Alkyl Dithiocarbamates . .... Flotation Characteristics of Alkyl Sulfonates and · Sulfates . ... Other Sulfonic Acid Derivatives and Sulfosuccinic · Acids.
Flotation Reagents: Applied Surface Chemistry on Minerals Flotation and Energy Resources Beneficiation
Dianzuo Wang
Flotation Reagents: Applied Surface Chemistry on Minerals Flotation and Energy Resources Beneficiation Volume 2: Applications
123
Dianzuo Wang Chinese Academy of Engineering Beijing China
ISBN 978-981-10-2025-4 DOI 10.1007/978-981-10-2027-8
ISBN 978-981-10-2027-8
(eBook)
Jointly published with Metallurgical Industry Press, Beijing, China ISBN: 978-7-5024-7146-0 Metallurgical Industry Press, Beijing, China Library of Congress Control Number: 2016945949 © Metallurgical Industry Press, Beijing and Springer Science+Business Media Singapore 2016 This work is subject to copyright. All rights are reserved by the Publishers, whether the whole or part of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation, broadcasting, reproduction on microfilms or in any other physical way, and transmission or information storage and retrieval, electronic adaptation, computer software, or by similar or dissimilar methodology now known or hereafter developed. The use of general descriptive names, registered names, trademarks, service marks, etc. in this publication does not imply, even in the absence of a specific statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use. The publishers, the authors and the editors are safe to assume that the advice and information in this book are believed to be true and accurate at the date of publication. Neither the publishers nor the authors or the editors give a warranty, express or implied, with respect to the material contained herein or for any errors or omissions that may have been made. Printed on acid-free paper This Springer imprint is published by Springer Nature The registered company is Springer Science+Business Media Singapore Pte Ltd.
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 separation and valuables recovery in metallurgical, coal, and chemical engineering. Flotation reagents have played vital roles in the progress of flotation process. The development and application of the reagents have made it possible for more and more traditional refractory ores and materials to be treated by flotation process with high efficiency. Several books on flotation principles and reagents have been published, however, 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. The author of this book took up investigation of flotation reagents in 1960s. 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 collector performance. Molecular orbit method incorporating with molecular design 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 of flotation reagents in the last fifty years. The Chinese edition of this book was published in 1982 and reprinted in 1994 by Metallurgical Industry Press. This English edition, on the basis of Chinese edition, has incorporated the new findings on the topic in particular the molecular design of reagents achieved by the author and his research group. This book is intended for worldwide university teachers, researchers, R&D engineers, and graduate students in minerals processing, extractive metallurgy and resources utilization who wish to explore innovative reagents and technologies that lead to more energy-efficient and environmentally sustainable solutions.
v
vi
Preface
In time of publication of the English edition, I would like to acknowledge cooperation and contributions to the contents of this book from my colleagues and graduate students. A special acknowledgment is warranted to Dr. Guihong Han, who completed the onerous translation of this book with his dedication and persistence. I give my sincere thanks to Prof. Tao Jiang, who undertook the proposal for the publication and helped to review the first draft. Thanks also to Mr. Xiaofeng Liu (editor of Metallurgical Industry Press), who encouraged and helped to complete this project. Beijing, China December 2015
Dianzuo Wang
Contents
1 Collectors for Sulfide Minerals . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.1 Xanthates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.1.1 Application of Xanthates . . . . . . . . . . . . . . . . . . . . . 1.1.2 Preparation of Xanthates . . . . . . . . . . . . . . . . . . . . . 1.1.3 Property of Xanthates . . . . . . . . . . . . . . . . . . . . . . . 1.1.4 Brief Introduction of Various Xanthates . . . . . . . . . 1.2 Dithiophosphates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.2.1 Property and Preparation of Dithiophosphates . . . . . 1.2.2 Brief Introduction of Various Dithiophosphates . . . . 1.3 Alkyl Dithiocarbamates . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.4 Amino ethanol Dithiocarbonates . . . . . . . . . . . . . . . . . . . . . . 1.5 Thiambutosines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.5.1 Urea and Thiocarbamides . . . . . . . . . . . . . . . . . . . . 1.5.2 N-Substituted Thiocarbamide [6–9] . . . . . . . . . . . . . 1.5.3 S-Substituted Thiocarbamides . . . . . . . . . . . . . . . . . 1.5.4 Other thiocarbamides . . . . . . . . . . . . . . . . . . . . . . . . 1.6 Mercapto-Benzothiazole . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.6.1 Mercapto-benzothiazole . . . . . . . . . . . . . . . . . . . . . . 1.6.2 Mercapto-Benzimidazole and Benzoxazole [15–17] 1.7 Dixanthogen and Xanthate Esters . . . . . . . . . . . . . . . . . . . . . 1.7.1 Dixanthogen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.7.2 Xanthate Ester . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.8 Thionocarbamates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.8.1 Preparation and Properties of Thiocarbamates [19] . 1.8.2 Flotation Performance and Mechanism of Thiocarbamates . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.8.3 Other Similar Thionocarbamates . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . .
1 2 2 2 3 5 10 10 11 16 20 22 22 24 29 32 33 33 35 38 38 40 42 42
.... ....
43 44
. . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . .
vii
viii
Contents
1.9
Other Collectors for Sulfide Minerals . . . . . . . . . . . . . 1.9.1 Disulfides and Esters of Dithiophosphates . . . 1.9.2 Mercapto-Collectors. . . . . . . . . . . . . . . . . . . . 1.9.3 Nitrogenous or Oxygenous Collector . . . . . . . 1.9.4 Acetenyl Collectors . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . .
52 52 58 63 66 66
2 Collectors for Nonsulfide Minerals . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.1 Fatty Acids and Soaps . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2 Oxidation Products of Petroleum Paraffin . . . . . . . . . . . . . . . . . . . 2.2.1 Brief Introduction to Synthetic Fatty Acids . . . . . . . . . . . 2.2.2 Production Process of Oxidized Paraffin Soaps . . . . . . . . 2.2.3 Characteristics of Oxidized Paraffin Soaps. . . . . . . . . . . . 2.2.4 Application of Oxidized Paraffin Soaps . . . . . . . . . . . . . . 2.3 Tar Oil and Paper Pulp Products . . . . . . . . . . . . . . . . . . . . . . . . . 2.3.1 Paper Pulp Products . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.3.2 Crude Tar Oils . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.3.3 Essential Tar Oils . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.4 Modified Products of Fatty Acids . . . . . . . . . . . . . . . . . . . . . . . . . 2.4.1 Modified Products of Saturated Fatty Acids . . . . . . . . . . 2.4.2 Modified Products of Unsaturated Fatty Acids . . . . . . . . 2.5 Carboxylic Acids and Derivative Collectors . . . . . . . . . . . . . . . . . 2.5.1 Polycarboxylic Acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.5.2 Ether Acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.6 Alkyl Sulfonates and Sulfates . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.6.1 Alkyl Sulfonic Acids and Sulfonates . . . . . . . . . . . . . . . . 2.6.2 Alkyl Sulfates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.6.3 Flotation Characteristics of Alkyl Sulfonates and Sulfates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.6.4 Industry Application of Alkyl Sulfonates and Sulfates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.6.5 Other Sulfonic Acid Derivatives and Sulfosuccinic Acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.7 Hydroximic Acids and Their Salts . . . . . . . . . . . . . . . . . . . . . . . . 2.8 Phosphonic Acids and Arsonic Acids . . . . . . . . . . . . . . . . . . . . . . 2.8.1 Preparation of Phosphonic Acids and Arsonic Acids . . . . 2.8.2 Flotation Performance of Phosphonic Acid . . . . . . . . . . . 2.8.3 Flotation Performance of Arsonic Acid . . . . . . . . . . . . . . 2.9 Amino Acids and Amphoteric Collectors . . . . . . . . . . . . . . . . . . . 2.10 Cationic Collectors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.11 Other Collectors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.11.1 Organofluorine Collector . . . . . . . . . . . . . . . . . . . . . . . . . 2.11.2 Organosilicone Collector . . . . . . . . . . . . . . . . . . . . . . . . .
69 69 69 69 71 73 75 76 76 76 78 79 79 82 83 83 85 86 86 87
. . . . . .
. . . . . .
. . . . . .
. . . . . .
. . . . . .
. . . . . .
. . . . . .
. . . . . .
88 89 92 93 96 96 99 103 103 105 109 109 109
Contents
2.11.3 Macromolecule Collector . . . . . . . . 2.11.4 Polymer Complexes Collector . . . . 2.11.5 Nonionic Collector . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
ix
. . . .
. . . .
. . . .
. . . .
. . . .
. . . .
. . . .
. . . .
. . . .
. . . .
110 111 112 112
3 Frothers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.1 Pine Oil and Modified Products . . . . . . . . . . . . . . . . . 3.2 Camphor Oils and Eucalyptus Oils . . . . . . . . . . . . . . . 3.3 Pyridines and Creasols . . . . . . . . . . . . . . . . . . . . . . . . 3.4 Aliphatic Alcohols . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.5 Polypropylene Glycols and Other Alcohol Ethers . . . . 3.6 Oxyalkanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.7 Other Frothers. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . .
. . . . . . . . .
. . . . . . . . .
. . . . . . . . .
. . . . . . . . .
. . . . . . . . .
. . . . . . . . .
. . . . . . . . .
. . . . . . . . .
115 115 119 119 120 120 122 122 123
4 Depressants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.1 Inorganic Depressants . . . . . . . . . . . . . . . . . . . . . 4.2 Micromolecule Organic Depressant . . . . . . . . . . 4.2.1 Carboxylic Acids and Hydroxy Acids . . 4.2.2 Amino Acids and Anilines . . . . . . . . . . 4.2.3 Sulfur-Containing Organics [1] . . . . . . . 4.2.4 Organic Nitriles [2] . . . . . . . . . . . . . . . . 4.2.5 Complexing Agents . . . . . . . . . . . . . . . . 4.3 Tannins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.4 Lignins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.5 Gums . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.5.1 Structure of Gum . . . . . . . . . . . . . . . . . . 4.5.2 Preparation of Gum . . . . . . . . . . . . . . . . 4.5.3 Application of Gum. . . . . . . . . . . . . . . . 4.6 Starchs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.7 Other Macromolecule Organic Depressants . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . .
125 125 128 128 130 130 131 131 132 134 137 137 139 139 139 143 143
5 Organic Flocculants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.1 Cellulose and Related Modified Products . . . . . . . . . . . . . . . 5.2 Polyacrylamide, Polyacrylonitrile, and Polyacrylic Acid . . . . 5.2.1 Polyacrylamide . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.2.2 Polyacrylonitrile . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.2.3 Polyacrylic Acid . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.3 Other Organic Flocculants and Selective Polymer Flocculation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.3.1 Selective Polymer Flocculation . . . . . . . . . . . . . . . . 5.3.2 Emulsion Floatation and Separation . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . . . .
. . . . . .
. . . . . .
. . . . . .
145 145 147 147 148 149
. . . .
. . . .
. . . .
. . . .
149 150 152 152
. . . .
. . . .
. . . .
. . . .
. . . .
. . . . . . . . . . . . . . . . .
. . . .
. . . . . . . . . . . . . . . . .
. . . .
. . . . . . . . . . . . . . . . .
. . . . . . . . . . . . . . . . .
x
6 Microanalysis of Flotation Reagents and Adsorption Measurement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.1 Principle of Microanalysis of Flotation Reagents . . . . . . . . . 6.1.1 Physical and Instrumental Analysis . . . . . . . . . . . . . 6.1.2 Chemical Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . 6.2 Common Analytical Method for Flotation Reagents . . . . . . . 6.2.1 Analysis of Xanthate . . . . . . . . . . . . . . . . . . . . . . . . 6.2.2 Analysis of 8-Hydroxyl Quinoline . . . . . . . . . . . . . . 6.2.3 Analysis of Fatty Acid . . . . . . . . . . . . . . . . . . . . . . 6.2.4 Analysis of Alkyl Sulfonate, Sulfate, and Fatty Amine . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.3 Measurement Method of Reagent Adsorption on Mineral Surface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.3.1 Adsorption Amount of Surfactant on Liquid–Gas Interface . . . . . . . . . . . . . . . . . . . . . 6.3.2 Adsorption Amount of Flotation Reagent on Mineral Surface . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Contents
. . . . . . . .
153 153 153 161 163 163 163 167
....
167
....
168
....
168
.... ....
169 171
. . . . . . . .
. . . . . . . .
. . . . . . . .
Appendix . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 173