Previous mineralogical investigations (QemSCAN) performed on all effluent flotation streams of Mimosa mine (Zimbabwe) indicated the presence of appreciable amounts of platinum group minerals (PGMs), which are not recovered. Most, generally in excess of 70%, of the liberated PGMs in these streams belonged to the Pt-Pd-Bi-Te class in all the samples investigated. In the first part of this work, electrochemical investigations, electrochemically-controlled contact angle measurements and Raman spectroscopy have been employed to investigate the interaction of ethyl xanthate with Pd-Bi-Te and PtAs2. Impedance measurements showed lower capacitance values in solutions containing KEX indicating the formation of a continuous surface layer. Anodic and cathodic polarization diagrams show the mixed potential to be higher than the reversible potential of the xanthate-dixanthogen equilibrium reaction, hence the formation of dixanthogen on the surface is possible. Electrochemically controlled in situ Raman spectroscopy has confirmed the co-presence of xanthate with dixanthogen indicating that xanthate retains its molecular integrity when it adsorbs on the surface of the Pd-Bi-Te. The result of this investigation has shown dixanthogen to be present on both the minerals (PtAs2 and Pd-Bi-Te) when the surfaces are anodically polarized. Chemisorbed xanthate could be identified within 120 seconds yielding a hydrophobic surface as indicated by electrochemically-controlled contact angle measurements. Maximum contact angles of 63o were measured in the case Pd-Bi-Te. As a result the mineral surface is expected to be hydrophobic and a lack of collector interaction with the mineral is not the reason for low PGM recoveries experienced. Secondly, the flotation recovery of synthetically prepared Pd-Bi-Te was compared with that of chalcopyrite (a typical fast-floating mineral) and pyrrhotite (a typical slow-floating mineral), with microflotation tests. These indicated Pd-Bi-Te to be a fast-floater with flotation rates exceeding that of chalcopyrite. Predicted flotation rate constants (from the Ralston model) were significantly lower for small particles (with diameters similar to those lost to the effluent streams) compared with those of particle with intermediate sizes. This supports the suggestion that losses to effluent streams are caused by particle size effects. / Thesis (PhD (Metallurgical Engineering))--University of Pretoria, 2006. / Materials Science and Metallurgical Engineering / unrestricted

Thesis (MScEng)--Stellenbosch University, 2002. / ENGLISH ABSTRACT: Flotation is notorious for its susceptibility to process upsets and consequently its poor performance, making successful flotation control systems an elusive goal. The control of industrial flotation plants is often based en the visual appearance of the froth phase, and depends to a large extent on the experience and ability of a human operator. Machine vision systems provide a novel solution to several of the problems encountered in conventional flotation systems for monitoring and control. The rapid development in computer VISIon, computational resources and artificial intelligence and the integration of these technologies are creating new possibilities in the design and implementation of commercial machine vision systems for the monitoring and control of flotation plants. Current machine vision systems are available but not without their shortcomings. These systems cannot deal with fine froths where the bubbles are very small due to the segmentation techniques employed by them. These segmentation techniques are cumbersome and computationally expensive making them slow in real time operation. The approach followed in this work uses neural networks to solve the problems mentioned above. Neural networks are able to extract information from images of the froth phase without regard to the type and structure of the froth. The parallel processing capability of neural networks, ease of implementation and the advantages of supervised or unsupervised training of neural networks make them potentially suited for real-time industrial machine vision systems. In principle, neural network models can be implemented in an adaptive manner, so that changes in the characteristics of processes are taken into account. This work documents the development of linear and non-linear principal component models, which can be used in a real-time machine vision system for the monitoring, and control of froth flotation systems. Features from froth images of flotation processes were extracted via linear and non-linear principal component analysis. Conventional linear principal component analysis and three layer autoassociative neural networks were used in the extraction of linear principal components from froth images. Non-linear principal components were extracted from froth images by a three and five layer autoassociative neural network, as well as localised principal component analysis based on k-means clustering. Three principal components were extracted for each image. The correlation coefficient was used as a measure of the amount of variance captured by each principal component. The principal components were used to classify the froth images. A probabilistic neural network and a feedforward neural network classifier were developed for the classification of the froth images. Multivariate statistical process control models were developed using the linear and non-linear principal component models. Hotellings T2 statistic and the squared prediction error based on linear and non-linear principal component models were used in the development of multivariate control charts. It was found that the first three features extracted with autoassociative neural networks were able to capture more variance in froth images than conventional linear principal components, the features extracted by the five layer autoassociative neural networks were able to classify froth images more accurately than features extracted by conventional linear principal component analysis and three layer autoassociative neural networks. As applied, localised principal component analysis proved to be ineffective, owing to difficulties with the clustering of the high dimensional image data. Finally the use of multivariate statistical process control models to detect deviations from normal plant operations are discussed and it is shown that Hotellings T2 and squared prediction error control charts are able to clearly identify non-conforming plant behaviour. / AFRIKAANSE OPSOMMING: Flottasie is berug daarvoor dat dit vatbaar vir prosesversteurings is en daarom dikwels nie na wense presteer nie. Suksesvolle flottasiebeheerstelsels bly steeds 'n ontwykende doelwit. Die beheer van nywerheidsflottasie-aanlegte word dikwels gebaseer op die visuele voorkoms van die skuimfase en hang tot 'n groot mate af van die ervaring en vaardighede van die menslike operateur. Masjienvisiestelsels voorsien 'n vindingryke oplossing tot verskeie van die probleme wat voorkom by konvensionele flottasiestelsels ten opsigte van monitering en beheer. Die vinnige ontwikkeling van rekenaarbeheerde visie, rekenaarverwante hulpbronne en kunsmatige intelligensie, asook die integrasie van hierdie tegnologieë, skep nuwe moontlikhede in die ontwerp en inwerkingstelling van kommersiële masjienvisiestelsels om flottasie-aanlegte te monitor en te beheer. Huidige masjienvisiestelsels is wel beskikbaar, maar is nie sonder tekortkominge nie. Hierdie stelsels kan nie fyn skuim hanteer nie, waar die borreltjies baie klein is as gevolg van die segmentasietegnieke wat hulle aanwend. Hierdie segmentasietegnieke is omslagtig en rekenaargesproke duur, wat veroorsaak dat dit stadig in reële tyd-aanwendings is. Die benadering wat in hierdie werk gevolg is, wend neurale netwerke aan om die bovermelde probleme op te los. Neurale netwerke is instaat om inligting te onttrek uit beelde van die skuimfase sonder om ag te slaan op die tipe en struktuur van die skuim. Die parallelle prosesseringsvermoëns van neurale netwerke, die gemak van implementering en die voordele van die opleiding van neurale netwerke met of sonder toesig maak hulle potensieel nuttig as reële tydverwante industriële masjienvisiestelsels. In beginsel kan neurale netwerke op 'n aanpassende wyse geïmplementeer word, sodat veranderinge in die kenmerke van die prosesse deurlopend in aanmerking geneem word. Kenmerke van die beelde van die skuim tydens die flottasieproses is verkry by wyse van lineêre en nie-lineêre hootkomponentsanalise. Konvensionele lineêre hoofkomponentsanalise en drie-laag outo-assosiatiewe neurale netwerke is gebruik in die onttrekking van lineêre hoofkomponente uit die beelde van die skuim. Nie-lineêre hoofkomponente is uit die beelde van die skuim onttrek by wyse van 'n drie- en vyf-laag outo-assosiatiewe neurale netwerk, asook deur 'n gelokaliseerde hoofkomponentsanalise wat op k-gemiddelde trosanalise gebaseer is. Drie hoofkomponente is vir elke beeld onttrek. Die korrelasiekoëffisiënt is gebruik as 'n maatstaf van die afwyking wat deur elke hoofkomponent aangetoon is. Die hoofkomponente is gebruik om die beelde van die skuim te klassifiseer. 'n Probalistiese neurale netwerk en 'n voorwaarts voerende neurale netwerk is vir die klassifisering van die beelde van die skuim ontwerp. Multiveranderlike statistiese prosesbeheermodelle is ontwerp met die gebruik van die lineêre en nie-lineêre hoofkomponentmodelle. Hotelling se T2 statistiek en die gekwadreerde voorspellingsfout, gebaseer op lineêre en nie-lineêre hoofkomponentmodelle, is gebruik in die ontwikkeling van multiveranderlike kontrolekaarte. Dit is gevind dat die eerste drie eienskappe wat met behulp van die outo-assosiatiewe neurale netwerke onttrek is, instaat was om meer variansie by beelde van skuim vas te vang as konvensionele lineêre hoofkomponente. Die eienskappe wat deur die vyf-laag outo-assosiatiewe neurale netwerke onttrek is, was instaat om beelde van skuim akkurater te klassifiseer as daardie eienskappe wat by wyse van konvensionele lineêre hoofkomponentanalalise en drie-laag outo-assosiatiewe neurale netwerke onttrek is. Soos toegepas, het dit geblyk dat gelokaliseerde hoofkomponentsanalise nie effektief is nie, as gevolg van die probleme rondom die trosanalise van die hoë-dimensionele beelddata. Laastens word die aanwending van multiveranderlike statistiese prosesbeheermodelle, om afwykings in normale aanlegoperasies op te spoor, bespreek. Dit word aangetoon dat Hotelling se T2 statistiek en gekwadreerdevoorspellingsfoutbeheerkaarte instaat is om afwykende aanlegwerksverrigting duidelik aan te dui.

<p>The growth and removal of inclusions in stirred ladles hasbeen studied. First, the importance of different growthmechanisms suggested in the literature were studied. Simulationresults from a fundamental model of an induction-stirred ladlehave been used as input in the calculations. Based on thegrowth calculations it was concluded that four of the growthmechanisms need not to be considered since they contribute solittle: i) diffusion of oxygen and aluminum to the inclusionsurface, ii) diffusion coalescence, iii) Brown motioncollision, and iv) laminar shear collision. The majorcontributor to inclusion growth is turbulent collision. Growthdue to Stoke's collisions is also somewhat important if largedifferences among inclusion sizes exist.</p><p>Growth of inclusions in gas stirred ladles was studied usinga similar approach as the one for induction stirred ladles, butwith use of simulation results from a fundamental mathematicalmodel of a gas-stirred ladle. Similarly to what was found inthe case of induction stirring, it was found that turbulentcollisions and Stokes collisions appeared to be the majormechanisms for inclusion growth. The contribution of laminarshear collisions to growth was deemed negligible compared tothat of turbulent collisions.</p><p>For the gas stirred ladle different removal mechanisms werealso studied, based on input data from a mathematical model ofa gas-stirred ladle. It was found that different modelssuggested to predict the inclusion removal due to bubbleflotation gave very different results. Also, all models assumeda spherical shape of the gas bubbles, which was found to beless realistic. Therefore, a new model for inclusion removal byspherical cap bubble flotation was developed. In the newcalculations, the most important mechanisms of inclusionremoval were found to be removal to the top slag and removal bybubble flotation, assuming spherical-cap bubbles and planecontact. When the bubbles were assumed to be spherical,resulting removal rates were lower than when they were assumedto be spherical caps. Based on these results it is concludedthat more research is needed to obtain a better understandingof the importance of bubble flotation on inclusion removal.Experiments are clearly needed to determine which modelconcepts produce predictions in best agreement withcorresponding data from actual steelmaking processes.</p>

Biosurfactants are compounds that exhibit surface activity (e.g., reduce surface and interfacial tension) and are derived from natural, biological sources. They are considered green substances due to their natural derivation, biodegradability, and relatively low toxicity. Biosurfactants from multiple classes have been shown to interact with metals, and a review of these interactions is provided. Rhamnolipids produced by Pseudomonas aeruginosa are attracting attention for metal remediation applications. The purpose of this dissertation is to evaluate rhamnolipids' ability to complex rare earth elements, determine the environmental compatibility of novel rhamnolipid diastereomers, and assess the efficacy of rhamnolipid as a collector in ion flotation. Previous research shows rhamnolipids selectively bind elements of environmental concern over common soil and water cations, but there had been no examination of transition metals from the f-block of the periodic table. The f-block elements include the rare earth elements, which are a vital component of nearly every modern technology and subject to supply risk. The interaction between monorhamnolipids and the rare earth elements was investigated by determining conditional stability constants using a resin-based ion exchange method. For the 27 metals examined, the conditional stability constants could be divided into three groups, albeit somewhat subjectively: weakly, moderately, and strongly bound. UO22+, Eu3+, Nd3+, Tb3+, Dy3+, La3+, Cu2+, Al3+, Pb2+, Y3+, Pr3+, and Lu3+are strongly bound with conditional stability constants ranging from 9.82 to 8.20; Cd2+, In3+, Zn2+, Fe3+, Hg2+, and Ca2+ are moderately bound with stability constants ranging from 7.17 to 4.10; and Sr2+, Co2+, Ni2+, UO22+, Cs+, Ba2+, Mn2+, Mg2+, Rb+, and K+ are weakly bound with stability constants ranging from 3.95 to 0.96. The uranyl ion is reported twice due to the ion demonstrating two distinct binding regions. The conditional stability constants were demonstrated to be an effective predictor of metal removal order. The metal parameters of enthalpy of hydration and ionic charge to radius ratio were shown to be determinants of complexation strength. Naturally produced rhamnolipids are a mixture of congeners. Synthetic rhamnolipid synthesis has recently enabled production of four monorhamnolipid diastereomers of a single congener. The biodegradability, acute toxicity (Microtox assay), embryo toxicity (Zebrafish assay), and metal binding capacity of the diastereomers was investigated and compared to natural monorhamnolipid. Biodegradability testing showed all the diastereomers were inherently biodegradable. By the Microtox assay, all of the monorhamnolipids were categorized as slightly toxic by Environmental Protection Agency ecotoxicity categories. Out of 22 parameters tested, the zebrafish toxicity assay showed only diastereomer toxicity for the mortality parameter, except for diastereomer R,R which showed no toxic effects. All the monorhamnolipids interacted with both Cd2+ and Pb2+. Ion flotation is one possible technology for metal recovery and remediation of metal contaminated waters. Ion flotation utilizes charged surfactants to collect and concentrate non-surface active ions at the surface of an aerated solution. Rhamnolipid's suitability as a collector in ion flotation was investigated. A flotation column was designed to test monorhamnolipid efficacy as a collector. Monorhamnolipids form foams and effectively remove Cs+, Cd2+, and La3+ from solution. The efficacy of the flotation process relies on the collector:colligend ratio and valency of the colligend. Flotation of metal solutions showed a removal order of Cd2+>La3+>>Cs+ when the metals were present individually and mixed at equimolar concentrations. When mixed at order of magnitude different concentrations, the flotation order was Cd2+>>Cs+>>La3+. These studies show rhamnolipid has potential to be used for environmentally-compatible metal recovery and metalliferous water remediation, especially for the rare earth elements.

The present study is targeted on the optimization of the flotation conditions for the improvement of the industrial flotation practice. Part I is focused on the improvement of the flotation of Mountain Pass mine ore for the beneficiation of rare earth elements. The objective is to improve the rare earth recovery of Mountain Pass ore by developing a novel flotation reagents' scheme, meanwhile reducing the flotation temperature to a cost-efficient level and simplifying the flowsheet. Surface chemistry study by contact angle, zeta potential and microflotation tests indicate that a mixed collector consisting of oleic acid (OA) and sodium octanohydroxamate hydrate (OHA) is beneficial for rare earth flotation. More importantly, salicylhydroxamic acid (SHA) is also a promising collector due to the high selectivity. Lab-scale flotation tests using SHA as collector show that 80-90% REE recovery and <20% gangue recovery are achieved at 40°C~60°C, which yield a rougher concentrate of 30%~40% REO. A novel flotation scheme has been developed towards Mountain Pass rare earth mine. The new scheme is of both high selectivity and high recovery, meanwhile the dosage of reagent required is much less, and the flotation temperature is also significantly reduced. Interactive adsorption models are built up through FT-IR and AFM study. The interaction of collector with bastnaesite surface is illustrated. Hydroxamic acid collectors (OHA and SHA) adsorb on bastnaesite surface by forming stable chelating complex. The selectivity of collectors towards bastnaesite flotation is summarized as SHA>OHA>OA. Part II is focused on the improvement of the flotation of Resolution Copper's Superior mine ore at an elevated temperature for the beneficiation of chalcopyrite. Because the Resolution Copper ore is mined from a deep, hot, underground mine, the temperature of ROM (run of mine ore) is much higher than that of the ore usually processed in a typical open-pit copper mine. The ore temperature will still be high during flotation. It is therefore critical to carry out a systemic study on the flotation of Resolution Copper ore at elevated temperatures and clarify the impact on flotation. An overall beneficial effect is observed in high temperature flotation through a lab-scale flotation study. Further action of temperature control is not necessary. The contact angle results indicate that surface hydrophobicity is enhanced at elevated temperature, of which the surface morphology change (shown by AFM images) of xanthate adsorption species (dixanthogen) is the key factor.

School of Chemical and Metallurgical Engineering, Faculty of Engineering and Built in Environment, University of Witwatersrand, Johannesburg, South AfricaMay, 2016 / Trojan Nickel Mine in Bindura, Zimbabwe, produces nickel concentrates which, until 2008, were then processed at their smelter operations (Bindura Smelter and Refinery) and the subsequent product sent to the hydrometallurgical plant to produce nickel cathodes. However, due to economic challenges the smelter and hydrometallurgical plant operations were closed down in 2008. Currently, Trojan Mine produces nickel concentrates through flotation which are then sold to Glencore International, in China, for further processing. Since 2002, the MgO (also known as talc) content in the Trojan Nickel Mine final concentrates has increased from around 12% to a peak of 22%. The average MgO content in the concentrates for the year ending in March 2015 was 16.14%. An offtake agreement of sale was made with Glencore International, in China, whereby a penalty is charged for all concentrates with MgO levels greater than 5%. In the year 2015 alone, monthly revenue due to smelter penalties amounted to an estimated total of US$141 000. Higher MgO levels in the concentrates are prevalent when processing low grade ores, with nickel content ranging from 0.65-1.2%. This research focused on reducing the MgO content of the Trojan’s final concentrate to 12%; which was the smelter’s set target while it was still operational. In order to investigate the effect of pH and chemical depressants on the MgO levels in the concentrate, batch flotation tests were carried out at pH 8.95 and 10.2, using several guargum depressants namely: Betamin DZT 245 (standard), Cytec S9349, DLM PDE, DLM RS, and CMC (carboxy methyl cellulose) depressants namely: Depramin 177, 267 and 347, and ND 521, 522 and 523. The concentrates were collected at 1, 5, 15 and 25 minute intervals in order to understand the stage-wise recovery of nickel and MgO minerals. A flotation test, without a depressant, was also carried out in order to understand the kinetics of the gangue minerals. Stage addition of depressants was investigated, by adding another 50g/t dose of the DZT 245 depressant after 1 minute into the flotation test. Collector combination tests using SIPX, SIPX:NC228, SIPX:NC236 and SIPX:PNBX, were also carried out to determine the best reagent suite. To understand the recovery of nickel and MgO in the flotation circuit, a plant survey was carried out, and the particle size distribution (PSD) and assays of collected samples were determined. Flotation tests results indicated that DLM RS and DLM PDE guargum depressants had better selectivity towards MgO and higher nickel recoveries as compared to the Betamin DZT 245 depressant that is currently used in the plant. It is recommended that a plant trial be carried out using the DLM RS depressant, which further reduced the MgO and mass of concentrate recovered by 3.79% and 32% respectively. The stage recovery of MgO for a test carried out without a depressant showed that 57.7% of the MgO was recovered during the first five minutes of the test. Thus, there is need to effectively depress the fast floating MgO during the early stages of the flotation process. Nickel recovery and grade were increased by 2.7% and 2.1% respectively, after adding the second dose of the depressant after 1 minute into the flotation test. The results indicated that the fast floating MgO can depress the valuable mineral if the depressing effect of the depressant is short-lived, which in turn leads to reduced nickel recoveries. Hence, reducing the time between the two stage additions of the depressant in the plant will help further supress the fast floating MgO silicates. It was also noted that at least 60% of the nickel was recovered during the first five minutes of the tests. Hence, reducing the residence time of the rougher flotation bank would reduce MgO recovery into the concentrates without adversely affecting the nickel recoveries. Plant survey results showed that the scavenger bank feed that was deslimed, had less finer MgO particles and MgO content as compared to the rougher bank feed. This indicates that desliming before the coarse flotation process could reduce MgO slimes in the feed, reduce the recovery of MgO due to slime coatings in the final concentrates and the reagent consumption in the bank. Introducing the desliming unit could be beneficial since the desliming cyclones have low installation and operational costs. / MT2016

Introdução Análise da qualidade da água do reservatório Billings, situado na região Metropolitana de São Paulo, em decorrência do bombeamento de água proveniente de duas estações de Flotação experimentais, situadas no rio Pinheiros. Objetivo Analisar parâmetros de qualidade da água revertida para o reservatório Billings, sob o aspecto de poluição e toxicidade, objetivando a utilização deste reservatório para reúso recreacional e também para geração de energia na Usina Henry Borden em Cubatão. Metodologia Para a pesquisa quantitativa foram utilizados dados secundários, coletados ao longo de 22 de agosto de 2007 a 31 de maio de 2008, sendo este o período de funcionamento do sistema de flotação, nos pontos de amostragem convencionais e também nos pontos com monitoramento contínuo, em locais previamente estabelecidos. Resultados A análise indicou que o primeiro ponto de monitoramento dentro da represa sofre os efeitos diretos do bombeamento, o que não se constata nos pontos mais distantes do corpo central do reservatório. Apontou também a presença de alguns contaminantes importantes como chumbo e clorofórmio na água, em quantidade acima do permitido na legislação. Conclusão - A utilização do reservatório para reúso recreacional com contato primário está contra indicada e o bombeamento das águas para geração de energia pode ser mantido, uma vez que a qualidade de água para esta aplicação deverá ter baixa quantidade de sólidos, que são removidos pela flotação. Recomendações - Realização de estudos que contemplem a análise conjunta da influência dos benefícios oriundos do Programa de Despoluição do Tietê, em implantação pela Companhia de Saneamento Básico de São Paulo, e também do sistema de tratamento por flotação. Ajustes operacionais e adequações no sistema de flotação. Mapeamento e identificação de fontes de lançamento de esgotos diretamente no corpo da represa, e eliminação destas emissões clandestinas. Controle rigoroso da ocupação de áreas no entorno da Billings. / Introduction - A quality assessment of the water pumped from two experimental floating plants on the Pinheiros River into the Billings Reservoir, located in the Sao Paulo Metropolitan Region. Objective: To analyze quality parameters of the water pumped into the Billings Reservoir, scrutinizing both pollution and toxicity; with focus on the recreational use of the reservoir as well as generating energy at the Henry Borden Plant in the city of Cubatão. Methodology For the quantitative research, secondary data was collected from August 22, 2007 to May 31, 2008 the functioning period of the flotation systems. The data was gathered in conventional sampling points as well as pre-established continuous monitoring sampling points. Results - The assessment has indicated that the first monitoring point inside the reservoir is affected by the pumping, however, this fact does not occur in distant points located in the reservoirs central body. Some important pollutants such as lead and chloroform showed levels above allowed by law. Conclusion Primary contact for Recreational reuse is not indicated for this reservoir; however, the water pumping for energy generation can be kept, since the water for this application must have low quantities of solids. Recommendation Development of studies that assess both the resulting benefits of the Tiete River Clean-Up Project, implemented by The Sanitation Company of The State of Sao Paulo (SABESP), as well as Flotation Treatment System; Operational adjustments on Flotation System; Identify and eliminate underhand sewage discharged into the reservoir; Strict control of the occupied areas surrounding the Billings reservoir.

Diferentes estratégias de flotação (reagentes, pH e rota) têm sido utilizadas na separação entre apatita e carbonatos em todo o mundo. Há evidências na literatura de que a cristalinidade afeta a flotação de apatitas e calcitas com oleato de sódio. Além disso, a dissolução dos sais semi-solúveis pode influenciar a interação entre a superfície dos minerais e os reagentes de flotação, uma vez que o mecanismo de adsorção mais importante é a precipitação de oleato de cálcio na interface sólido/líquido. Portanto, o objetivo deste trabalho é investigar a relação entre cristalinidade, cinética de dissolução e resposta à flotação de apatitas e calcitas de diferentes gêneses (ígnea, metamórfica e sedimentar) e origens. Quatro tipos de minerais foram utilizados: purificados a partir de minérios, previamente purificados, naturalmente puros e amostras de coleção. As amostras foram caracterizadas por fluorescência de raios-X e microanálise (WDS/EDS). Características físicas como densidade (d), área superficial (S) e porosidade (P) também foram determinadas. O método de Rietveld aplicado à difração de raios-X foi usado tanto para comprovar a pureza das amostras como para estudar a cristalinidade dos minerais por meio da determinação dos parâmetros de rede (distâncias a e c, e volume da cela unitária- VCU), além do grau de cristalinidade (GC), tamanho de cristalito (TC) e microdeformação (MD). Ensaios de dissolução, conduzidos na ausência de CO2, forneceram a quantidade (mol) de íons Ca2+ (nCa2+) dissolvidos em função do tempo (t) e normalizada em relação à área superficial. Os resultados se ajustam a um modelo de primeira ordem: nCa2+ = Ca2+MAX(1- e-kt). Este procedimento permitiu calcular os valores da quantidade máxima de íons Ca2+ dissolvidos (Ca2+MAX), bem como da constante cinética (k). Além disso, a velocidade de dissolução foi determinada para a etapa rápida (VR), que caracteriza o início da reação, e para a etapa lenta (VL), que ocorre nas proximidades do estado estacionário. A resposta à flotação com oleato de sódio foi determinada por meio de experimentos de microflotação. Várias relações de causa e efeito são encontradas: flotabilidade (F) versus VR, e VR versus características intrínsecas (parâmetros de rede, de cristalinidade e físicos). VR foi selecionado para participar de tais modelos, pois, caracteriza o intervalo de tempo em que o condicionamento (1 minuto) e a microflotação (1 minuto) ocorrem. Observa-se que a flotabilidade dos minerais aumenta com o aumento de VR, sugerindo que apatitas e calcitas que disponibilizam mais íons Ca2+ em solução para interagir com o oleato, exibem mais elevada flotabilidade. Equações lineares de F em função de VR em pH 8 (R = 0,97 para apatitas e R = 0,66 para calcitas) e pH 10 (R = 0,95 para apatitas e R = 0,63 para calcitas) foram encontradas. Correlações lineares múltiplas foram utilizadas para relacionar VR (em pH 8 e 10) com as características intrínsecas que exercem maior influência sobre este parâmetro. Para as apatitas, VR foi equacionado em função de GC, TC e c, enquanto para as calcitas, os parâmetros GC, TC, d e P foram selecionados para compor o modelo. Os valores de VR calculados se ajustam aos observados dentro de um intervalo de confiança de 95%. As equações lineares propostas para as apatitas foram usadas para se estimar F das amostras de Anitápolis-SC e Tapira-MG, que não foram submetidas aos ensaios de dissolução. Os valores de F calculados estão em concordância com aqueles experimentalmente determinados. / Different flotation strategies (reagents, pH and route) have been adopted to separate apatite from carbonates around the world. Literature provides evidences that crystallinity affects flotation response of apatite and calcite with sodium oleate. Furthermore, dissolution of salt-type minerals influences the interaction between mineral surface and flotation reagents, because the most important adsorption mechanism is the surface precipitation of calcium oleate onto mineral/water interface. Therefore, the objective of this research is to investigate the relationship between crystallinity, dissolution kinetics and flotation response of apatites and calcites from different genesis (igneous, metamorphic and sedimentary) and origins. Four sorts of minerals were utilized: minerals purified from ores, minerals previously purified, naturally pure minerals and collection samples. They were characterized by X-ray fluorescence and X-ray microanalysis (WDS/EDS). Physical characteristics, as specific gravity (d), surface area (S) and porosity (P), were also determined. The Rietveld method applied to X-ray diffraction data was used either to probe the purity of samples or to study the crystallinity of the minerals by means of determining their lattice parameters (a and c dimensions plus lattice volume-VCU), in addition to crystallinity degree (GC), crystallite size (TC) and microstrain (MD). Dissolution experiments, conducted in the absence of CO2, yielded curves which relate the amount (mol) of dissolved Ca2+ ions (nCa2+) versus time (t), normalized by the surface area. They fit a first order model: nCa2+ = Ca2+MAX(1- e-kt). Curve fitting via exponential adjustment was accomplished to calculate values of the maximum amount of dissolved Ca2+ ions (Ca2+MAX) and the kinetic constant (k). In addition, the dissolution rate was determined for the fast step (VR), which characterizes the beginning of the reaction, and for the slow step (VL), as it tends to the steady state. Flotation response with sodium oleate was determined by microflotation experiments. Several cause-effect relationships are found: floatability (F) versus VR, and VR versus intrinsic characteristics of minerals (lattice, crystallinity and physical parameters). VR was selected to participate in the model because it characterizes the length of time along which reagent conditioning (1 minute) plus microflotation (1 minute) take place. It is observed that F increases as VR becomes greater, suggesting that samples of apatites and calcites which place more Ca2+ ions in solution to interact with oleate exhibit higher flotation performance. Linear equations of F versus VR at pH 8 (R = 0,97 for apatites and R = 0,66 for calcites) and pH 10 (R = 0,95 for apatites and R = 0,63 for calcites) were found. Likewise, multiple linear correlations were used to relate VR (at pH 8 and 10) with the intrinsic characteristics of apatites and calcites that affect VR to a greater extent. For apatites, VR was modeled as a function of GC, TC and c, while for calcites, the parameters GC, TC d and P were selected to compose the model. The calculated VR values fit the experimental ones within 95% of confidence. The linear equations developed for apatites were used to estimate floatability of the samples from Anitápolis-SC and Tapira-MG, which were not submitted to dissolution experiments. The values of calculated floatability are in agreement with the experimental ones.

Este trabalho aborda a molhabilidade de apatita por água em temperatura ambiente (20-25°C) objetivando contribuir para um melhor entendimento de seu comportamento em sistemas de flotação. Água, devido às fortes forças atrativas entre suas moléculas, não espalha completamente sobre sólidos de baixa energia como apatita pré-tratada com surfatantes aniônicos de cadeia longa. Este comportamento é explorado por engenheiros de processamento mineral para separar apatita de minerais de ganga via flotação aniônica direta em circuitos industriais ao redor do mundo. Nesta tese, a molhabilidade de apatita (tratada ou não com oleato de sódio-NaOl em pH=10,5) foi caracterizada pelo ângulo de contato de avanço da água (TETAa), trabalho de adesão (Wa) da água sobre apatita e coeficiente de espalhamento (S) de água sobre o sólido. Medidas diretas de TETAa sobre os planos frontal (010) e basal (001) de um cristal de apatita bem definido proveniente de Ipirá- BA (apatita-Ipirá) foram executadas pelo Método da Bolha Cativa (MBC), enquanto determinações indiretas de TETAa foram realizadas pelo Método da Ascensão Capilar (MAC) através da percolação de líquidos (água e/ou metanol) através de leitos partículas de apatita-Ipirá ou apatita-Cajati (proveniente de Cajati-SP). No MAC, o uso de hexano foi adequado para determinar a magnitude da constante de empacotamento (c) para partículas de apatita de baixa molhabilidade (TETAa>>0°), enquanto que a água se mostrou mais apropriada para ser usada na determinação da constante c para partículas de apatita não tratadas com surfatantes (TETAa~0o). Ensaios de microflotação foram conduzidos com apatita-Ipirá em pH=10,5 e com NaOl (0-75mg/L) enquanto ensaios de flotação gama foram executados com minério de fosfato proveniente de Cajati-SP previamente tratado com amido (37,5mg/L) e alquil sarcosinato de sódio-Berol®867 (25mg/L) em pH=10,6. Os resultados das medidas de TETAa e dos ensaios de microflotação indicaram uma relação de causa-efeito entre a concentração de NaOl (0-75mg/L), molhabilidade de apatita-Ipirá e sua resposta à microflotação: as maiores recuperações foram obtidas com as maiores concentrações do coletor NaOl, maiores valores de TETAa, menores valores de Wa e valores mais negativos de S. Os valores de TETAa diretamente medidos sobre as faces de um cristal de apatita-Ipirá pelo MBC mostrou que NaOl adsorve preferencialmente sobre o plano (010) comparado ao plano (001). Além disso, a tensão superficial crítica de molhabilidade (GAMAc) da apatita-Ipirá, pré-tratada com 75mg/L de NaOl, foi de 30,2erg/cm2 para o plano (001) versus 29,6erg/cm2 para o plano (010). Após serem condicionadas com reagentes de flotação (amido=37,5mg/L e Berol®867=25mg/L em pH=10,6) e flotadas em estágio rougher, partículas de apatita-Cajati exibiram TETAa=64.2°±1.1°. O valor de GAMAc, determinado via experimentos de flotação gama foi GAMAc~34,5erg/cm2; enquanto GAMAc determinado por diagramas cosTETA x GAMALV foi de GAMAc~33,9erg/cm2. Os resultados de flotação gama com o minério de fosfato de Cajati mostrou um platô de máxima recuperação de apatita (95-98%) quando 52,7erg/cm2<GAMALV<72,9erg/cm2. Ao contrário da apatita, a recuperação dos minerais de ganga (silicatos e carbonatos) foi estritamente ascendente com o aumento de GAMALV. A maior Eficiência de Separação apatita/ganga (E.S. = recuperação de apatita menos a recuperação de ganga) foi obtida em GAMALV=50,5erg/cm2 para apatita/silicatos e em GAMALV=51,4erg/cm2 para apatita/carbonatos. Os resultados dos experimentos de flotação gama indicaram que, no circuito industrial de Cajati-SP, GAMALV pode ser modulada pela dosagem do coletor, e sua magnitude pode guiar engenheiros na tomada de decisões a respeito da dosagem de coletor que promova a maior seletividade de separação apatita/ganga. Entretanto, a falta de instrumentos apropriados para realizar medidas on-line confiáveis de GAMALV tem impedido a execução destas medidas em circuitos industriais. Deste modo, decisões a respeito da dosagem do coletor feitas pelos engenheiros continuam a ser baseadas em uma abordagem empírica ao invés de científica. / This work approaches the wetting of apatite by water at room temperature (20-25°C) aiming at to contribute towards a better understanding of its behavior in flotation systems. Water, because of its powerful attractive forces, does not readily spread over the surface of low energy solids as apatite pre-treated with anionic long chain surfactants. This behavior is exploited by mineral processing engineers to separate apatite from gangue minerals via direct anionic flotation in industrial plants around the world. In this thesis, the wettability of apatite (treated or not with sodium oleate- NaOl at pH=10.5) was characterized by the advancing water contact angle (TETAa), work of adhesion (Wa) of water to apatite and the spreading coefficient (S) of water over the solid. Direct measurements of TETAa on either frontal-(010) or basal-(001) planes of a well formed apatite crystal from Ipirá-BA (apatite-Ipirá) were carried out via Captive Bubble (CB) method, whereas indirect determinations of TETAa were accomplished via Capillary Rise (CR) method by means of percolation of liquids (water and/or methanol) through particle beds of apatite-Ipirá and apatite-Cajati (from Cajati-SP). At CR method, the use of hexane was adequate to determine the magnitude of packing constant (c) for apatite particles of low wettability (TETAa>>0o), whereas water proved to be more appropriate to be used in the determination constant c for apatite particles non-treated with surfactants (TETAa~0o). Microflotation tests were conducted with apatite-Ipirá at pH=10.5 with NaOl (0-75mg/L) whereas gamma flotation tests were carried out with phosphate ore from Cajati-SP previously treated with starch (37.5mg/L) and sodium alkyl sarcosinate-Berol®867 (25mg/L) at pH=10.6. Results from measurements of TETAa and microflotation experiments indicated a cause-effect relationship between concentration of NaOl (0-75mg/L), wettability of apatite-Ipirá and its microflotation response: the highest recoveries were yielded at higher concentration of collector NaOl, higher values of TETAa, lower values of Wa and more negative the values of S. Values of TETAa directly measured on the faces of a crystal of apatite-Ipirá by CB method showed that NaOl adsorbs preferentially onto (010) plane compared to (001) plane. Moreover, the critical surface tension of wettability (GAMAc) of apatite-Ipirá, pre-treated with 75mg/L of NaOl, was 30.2erg/cm2 for (001)-plane versus 29.6erg/cm2 for (010)-plane. After being conditioned with flotation reagents (starch=37.5mg/L and Berol®867=25mg/L at pH=10.6) and floated at rougher stage, particles of apatite-Cajati exhibited TETAa=64.2o±1.1o. The value of GAMAc, determined via gamma flotation experiments was GAMAc~34.5erg/cm2; whereas GAMAc determined by cosTETA x GAMALV plots was GAMAc~33.9erg/cm2. Results from gamma flotation experiments with phosphate ore from Cajati showed a plateau of maximum apatite recovery (95-98%) when 52.7erg/cm2<GAMALV<72.9erg/cm2. Unlike apatite, the recovery of gangue minerals (silicates and carbonates) was strictly ascending when GAMALV was increased. The highest Efficiency of Separation apatite/gangue (E.S. = recovery of apatite minus recovery of gangue) was attained at GAMALV=50.5erg/cm2 for apatite/silicates and at GAMALV=51.4erg/cm2 for apatite/carbonates. The results from gamma flotation experiments indicate that, at the industrial plant of Cajati-SP, GAMALV can be modulated by collector dosage, and its magnitude can provide guidance to practitioners to make decision on collector dosage to achieve a desired value of GAMALV which promotes the best selectivity of the separation apatite/gangue. Notwithstanding, the lack of suitable instruments to accomplish on-line reliable measurements of GAMALV has been hindering the implementation of those measurements at industrial circuits. This way, decisions on collector dosage made by practitioners continue to be based rather on empirical than on scientific approach.

Este estudo foi feito a partir de uma amostra de carvão extraído na mina da Vale- Moçambique, localizada no distrito de Moatize, Província de Tete. O trabalho visa analisar o sistema de reagentes na flotação de finos de carvão mineral pertencente à camada UCB. Dentre os métodos de beneficiamento de carvão, a flotação se destaca como um dos mais importantes para a concentração deste material, em particular no tratamento de partículas finas. A alimentação total da planta de processamento da Vale- Moçambique é de 8000 tph de carvão, onde 10% dessa alimentação corresponde a fração fina que alimenta o circuito de flotação. O material utilizado nesse estudo apresentou uma granulometria 96% menor do que 0,25 mm. Os reagentes utilizados nos ensaios de flotação foram betacol e óleo diesel como agentes hidrofobizantes e MIBC como espumante. O intervalo de concentrações de betacol na primeira fase de ensaios foi de 200 g/t a 500 g/t, e na segunda fase foi de 200 g/t a 500g/t de óleo diesel e manteve-se constante o MIBC em 300 g/t. Os resultados mostraram que é possível, a partir de uma alimentação com o teor de cinzas em torno de 22,84%, obter produtos com teores abaixo de 10% de cinzas, com uma recuperação mássica em torno de 50%. A recuperação de matéria carbonosa também foi avaliada e apresentou resultados positivos. Complementando esse estudo, foi avaliado o efeito da recuperação de H2O e foi observado que para as concentrações de betacol as recuperações variaram de 6 a 9%, e para óleo diesel mais MIBC foram de 4 a7%. / This study was done from a sample of coal mined at the Vale-Mozambique mine, located in Moatize district, Tete Province. The aim of this work is to analyze the reagent system in the flotation of coal fines belonging to the UCB layer. Among coal processing methods, flotation stands out as one of the most important for the concentration of this material, in particular in the treatment of fine particles. The total feed of the Vale-Mozambique processing plant is 8000 tph of coal, where 10% of this feed corresponds to the fine fraction that feeds the flotation circuit. The material used in this study had a particle size of 96% smaller than 0.25 mm. The reagents used in the flotation tests were betacol and diesel oil as hydrophobizing agents and MIBC as frother. The range of betacol concentrations in the first test phase was 200 g / t at 500 g / t, and in the second phase 200 g / t at 500 g / t of diesel oil and MIBC were kept constant at 300 g / t. The results showed that it is possible, from a feed with the ash content around 22.84%, to obtain products with levels below of 10% ash, with a mass recovery around 50%. The recovery of carbonaceous matter was also evaluated and presented positive results. Complementing this study, the effect of H2O recovery was evaluated and it was observed that for the concentrations of betacol the recoveries ranged from 6 to 9%, and for diesel oil plus MIBC were 4 to 7%.