Dianzuo Wang Flotation Reagents: Applied Surface Chemistry on Minerals Flotation and Energy Resources Beneficiation Volume 2: Applications 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 2: Applications 123 Dianzuo Wang ChineseAcademy of Engineering Beijing China ISBN978-981-10-2025-4 ISBN978-981-10-2027-8 (eBook) DOI 10.1007/978-981-10-2027-8 JointlypublishedwithMetallurgicalIndustryPress,Beijing,China ISBN:978-7-5024-7146-0MetallurgicalIndustryPress,Beijing,China LibraryofCongressControlNumber:2016945949 ©MetallurgicalIndustryPress,BeijingandSpringerScience+BusinessMediaSingapore2016 Thisworkissubjecttocopyright.AllrightsarereservedbythePublishers,whetherthewholeorpart 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 orinformationstorageandretrieval,electronicadaptation,computersoftware,orbysimilarordissimilar methodologynowknownorhereafterdeveloped. The use of general descriptive names, registered names, trademarks, service marks, etc. in this publicationdoesnotimply,evenintheabsenceofaspecificstatement,thatsuchnamesareexemptfrom therelevantprotectivelawsandregulationsandthereforefreeforgeneraluse. Thepublishers,theauthorsandtheeditorsaresafetoassumethattheadviceandinformationinthis book are believed to be true and accurate at the date of publication. Neither the publishers nor the authorsortheeditorsgiveawarranty,expressorimplied,withrespecttothematerialcontainedhereinor foranyerrorsoromissionsthatmayhavebeenmade. Printedonacid-freepaper ThisSpringerimprintispublishedbySpringerNature TheregisteredcompanyisSpringerScience+BusinessMediaSingaporePteLtd. 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. Theauthorofthisbooktookupinvestigationofflotationreagentsin1960s.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 usedtohaveobtainedquantumchemistryparameters,stericconfiguration,HOMO, andLUMO surfaceofvariousreagents. Thisbookhassummarizedtheresultsthat theauthorhasachievedonfunctionalprincipleofflotationreagentsinthelastfifty 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,extractivemetallurgyandresourcesutilizationwhowishto exploreinnovativereagentsandtechnologiesthatleadtomoreenergy-efficientand 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 Collectors for Sulfide Minerals.. .... .... .... .... .... ..... .... 1 1.1 Xanthates . .... .... ..... .... .... .... .... .... ..... .... 2 1.1.1 Application of Xanthates.... .... .... .... ..... .... 2 1.1.2 Preparation of Xanthates.... .... .... .... ..... .... 2 1.1.3 Property of Xanthates .. .... .... .... .... ..... .... 3 1.1.4 Brief Introduction of Various Xanthates .... ..... .... 5 1.2 Dithiophosphates ... ..... .... .... .... .... .... ..... .... 10 1.2.1 Property and Preparation of Dithiophosphates..... .... 10 1.2.2 Brief Introduction of Various Dithiophosphates.... .... 11 1.3 Alkyl Dithiocarbamates ... .... .... .... .... .... ..... .... 16 1.4 Amino ethanol Dithiocarbonates. .... .... .... .... ..... .... 20 1.5 Thiambutosines. .... ..... .... .... .... .... .... ..... .... 22 1.5.1 Urea and Thiocarbamides ... .... .... .... ..... .... 22 1.5.2 N-Substituted Thiocarbamide [6–9].... .... ..... .... 24 1.5.3 S-Substituted Thiocarbamides .... .... .... ..... .... 29 1.5.4 Other thiocarbamides... .... .... .... .... ..... .... 32 1.6 Mercapto-Benzothiazole... .... .... .... .... .... ..... .... 33 1.6.1 Mercapto-benzothiazole. .... .... .... .... ..... .... 33 1.6.2 Mercapto-Benzimidazole and Benzoxazole [15–17] .... 35 1.7 Dixanthogen and Xanthate Esters.... .... .... .... ..... .... 38 1.7.1 Dixanthogen ..... .... .... .... .... .... ..... .... 38 1.7.2 Xanthate Ester.... .... .... .... .... .... ..... .... 40 1.8 Thionocarbamates... ..... .... .... .... .... .... ..... .... 42 1.8.1 Preparation and Properties of Thiocarbamates [19] . .... 42 1.8.2 Flotation Performance and Mechanism of Thiocarbamates... .... .... .... .... .... ..... .... 43 1.8.3 Other Similar Thionocarbamates.. .... .... ..... .... 44 vii viii Contents 1.9 Other Collectors for Sulfide Minerals. .... .... .... ..... .... 52 1.9.1 Disulfides and Esters of Dithiophosphates... ..... .... 52 1.9.2 Mercapto-Collectors.... .... .... .... .... ..... .... 58 1.9.3 Nitrogenous or Oxygenous Collector... .... ..... .... 63 1.9.4 Acetenyl Collectors.... .... .... .... .... ..... .... 66 References.. .... .... .... ..... .... .... .... .... .... ..... .... 66 2 Collectors for Nonsulfide Minerals... .... .... .... .... ..... .... 69 2.1 Fatty Acids and Soaps .... .... .... .... .... .... ..... .... 69 2.2 Oxidation Products of Petroleum Paraffin.. .... .... ..... .... 69 2.2.1 Brief Introduction to Synthetic Fatty Acids.. ..... .... 69 2.2.2 Production Process of Oxidized Paraffin Soaps.... .... 71 2.2.3 Characteristics of Oxidized Paraffin Soaps... ..... .... 73 2.2.4 Application of Oxidized Paraffin Soaps. .... ..... .... 75 2.3 Tar Oil and Paper Pulp Products .... .... .... .... ..... .... 76 2.3.1 Paper Pulp Products ... .... .... .... .... ..... .... 76 2.3.2 Crude Tar Oils ... .... .... .... .... .... ..... .... 76 2.3.3 Essential Tar Oils . .... .... .... .... .... ..... .... 78 2.4 Modified Products of Fatty Acids.... .... .... .... ..... .... 79 2.4.1 Modified Products of Saturated Fatty Acids . ..... .... 79 2.4.2 Modified Products of Unsaturated Fatty Acids .... .... 82 2.5 Carboxylic Acids and Derivative Collectors.... .... ..... .... 83 2.5.1 Polycarboxylic Acids... .... .... .... .... ..... .... 83 2.5.2 Ether Acids. ..... .... .... .... .... .... ..... .... 85 2.6 Alkyl Sulfonates and Sulfates... .... .... .... .... ..... .... 86 2.6.1 Alkyl Sulfonic Acids and Sulfonates... .... ..... .... 86 2.6.2 Alkyl Sulfates .... .... .... .... .... .... ..... .... 87 2.6.3 Flotation Characteristics of Alkyl Sulfonates and Sulfates.... ..... .... .... .... .... .... ..... .... 88 2.6.4 Industry Application of Alkyl Sulfonates and Sulfates. ..... .... .... .... .... .... ..... .... 89 2.6.5 Other Sulfonic Acid Derivatives and Sulfosuccinic Acids.. .... ..... .... .... .... .... .... ..... .... 92 2.7 Hydroximic Acids and Their Salts ... .... .... .... ..... .... 93 2.8 Phosphonic Acids and Arsonic Acids. .... .... .... ..... .... 96 2.8.1 Preparation of Phosphonic Acids and Arsonic Acids.... 96 2.8.2 Flotation Performance of Phosphonic Acid.. ..... .... 99 2.8.3 Flotation Performance of Arsonic Acid. .... ..... .... 103 2.9 Amino Acids and Amphoteric Collectors.. .... .... ..... .... 103 2.10 Cationic Collectors.. ..... .... .... .... .... .... ..... .... 105 2.11 Other Collectors.... ..... .... .... .... .... .... ..... .... 109 2.11.1 Organofluorine Collector.... .... .... .... ..... .... 109 2.11.2 Organosilicone Collector.... .... .... .... ..... .... 109 Contents ix 2.11.3 Macromolecule Collector.... .... .... .... ..... .... 110 2.11.4 Polymer Complexes Collector.... .... .... ..... .... 111 2.11.5 Nonionic Collector .... .... .... .... .... ..... .... 112 References.. .... .... .... ..... .... .... .... .... .... ..... .... 112 3 Frothers... .... .... .... ..... .... .... .... .... .... ..... .... 115 3.1 Pine Oil and Modified Products . .... .... .... .... ..... .... 115 3.2 Camphor Oils and Eucalyptus Oils... .... .... .... ..... .... 119 3.3 Pyridines and Creasols.... .... .... .... .... .... ..... .... 119 3.4 Aliphatic Alcohols .. ..... .... .... .... .... .... ..... .... 120 3.5 Polypropylene Glycols and Other Alcohol Ethers.... ..... .... 120 3.6 Oxyalkanes.... .... ..... .... .... .... .... .... ..... .... 122 3.7 Other Frothers.. .... ..... .... .... .... .... .... ..... .... 122 References.. .... .... .... ..... .... .... .... .... .... ..... .... 123 4 Depressants .... .... .... ..... .... .... .... .... .... ..... .... 125 4.1 Inorganic Depressants..... .... .... .... .... .... ..... .... 125 4.2 Micromolecule Organic Depressant .. .... .... .... ..... .... 128 4.2.1 Carboxylic Acids and Hydroxy Acids.. .... ..... .... 128 4.2.2 Amino Acids and Anilines .. .... .... .... ..... .... 130 4.2.3 Sulfur-Containing Organics [1] ... .... .... ..... .... 130 4.2.4 Organic Nitriles [2].... .... .... .... .... ..... .... 131 4.2.5 Complexing Agents.... .... .... .... .... ..... .... 131 4.3 Tannins... .... .... ..... .... .... .... .... .... ..... .... 132 4.4 Lignins... .... .... ..... .... .... .... .... .... ..... .... 134 4.5 Gums .... .... .... ..... .... .... .... .... .... ..... .... 137 4.5.1 Structure of Gum.. .... .... .... .... .... ..... .... 137 4.5.2 Preparation of Gum.... .... .... .... .... ..... .... 139 4.5.3 Application of Gum.... .... .... .... .... ..... .... 139 4.6 Starchs ... .... .... ..... .... .... .... .... .... ..... .... 139 4.7 Other Macromolecule Organic Depressants .... .... ..... .... 143 References.. .... .... .... ..... .... .... .... .... .... ..... .... 143 5 Organic Flocculants . .... ..... .... .... .... .... .... ..... .... 145 5.1 Cellulose and Related Modified Products.. .... .... ..... .... 145 5.2 Polyacrylamide, Polyacrylonitrile, and Polyacrylic Acid.... .... 147 5.2.1 Polyacrylamide ... .... .... .... .... .... ..... .... 147 5.2.2 Polyacrylonitrile .. .... .... .... .... .... ..... .... 148 5.2.3 Polyacrylic Acid .. .... .... .... .... .... ..... .... 149 5.3 Other Organic Flocculants and Selective Polymer Flocculation ..... .... .... .... .... .... ..... .... 149 5.3.1 Selective Polymer Flocculation ... .... .... ..... .... 150 5.3.2 Emulsion Floatation and Separation ... .... ..... .... 152 References.. .... .... .... ..... .... .... .... .... .... ..... .... 152 x Contents 6 Microanalysis of Flotation Reagents and Adsorption Measurement... .... .... ..... .... .... .... .... .... ..... .... 153 6.1 Principle of Microanalysis of Flotation Reagents .... ..... .... 153 6.1.1 Physical and Instrumental Analysis.... .... ..... .... 153 6.1.2 Chemical Analysis. .... .... .... .... .... ..... .... 161 6.2 Common Analytical Method for Flotation Reagents.. ..... .... 163 6.2.1 Analysis of Xanthate... .... .... .... .... ..... .... 163 6.2.2 Analysis of 8-Hydroxyl Quinoline. .... .... ..... .... 163 6.2.3 Analysis of Fatty Acid . .... .... .... .... ..... .... 167 6.2.4 Analysis of Alkyl Sulfonate, Sulfate, and Fatty Amine .. .... .... .... .... .... ..... .... 167 6.3 Measurement Method of Reagent Adsorption on Mineral Surface... .... .... ..... .... .... .... .... .... ..... .... 168 6.3.1 Adsorption Amount of Surfactant on Liquid–Gas Interface .... .... .... .... ..... .... 168 6.3.2 Adsorption Amount of Flotation Reagent on Mineral Surface .... .... .... .... .... ..... .... 169 References.. .... .... .... ..... .... .... .... .... .... ..... .... 171 Appendix. .... .... .... .... ..... .... .... .... .... .... ..... .... 173