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Advanced Techniques of Saponite Recovery from Diamond Processing Plant Water and Areas of Saponite Application

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Advanced Techniques of Saponite Recovery from Diamond Processing Plant Water and Areas of Saponite Application minerals Review Advanced Techniques of Saponite Recovery from Diamond Processing Plant Water and Areas of Saponite Application Valentine A. Chanturiya 1, Vladimir G. Minenko 1, Dmitriy V. Makarov 2,*, Olga V. Suvorova 3 and Ekaterina A. Selivanova 4 1 Institute of Comprehensive Exploitation of Mineral Resources of the Russian Academy of Sciences, Kryukovsky Tupik, 4, 111020 Moscow, Russia; [email protected] (V.A.C.); [email protected] (V.G.M.) 2 Institute of North Industrial Ecology Problems, Kola Science Centre of the Russian Academy of Sciences, Fersman St., 14a, 184209 Apatity, Russia 3 I.V. Tananaev Institute of Chemistry and Technology of Rare Elements and Mineral Raw Materials, Kola Science Centre of the Russian Academy of Sciences, Fersman St., 26a, 184209 Apatity, Russia; [email protected] 4 Geological Institute, Kola Science Centre of the Russian Academy of Sciences, Fersman St., 14, 184209 Apatity, Russia; [email protected] * Correspondence: [email protected]; Tel.: +7-81555-79-3-37 Received: 22 October 2018; Accepted: 22 November 2018; Published: 26 November 2018 Abstract: Methods of cleaning and processing of saponite-containing water from diamond processing plants in the Arkhangelsk region, Russia, are discussed. The advantages of electrochemical separation of saponite from process water enabling to change its structural-texture, physico-chemical and mechanical properties are demonstrated. Possible areas of saponite and modified-saponite products application are considered. Keywords: saponite-containing waters; diamond processing plants; cryogenic treatment; electrochemical separation; saponite product applications 1. Introduction The Lomonosov diamond deposit (Archangelsk province, Russia) currently contains 10 kimberlite pipes. Before launching quarrying operations, it is necessary to extract about 300 million tons of diamond-bearing ore and barren rock [1,2]. Almost all rock in the deposit pipes is represented by clay minerals, mostly saponite, the share of which reaches 90% in the vent facies [1]. Saponite belongs to the smectite group and is characterized by high physico-chemical activity and low density in aqueous media due to its tendency to hydrate. When in an aqueous medium, saponite disperses, forming a suspension, hindering the managing of both the tailing ponds and water circulation at the processing plants (Figure1). Minerals 2018, 8, 549; doi:10.3390/min8120549 www.mdpi.com/journal/minerals Minerals 2018, 8, 549 2 of 18 Minerals 2018, 8, x FOR PEER REVIEW 2 of 18 Figure 1. FigureTailing 1. pondTailing ofpond processing of processing plant, plant, Lomonosov Lomonosov GOK, GOK, Severalmaz Severalmaz JSC. Reproduced JSC. Reproduced with with permission from the author, V.I. Bogachev. permission from the author, V.I. Bogachev. 2. Structure and Properties of Saponite Therefore, searching, validating and developing effective techniques for recovery of The structure and properties of saponite, which are highly attractive for the industry, are saponite-containingdescribed in waterdetail atin diamondtextbooks, reference processing book plantss, and isprofessional a current reports. issue. TheAccording immediate to the objective is to developInternational an effective Mineralogical water Association rotating system,(IMA) list which[3], the saponite will boost mineral diamond consists of recovery, the formula reduce the ecological(Ca,Na) stress,0.3 and(Mg,Fe) open3(Si,Al) ways4O10(OH) for manufacturing2·4H2O; it is one of of the target-oriented three most common saponite-containing members in the products for multi-sectorsmectite applications. group, along with montmorillonite and nontronite [4]. Like all smectites, saponite has unique physical and chemical properties that arouse scientific interest, namely, high cation exchange capacity, swelling and rheological properties, hydration and 2. Structure and Properties of Saponite dehydration, high plasticity, bonding capacity, and the ability to react with inorganic and organic The structurereagents [5]. andThese properties properties are of the saponite, results of: which are highly attractive for the industry, are described in-the detail layered in nature textbooks, of the crystal reference structure books, containing and weakly professional bound cations; reports. According to the International Mineralogical-a wide range of chemical Association composition (IMA) variations; list [3], the saponite mineral consists of the formula -extremely small particle size, flat shape and, accordingly, great surface area. (Ca,Na)0.3(Mg,Fe)3(Si,Al)4O10(OH)2·4H2O; it is one of the three most common members in the smectite group, along2.1. Crystal with montmorilloniteStructure and nontronite [4]. Like all smectites,The basic structure saponite of smectite has unique group minerals physical is well and known chemical and has properties been illustrated that in arouse many scientific interest, namely,publications high (one cation of them exchange is shown in capacity, Figure 2). swellingSmectites are and three-layer rheological minerals. properties, This three-layer hydration and dehydration,package high has plasticity, two silica tetrahedral bonding sheets capacity, joined andto a ce thentral ability octahedral to reactsheet. On with this inorganic basis, smectite and organic structures can be classified as 2:1 phyllosilicates. Due to substitutions in the tetrahedral or reagents [5octahedral]. These sheets, properties or the areexistence the resultsof vacancies of: in the octahedral sheet, the surface of the three-layer package has a negative charge, which creates a charge imbalance. -the layered nature of the crystal structure containing weakly bound cations; According to the Nomenclature Committee of the Association Internationale pour l’Etude des -a wide rangeArgiles of (AIPEA) chemical [6] compositionthe layer charge variations; of smectites varies from 0.2 to 0.6 electrons per half unit cell -extremely(e/h.u.c.). small particle The layer size, charge flat is balanced shape and, by the accordingly, interlayer cations great Na, surface Ca, K, Mg, area. Fe, which are weakly bonded and exchangeable. The interlayer space contains water molecules. The number of molecules 2.1. Crystalis Structurenot constant and may increase depending on the grade of the interlayer cation, causing the mineral particle to swell. The interlayer space also contains water molecules in varying quantities, The basicwhich structuremay increase of depending smectite on group the interlayer minerals cation is wellkind and known cause andthe la hasyers beento distend illustrated and the in many mineral particles to swell. Indeed, it has been shown that the layer charge is related to the colloidal publicationsproperties (one of of them smectites is shown such as in swelling. Figure2 ).Char Smectitesge heterogeneity, are three-layer which includes minerals. both Thischarge three-layer package hasmagnitude two silica and charge tetrahedral localization, sheets is al joinedso related to to a these central properties octahedral [7]. sheet. On this basis, smectite structures canSaponite be classified belongs as to 2:1the phyllosilicates.trioctahedral series Dueof minerals to substitutions of the smectite in group. the tetrahedral Notwithstanding or octahedral sheets, or theboth existencethe wide occurrence of vacancies of saponite in the in octahedralnature and extensive sheet, theprevious surface study, of the the saponite three-layer structure package has has not been determined yet. The authors are of the opinion that the reason for it is the absence of a negativematerial charge, applicable which createsfor single-crystal a charge investigations. imbalance. According to the Nomenclature Committee of the Association Internationale pour l’Etude des Argiles (AIPEA) [6] the layer charge of smectites varies from 0.2 to 0.6 electrons per half unit cell (e/h.u.c.). The layer charge is balanced by the interlayer cations Na, Ca, K, Mg, Fe, which are weakly bonded and exchangeable. The interlayer space contains water molecules. The number of molecules is not constant and may increase depending on the grade of the interlayer cation, causing the mineral particle to swell. The interlayer space also contains water molecules in varying quantities, which may increase depending on the interlayer cation kind and cause the layers to distend and the mineral particles to swell. Indeed, it has been shown that the layer charge is related to the colloidal properties of smectites such as swelling. Charge heterogeneity, which includes both charge magnitude and charge localization, is also related to these properties [7]. Minerals 2018, 8, 549 3 of 18 Saponite belongs to the trioctahedral series of minerals of the smectite group. Notwithstanding both the wide occurrence of saponite in nature and extensive previous study, the saponite structure has not been determined yet. The authors are of the opinion that the reason for it is the absence of material applicable for single-crystal investigations. 2.2. Chemical Composition and Properties The chemical composition of naturally occurring saponite is highly variable due to common Fe2+, 3+ 3+ 2+ 3+ Fe and AlMineralssubstitutions 2018, 8, x FOR PEER for REVIEW Mg in the octahedral sheet, which are accompanied by partial3 of 18 Al and Fe3+ substitutions for Si4+ in the tetrahedral sheet [8,9]. Thus, saponite from the Arkhangelsk kimberlite 2.2. Chemical Composition and Properties province contains 5.09% Al2O3, 3.14% Fe2O3 and 2.56% FeO [10]; crystal-chemical formula, calculated
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