare sig
det relativa ordet är utsatt eller icke). Ex. Lycklig är den, som (relativet)
är nöjd med sin lott. I Paris, der (hvarest) han uppehållit sig flera år, har
han många vänner. Den son, för hvilken modern var mest svag, har
artat sig sämst. (Märk, komma framför för!). De skäl, på grund af hvilka
han fattade sitt beslut, äro i alla afseenden bindande.
3) För att skilja hufvudsatser från fullständiga konjunktivbisatser
(äfven om den inledande konjunktionen skulle vara utelemnad). Ex. Hon
var mycket glad, när (konjunktionen) hon var ung. Han sprang, tills (ell.
till dess, icke tills dess) han tappade andan. Herr X. besöker sin mor, så
ofta han kan.
 4) För att skilja bisatser af olika slag (öfver- och underordnade). Ex.
Den, som vet, att kamraterna blygas för honom, emedan han är
oordentlig, måste äfven blygas öfver sig sjelf. (Detta exempel innehåller
4 satser: “Den måste äfven blygas öfver sig sjelf” är hufvudsatsen; som
vet är en bisats; att kamraterna blygas för honom en annan; emedan
han är oordentlig en tredje. Alltså en hufvudsats och tre bisatser, alla
åtskilda medels komma. Detta exempel torde vara värdt att noga
studeras af dem, som vilja göra sig bekanta med bruket af komma).
5) Vid participialkonstruktion och sjelfständig ackusativ. (Den, som är
obekant med grammatiska termer torde dock hafva godt af att studera
exemplen). Sjelf lycklig, söker han äfven främja sina medmenniskors
glädje. Väckt af bullret, rusade han upp. Sjuk, (= då han var sjuk eller
emedan han var sjuk) önskade han sig döden. (Deremot: Sjuk ville han
icke blifva; utan skiljetecken). Olik andra, ville han ej mottaga lön för sitt
arbete. Huset, uppfördt efter en framstående konstnärs ritning, är en
vacker byggnad.
Observera äfven följande exempel: Lyran i handen, står der en ängel
så skön (Tegnér.) (I st. f. Med lyran i handen o. s. v.).
6) Ofta omkring ord och satser, hvilka äro inskjutna i texten, fastän de
icke utgöra nödvändiga beståndsdelar af sammanhanget. Ex. Sveriges
öde, liksom alla andra lands, hvilar på medborgarnes fosterlandskärlek.
Briggen Svalan, kapten Svensson, har hemkommit.
7) Mellan samordnade satsdelar då ett och eller annat
sammanbindande ord är utelemnadt. Ex. Geijer, Tegnér, Stagnelius och
Runeberg voro store skalder. (Här sättes komma mellan namnen i st. f.
att säga Geijer och Tegnér och Stagnelius o. s. v.) Det nya, vackra huset.
Den sanna menniskokärleken är tålig, mild, välgörande och oegennyttig.
8) Omkring appositioner, äfven att- satser, som stå efter hufvudordet.
Ex. Andeskådaren Emanuel Svedenborgs fader, Jesper Svedberg, var
biskop. Sveriges nuvarande konung, Oskar II, är skald och
häfdatecknare.
9) För att afskilja adverbial, när menings-sammanhanget sådant
kräfver (för undvikande af missförstånd, och då uppfattningen
derigenom underlättas). Ex. På afstånd synes en vacker ö, med höga
träd på och mellan boningshusen åkrar.
 10) För att åtskilja utrops- och tilltalsord från de egentliga
satsdelarne. Ex. Ni, herr doktor, är en lärd man. Sjung, min själ, din
skapares lof!
11) När, för större eftertrycks skull, något eller några ord upprepas två
eller flera gånger efter hvarandra. Ex. Skuggan faller så tjock, så tjock.
(Geijer). Gå sakta, sakta! Tack, tack, tack! ropade han.
12) När ett föregående ord upprepas på annat ställe i meningen, och
när betydelsen af ett eller flera ord sammanfattas i ett följande. Ex. Jag
är en fattig gosse, jag, som äter andras bröd. (Runeberg). Det skall han
säga, han(,) som är så rik. Fästmön var förtjust, ja öfverlycklig.
13) Stundom kan det för tydlighetens skull blifva nödvändigt att sätta
komma till och med i uppenbar strid mot allmänt gällande
interpunktionslagar. Ex. Att lefva eller dö, för asarne var ett. (Märk
dubbelmeningen i orden “Förlåt oss alla våra synder!”)
Ex. Han är redlig och gör alla rätt. (Intet komma här framför och,
emedan satsbindningen är sammandragen. Utfyld skulle den blifva: Han
är redlig, och han gör alla rätt.) Jag faders rostiga svärd tog i hand och
svor att eröfra mig rike och land. (Geijer.) Sven är både flitig och snäll.
Konungen och drottningen samt prinsarne äfvensom de här varande
utländske furstarne jemte deras uppvaktning hafva besökt staden.
Soldaten hvarken fruktar eller önskar döden. Han blef glad öfver att du
kom. (Man brukar vanligen ej sätta komma framför att-satser, som
styras af en preposition.) Jag förlorade på att jag sålde min vara för
tidigt.
Ofvanstående korta regler torde vara tillräckliga för att gifva några
hållpunkter för kommats användning. Dock må tilläggas, att bruket af
detta skiljetecken är i svenskan underkastadt stor omvexling, dels på
grund af författares olika åsigter och tycken, dels såsom följd af
bristande eftertanke. Många sätta t. ex. komma vid alla relativbisatser,
då deremot andra utelemna det vid relativsatser, der relativet är
utelemnadt. I öfverensstämmelse med det franska
interpunktionssystemet utelemna ganska många komma vid sådana
relativbisatser, hvilka till hufvudsatsen foga en nödvändig bestämning
och som följaktligen icke kunna borttagas, utan att sammanhanget blir
ofullständigt eller felaktigt, men utsätta kommat, om bisatsen endast
innehåller en tillfällig bestämning och kan, utan att stympa eller förändra
meningen, borttagas. Men att ingå på alla dessa olika och i många fall
godtyckliga bruk af kommat är icke förenligt med planen för
föreliggande arbete. Det ofvan sagda må derför vara nog.

Semikolon (;) äfven kalladt komma med punkt (comma cum

puncto), är ett slags förstärkning af kommat och begagnas derför
hufvudsakligen för att åtskilja längre afdelningar i en mening. Det
nyttjas:
1) Framför det motsättande inledningsordet men, då detta föregås
och efterföljes af längre satsföreningar. Ex. Föräldrarne, hvilka bo i
Chicago, äro hederliga menniskor; men barnen, som flyttat till
Californien, der de försökt slå sig fram, åtnjuta ingen aktning. (Deremot:
Han ropade, men ingen hörde honom. Han kom, men utan sina böcker.)
2) I längre satsbindningar före följdsatser (konklusiva satser). Ex.
Salig är den menniska, som Gud straffar; derför förkasta icke den
allsmäktiges tuktan! (Här kunde också sättas punkt framför derför, i
hvilket fall detta ord naturligtvis skulle komma att skrifvas med stor
begynnelsebokstaf.)
3) Ofta i längre satsföreningar mellan försats och eftersats. Ex.
Emedan Gustaf II Adolf, som 1632 stupade vid Lützen, utförde härliga
och evigt minnesrika bragder; så har han, med bättre rätt än mången
annan, blifvit kallad “den store.”
4) Stundom emellan satser, hvilka, ehuru grammatiskt sjelfständiga
och icke sammanbundna genom konjunktion, dock stå i ett närmare
sammanhang för tanken. Ex. Med humle brygges mjödet, ej blott med
honung; lägg stål i svärd och allvar i leken, konung! (Tegnér.) I sådana
fall kan man ock nyttja kolon eller punkt.
5) Vid uppräkningar för att beteckna grupper. Ex. I Småland finnas
åtta städer: Kalmar, Oskarshamn, Vestervik, Vimmerby; Vexiö;
Jönköping, Eksjö och Grenna. (Obs. Städerna här grupperade efter
länsindelningen.) Salomos Ordspr. 2: 6; 3: 11; 10: 1, (= 2 kap. 6 vers; 3
kap. 11 vers; 10 kap. 1 vers).
Anm. Undvik slöseri med detta tecken!
 Det heliga korsets berg i Kolorado.

(Skrif t. ex. icke “G; F; Carlsson,” utan G. F. Carlsson.)

Kolon (:) nyttjas:

1) Framför direkta anföranden, som hafva anföringsord framför sig
(jemte anföringstecken). Ex. Gud sade: “Varde ljus!” och det vardt ljus.
2) Framför indelningar, exempel, förklaringar, bevis o. d. Ex. Det
finnes många slags löfträd: al, alm, ask, björk, lind o. s. v.
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