Flotation Reagents: Applied Surface Chemistry on Minerals Flotation and Energy Resources Beneficiation: Volume 1: Functional Principle

390 Pages·2016·25.28 MB·English

by  Dianzuo Wang (auth.)

Dianzuo Wang
Flotation Reagents:
Applied Surface
Chemistry on Minerals
Flotation and Energy
Resources Beneficiation
Volume 1: Functional Principle
Flotation Reagents: Applied Surface Chemistry
on Minerals Flotation and Energy Resources
fi
Bene ciation
Dianzuo Wang
Flotation Reagents: Applied
Surface Chemistry
on Minerals Flotation
and Energy Resources
fi
Bene ciation
Volume 1: Functional Principle
123
Dianzuo Wang
General Research Institute for Nonferrous
Metals(GRINM)
ChineseAcademy of Engineering
Beijing
China
ISBN978-981-10-2028-5 ISBN978-981-10-2030-8 (eBook)
DOI 10.1007/978-981-10-2030-8
JointlypublishedwithMetallurgicalIndustryPress,Beijing,China
ISBN:978-7-5024-7145-3MetallurgicalIndustryPress,Beijing,China
LibraryofCongressControlNumber:2016945949
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Preface
The development of minerals processing over one hundred years has shown
flotation a predominant process of materials separation. Nowadays, flotation is
widely used in minerals separation, treatments of slag and wastes, materials sepa-
ration, and valuables recovery in metallurgical, coal, and chemical engineering.
Flotation reagents have played vital roles in the progress offlotation process. The
development and application of the reagents have made it possible for more and
moretraditionalrefractoryoresandmaterialstobetreatedbyflotationprocesswith
high efficiency.
Several books on flotation principles and reagents have been published, how-
ever, for further improvement of current minerals processing performance and for
the treatment and recovery of refractory and nontraditional mineral and energy
resources, scientists need to develop new reagents and innovative processes.
Theauthorofthis booktook upinvestigationofflotationreagentsinthe1960s.
The fundamentals and approaches of surface chemistry have been applied in the
round to discuss the structure, performance of the reagents, and the interaction
between the reagents and minerals, as well as to set up theoretical criteria for
collectorperformance.Molecularorbitmethodincorporatingwithmoleculardesign
was used to have obtained quantum chemistry parameters, steric configuration,
HOMO, and LUMO surface of various reagents. This book has summarized the
results that the author has achieved on functional principle offlotation reagents in
the last 50 years.
TheChineseeditionofthisbookwaspublishedin1982andreprintedin1994by
Metallurgical Industry Press. ThisEnglish edition, on thebasis ofChinese edition,
hasincorporatedthenewfindingsonthetopicinparticularthemoleculardesignof
reagents achieved by the author and his research group. This book is intended for
worldwide university teachers, researchers, R&D engineers, and graduate students
inmineralsprocessing,extractivemetallurgy,andresourcesutilizationwhowishto
exploreinnovativereagentsandtechnologiesthatleadtomoreenergyefficientand
environmentally sustainable solutions.
v
vi Preface
In time of publication of the English edition, I would like to acknowledge
cooperation andcontributionstothecontentsofthis bookfrom mycolleagues and
graduate students. A special acknowledgment is warranted to Dr. Guihong Han,
who completed the onerous translation of this book with his dedication and per-
sistence. I give my sincere thanks to Prof. Tao Jiang, who undertook the proposal
forthepublicationandhelpedtoreviewthefirstdraft.ThanksalsotoMr.Xiaofeng
Liu (editor of Metallurgical Industry Press), who encouraged and helped to com-
plete this project.
Beijing, China Dianzuo Wang
December 2015
Contents
1 Introduction... .... .... ..... .... .... .... .... .... ..... .... 1
1.1 Brief History of Research and Application of Flotation
and Reagents . .... ..... .... .... .... .... .... ..... .... 1
1.2 Classification and Significance of Flotation Reagents..... .... 4
1.2.1 Classification of Flotation Reagents According
to Their Uses.... .... .... .... .... .... ..... .... 4
1.2.2 Classification of Flotation Reagents According
to Their Roles... .... .... .... .... .... ..... .... 5
1.2.3 Classification of Flotation Reagents According
to Their Structures.... .... .... .... .... ..... .... 5
1.2.4 Classification of Flotation Reagents According
to Their Chemical Constituents.. .... .... ..... .... 5
1.2.5 Classification of Flotation Reagents According
to Characteristics of Coordination Chemistry .... .... 7
References. .... .... .... ..... .... .... .... .... .... ..... .... 8
2 Interaction Between Minerals and Reagents.. .... .... ..... .... 9
2.1 Various Theories on Interaction Between Collectors
and Minerals.. .... ..... .... .... .... .... .... ..... .... 9
2.1.1 Main Interactions Between Collector and Mineral. .... 9
2.1.2 Adsorption Models of Collector on Mineral ..... .... 10
2.2 Adsorption Equation of Flotation Reagent on Mineral
Surface.. .... .... ..... .... .... .... .... .... ..... .... 18
2.2.1 Adsorption Isotherm Model. .... .... .... ..... .... 18
2.2.2 Adsorption Isotherm of Flotation Reagent
on Mineral Surface ... .... .... .... .... ..... .... 21
2.2.3 Adsorption Kinetics Equation of Flotation Reagent
on Mineral Surface ... .... .... .... .... ..... .... 27
vii
viii Contents
2.3 Structure of Adsorption Film and Flotation Behavior
of Mineral.... .... ..... .... .... .... .... .... ..... .... 27
2.3.1 Structure of Adsorbed Layer.... .... .... ..... .... 27
2.3.2 Relationship of Collector Adsorption and Mineral
Flotation .. ..... .... .... .... .... .... ..... .... 28
2.4 Mineral Structure, Bonding Characteristics, and the Reaction
of Reagents... .... ..... .... .... .... .... .... ..... .... 33
2.4.1 Geochemical Classification of Mineral Elements
and Their Interaction With reagent ... .... ..... .... 33
2.4.2 Structure and Valence Bond of Mineral and Their
Reactions with Reagents ... .... .... .... ..... .... 34
References. .... .... .... ..... .... .... .... .... .... ..... .... 37
3 Structure and Property of Polar Group of Collector ... ..... .... 39
3.1 Structural Characteristics of Collector Molecule and
Independent Effect of Chemical Groups Belong to Surface
Chemistry.... .... ..... .... .... .... .... .... ..... .... 39
3.2 Effect of Polar Group Structure on Dissociation of Reagent
and Adsorption in Electrical Double Layer of Mineral
Surface.. .... .... ..... .... .... .... .... .... ..... .... 40
3.2.1 Dissociation of Collector and Its Flotation Function ... 40
3.2.2 Zero Charge Point of Mineral and Dissociation
Constant of Collector, and Their Interrelation
in Flotation ..... .... .... .... .... .... ..... .... 46
3.2.3 Adsorption of Amphoteric Collector in Electric
Double Layer.... .... .... .... .... .... ..... .... 50
3.2.4 Effect of Polar Group Structure on Dissociation
of Collector..... .... .... .... .... .... ..... .... 52
3.3 Molecular Structure of Nonionic Reagent and Adsorption
by van der Waals Force .. .... .... .... .... .... ..... .... 52
3.3.1 van der Waals Force Between Collector Molecules.... 53
3.3.2 Relation between Reagent Molecular Structure
and van der Waals Force... .... .... .... ..... .... 56
3.3.3 Hydrogen Bonding Adsorption of Reagent . ..... .... 56
3.4 Polar Group Structure and Chemisorption .... .... ..... .... 58
3.4.1 Common Solidophilic Atoms in Polar Group .... .... 58
3.4.2 Bonding Capability of Solidophilic Atoms . ..... .... 60
3.5 Inductive Effect in Polar Group of Collector .. .... ..... .... 64
3.5.1 Introduction of Inductive Effect.. .... .... ..... .... 64
3.5.2 Inductive Effect in Xanthate Molecule. .... ..... .... 64
3.5.3 Inductive Effect in Thionocarbamates Molecule
as Collector [9] .. .... .... .... .... .... ..... .... 66
3.5.4 Inductive Effect in Aerofloat Collector Molecule.. .... 67
Contents ix
3.5.5 Comparison of Inductive Effect in Xanthate,
Dithiocarbamate, and Aerofloat.. .... .... ..... .... 70
3.5.6 Inductive Effect in Collector of Nonsulfide
Minerals .. ..... .... .... .... .... .... ..... .... 71
3.6 Conjugative Effect in Polar Group of Collector .... ..... .... 75
3.6.1 Introduction of Conjugative Effect.... .... ..... .... 75
3.6.2 Conjugative Effect in Xanthate Molecule .. ..... .... 77
3.6.3 Conjugative Effect in Aromatic Collector .. ..... .... 79
3.7 Polar Group of Coordinating Collector... .... .... ..... .... 81
3.7.1 Major Features of Coordinating Collector.. ..... .... 81
3.7.2 Structure and Property of Polar Group
of Coordinating Collector .. .... .... .... ..... .... 82
3.7.3 Functional Mechanism of the Coordinating
Collector .. ..... .... .... .... .... .... ..... .... 87
3.7.4 Classification of the Coordinating Collector ..... .... 89
References. .... .... .... ..... .... .... .... .... .... ..... .... 91
4 Structure and Property of Nonpolar Group of Collector..... .... 93
4.1 Role of Nonpolar Group of Collector.... .... .... ..... .... 93
4.2 Structure, Solubility, and Surface Activity of Nonpolar
Group for Flotation Reagent... .... .... .... .... ..... .... 96
4.2.1 Solubility of Organic Liquid in Water. .... ..... .... 97
4.2.2 Surface Activity and Solubility of Organic
Liquid in Water.. .... .... .... .... .... ..... .... 99
4.2.3 Solubility and Surface Activity of Heteropolarity
Organic Solid Matter.. .... .... .... .... ..... .... 99
4.2.4 Comparison of Hydrophobic Association Energy
of Nonpolar Group and Electrostatic Interaction
Energy of Collector During Double Electric Layer
Adsorption. ..... .... .... .... .... .... ..... .... 101
4.3 Normal Alkyl Chain..... .... .... .... .... .... ..... .... 102
4.4 Isoalkyl Group .... ..... .... .... .... .... .... ..... .... 107
4.5 Unsaturated Hydrocarbon Chain.... .... .... .... ..... .... 111
4.6 Aromatic Group ... ..... .... .... .... .... .... ..... .... 120
4.7 Other Kinds of Nonpolar Groups ... .... .... .... ..... .... 122
4.7.1 Cycloalkyl. ..... .... .... .... .... .... ..... .... 122
4.7.2 Alkoxyl... ..... .... .... .... .... .... ..... .... 122
References. .... .... .... ..... .... .... .... .... .... ..... .... 124
5 Structure Relationship Between Polar and NonPolar
Group in Collector Molecule .. .... .... .... .... .... ..... .... 127
5.1 Correlation Between Size of NonPolar Group and Variety
of Polar Group .... ..... .... .... .... .... .... ..... .... 127
5.2 Relationship Between Number and Position
of Polar Group and NonPolar Group .... .... .... ..... .... 130
x Contents
5.2.1 Two or More of Polar Groups in a Collector
Molecule.. ..... .... .... .... .... .... ..... .... 130
5.2.2 Two or More of NonPolar Groups in Collector
Molecule.. ..... .... .... .... .... .... ..... .... 131
5.2.3 Position of Polar Group in Collector Molecule ... .... 131
Reference . .... .... .... ..... .... .... .... .... .... ..... .... 133
6 Theoretical Criteria and Calculation for Collector
Performance... .... .... ..... .... .... .... .... .... ..... .... 135
6.1 Solubility Product Theory of Reaction of Flotation
Reagent and Related Calculation ... .... .... .... ..... .... 135
6.1.1 Solubility Product Theory of Collector Reaction.. .... 135
6.1.2 Calculation for the Optimum Conditions
of Interaction Between Collector and Mineral
Using Solubility Product... .... .... .... ..... .... 140
6.1.3 Diagram of Solubility Product Calculation . ..... .... 145
6.1.4 Comparison and Discussion of Computational
Methods of Solubility Product... .... .... ..... .... 148
6.1.5 Research on Structure and Performance
of Reagent via Solubility Product Calculation.... .... 150
6.2 Critical Micelle Concentration and Related Calculation
for Flotation Reagent .... .... .... .... .... .... ..... .... 155
6.2.1 Critical Micelle Concentration (CMC) and Related
Calculation Methods .. .... .... .... .... ..... .... 155
6.2.2 General Relation Between CMC and Structure
of Reagent. ..... .... .... .... .... .... ..... .... 156
6.2.3 Application of CMC to Predict Reagent
Performance..... .... .... .... .... .... ..... .... 161
6.3 Hydrophile-Lipophile Balance (HLB) for Flotation Reagent.... 164
6.3.1 Hydrophile-Lipophile Balance (HLB) and Related
Calculation Methods .. .... .... .... .... ..... .... 164
6.3.2 Relationship Between HLB and Other Physical
Property Values of Reagents.... .... .... ..... .... 168
6.3.3 Application of Molecular Fragment Method
to Calculate Hydrophile-Lipophile Property
for Flotation Reagent.. .... .... .... .... ..... .... 170
6.3.4 The Prediction of Uses of Reagent ... .... ..... .... 177
6.4 Electronegativity and Related Calculation for Flotation
Reagent.. .... .... ..... .... .... .... .... .... ..... .... 180
6.4.1 Electronegativity and Related Calculations . ..... .... 180
6.4.2 Calculation of Group Electronegativity of Flotation
Reagent... ..... .... .... .... .... .... ..... .... 182
6.4.3 Relation Between Group Electronegativity
and Physical and Chemical Properties of General
Surfactant . ..... .... .... .... .... .... ..... .... 188