This work represents a study on the biological oxidation of molybdenite, MoS2. The principal objective of this study was to investigate the possibility of the biological oxidation of molybdenite, to determine the physical and chemical conditions under which the oxidative process occurs, and to develop a strain of bacteria or alter the activity of the microorganisms by acclimatization to increase their activity on sulfide minerals, in particular molybdenite. Minerals used in this study were pyrite (FeS2), chalcopyrite (CuFeS2), molybdenite concentrate, and molybdenite ore. The microorganisms used in this investigation were autotrophic bacteria obtained from the leaching streams of Bingham Canyon, Utah. The apparatus consisted of sixty-four airlift percolators containing Ottawa sand (SiO2) as a dispersing medium for the finely divided sulfide minerals. The studies were perfomed by inoculating the solutions in the percolators with active cultures and comparing the amount of soluble molybdenum and other desired components produced with the amount found in a controlled sample. The effect of the following ions in the nutrient requirements: phosphate, ferrous iron, cupric copper, and aluminum on the molybdenite oxidative process were studied. The result of mixing pyrite and chalcopyrite with molybdenite concentrate for oxidation was also determined. The effect of the molybdate ion and phosphate ion concentrations were determined on the biological oxidation of pyrite. Studies were performed on the biological oxidation of molybdenite ore and molybdenite ore mixed with pyrite to determine the percentage molybdenum solublized, also the relative oxidation states or the solublized molybdenum. The effect of repeated bacterial transfer and molybdenite ore particle size was determined upon the biological oxidation. There were no components found in the Bingham Canyon streams that would precipitate the molybdate ion. Although these results were obtained from a synthetic media under laboratory conditions, they have provided conclusive evidence that it is possible to oxidize molybdenite by the aid of soil microorganisms.

The Ertsberg-Grasberg Mining District of Papua, Indonesia (Western New Guinea) hosts the Ertsberg Cu-Au Skarn, the giant Grasberg Porphyry Cu-Au deposit, and several other orebodies. Two 1700-meter-long cores beneath the Kucing Liar ore skarn (KL98-10-22) and the Grasberg Igneous Complex (KL98-10-21) contain high concentrations of vein and disseminated molybdenite. KL98-10-22, the focus of this study, intersects two previously unencountered intrusions, the “Tertiary intrusion Kucing Liar” (Tikl) and “Tertiary Pliocene intrusion” (Tpi). An intense dilatational quartz vein stockwork cuts Tikl and Ekmai Sandstone (Kkes) units, predating Tpi intrusion. Prior to these ultradeep cores, which extend almost 3 km below pre-mining surface, molybdenite was rarely observed in the district. Geochemistry and isotopic data indicate that Tikl and Tpi intrusions originated from the same large magmatic system that emplaced other ore-forming Ertsberg-Grasberg district intrusions. Magma in a lower crustal chamber was recharged at least twice, according to Sr-Nd data. Laser-ablation inductively-coupled plasma mass spectrometry of magmatic zircons yields 238U-206Pb ages between 3.40 ± 0.12 Ma (Dalam Andesite) and 2.77 ± 0.15 Ma (Ertsberg intrusion), revealing a shorter period of igneous activity than previously measured by K-Ar and Ar-Ar dating. Analyses include composite ages of 3.28 ± 0.08 Ma for Tikl and 3.18 ± 0.11 Ma for Tpi. Inherited zircon cores indicate Precambrian (mostly Proterozoic) basement. Molybdenite veining beneath the Kucing Liar Skarn and Grasberg Igneous Complex postdates stockwork veining and occurred before the 2.99 ± 0.11 Ma Kali dikes. Only one molybdenite vein was observed cutting Tpi. Molybdenites yielded ~3 Ma Re-Os ages and anomalous >4 Ma and <0.5 Ma ages; anomalous ages were not reproducible in follow-up analyses (this study). Smearing deformation of molybdenite (through fault activity) causes crystal strain, likely leading to annealing recrystallization. Recrystallization possibly redistributes daughter-product Os, resulting in anomalous ages from annealed material. Fluids with high Mo/Cu ratios (which were likely supercritical) precipitated late-stage molybdenite deep in the system. These fluids developed through magma chamber crystallization, which concentrated molybdenum in the melt as an incompatible element, and stripping of Cu from the magma chamber during hydrothermal activity. / text

The Ertsberg-Grasberg Mining District of Papua, Indonesia (Western New Guinea) hosts the Ertsberg Cu-Au Skarn, the giant Grasberg Porphyry Cu-Au deposit, and several other orebodies. Two 1700-meter-long cores beneath the Kucing Liar ore skarn (KL98-10-22) and the Grasberg Igneous Complex (KL98-10-21) contain high concentrations of vein and disseminated molybdenite. KL98-10-22, the focus of this study, intersects two previously unencountered intrusions, the “Tertiary intrusion Kucing Liar” (Tikl) and “Tertiary Pliocene intrusion” (Tpi). An intense dilatational quartz vein stockwork cuts Tikl and Ekmai Sandstone (Kkes) units, predating Tpi intrusion. Prior to these ultradeep cores, which extend almost 3 km below pre-mining surface, molybdenite was rarely observed in the district. Geochemistry and isotopic data indicate that Tikl and Tpi intrusions originated from the same large magmatic system that emplaced other ore-forming Ertsberg-Grasberg district intrusions. Magma in a lower crustal chamber was recharged at least twice, according to Sr-Nd data. Laser-ablation inductively-coupled plasma mass spectrometry of magmatic zircons yields 238U-206Pb ages between 3.40 ± 0.12 Ma (Dalam Andesite) and 2.77 ± 0.15 Ma (Ertsberg intrusion), revealing a shorter period of igneous activity than previously measured by K-Ar and Ar-Ar dating. Analyses include composite ages of 3.28 ± 0.08 Ma for Tikl and 3.18 ± 0.11 Ma for Tpi. Inherited zircon cores indicate Precambrian (mostly Proterozoic) basement. Molybdenite veining beneath the Kucing Liar Skarn and Grasberg Igneous Complex postdates stockwork veining and occurred before the 2.99 ± 0.11 Ma Kali dikes. Only one molybdenite vein was observed cutting Tpi. Molybdenites yielded ~3 Ma Re-Os ages and anomalous >4 Ma and <0.5 Ma ages; anomalous ages were not reproducible in follow-up analyses (this study). Smearing deformation of molybdenite (through fault activity) causes crystal strain, likely leading to annealing recrystallization. Recrystallization possibly redistributes daughter-product Os, resulting in anomalous ages from annealed material. Fluids with high Mo/Cu ratios (which were likely supercritical) precipitated late-stage molybdenite deep in the system. These fluids developed through magma chamber crystallization, which concentrated molybdenum in the melt as an incompatible element, and stripping of Cu from the magma chamber during hydrothermal activity. / text

The Ertsberg-Grasberg Mining District of Papua, Indonesia (Western New Guinea) hosts the Ertsberg Cu-Au Skarn, the giant Grasberg Porphyry Cu-Au deposit, and several other orebodies. Two 1700-meter-long cores beneath the Kucing Liar ore skarn (KL98-10-22) and the Grasberg Igneous Complex (KL98-10-21) contain high concentrations of vein and disseminated molybdenite. KL98-10-22, the focus of this study, intersects two previously unencountered intrusions, the “Tertiary intrusion Kucing Liar” (Tikl) and “Tertiary Pliocene intrusion” (Tpi). An intense dilatational quartz vein stockwork cuts Tikl and Ekmai Sandstone (Kkes) units, predating Tpi intrusion. Prior to these ultradeep cores, which extend almost 3 km below pre-mining surface, molybdenite was rarely observed in the district. Geochemistry and isotopic data indicate that Tikl and Tpi intrusions originated from the same large magmatic system that emplaced other ore-forming Ertsberg-Grasberg district intrusions. Magma in a lower crustal chamber was recharged at least twice, according to Sr-Nd data. Laser-ablation inductively-coupled plasma mass spectrometry of magmatic zircons yields 238U-206Pb ages between 3.40 ± 0.12 Ma (Dalam Andesite) and 2.77 ± 0.15 Ma (Ertsberg intrusion), revealing a shorter period of igneous activity than previously measured by K-Ar and Ar-Ar dating. Analyses include composite ages of 3.28 ± 0.08 Ma for Tikl and 3.18 ± 0.11 Ma for Tpi. Inherited zircon cores indicate Precambrian (mostly Proterozoic) basement. Molybdenite veining beneath the Kucing Liar Skarn and Grasberg Igneous Complex postdates stockwork veining and occurred before the 2.99 ± 0.11 Ma Kali dikes. Only one molybdenite vein was observed cutting Tpi. Molybdenites yielded ~3 Ma Re-Os ages and anomalous >4 Ma and <0.5 Ma ages; anomalous ages were not reproducible in follow-up analyses (this study). Smearing deformation of molybdenite (through fault activity) causes crystal strain, likely leading to annealing recrystallization. Recrystallization possibly redistributes daughter-product Os, resulting in anomalous ages from annealed material. Fluids with high Mo/Cu ratios (which were likely supercritical) precipitated late-stage molybdenite deep in the system. These fluids developed through magma chamber crystallization, which concentrated molybdenum in the melt as an incompatible element, and stripping of Cu from the magma chamber during hydrothermal activity. / text

[pt] Os minérios de cobre-molibdênio são beneficiados juntos normalmente pelo processo de flotação com a ajuda de coletores sulfidrílicos de relativa seletividade. Os concentrados bulk obtidos devem ser processados com o intuito de remover aqueles coletores empregados, pois eles são prejudiciais na etapa de separação por flotação diferencial, ou seja, na obtenção de concentrados de molibdênio de alta qualidade com baixos conteúdos de cobre e ferro. O processo de flotação bulk é realizado em condições oxidantes na presença de coletores sulfidrílicos (xantatos, etc.). Na prática industrial na etapa de flotação diferencial, estes concentrados bulk são separados por modificação do potencial eletroquímico da polpa para valores considerados redutores -300 a -450 mV, com hidrosulfeto de sódio (NaSH) ou o reagente Nokes (Penta-sulfeto de fósforo dissolvido em hidróxido de sódio) além de cianeto de sódio em alguns dos casos, para melhorar a eficiência do processo. Neste quadro, o processo industrial de separação seletiva produz efluente e gases perigosos como o H2S e HCN que devem ser controlados adequadamente. Este trabalho visa avaliar o uso do reagente ácido pseudo glicol tiouréia (PGA) e ácido tioglicólico (TGA) como alternativas ao processo industrial voltado para a separação seletiva dos minerais de cobre e molibdênio. Para a avaliação do depressor foram empregadas medições de ângulo de contato, potencial zeta, testes de flotação em célula Partridge-Smith (PS), FTIR e testes em célula de bancada em um planejamento experimental. O reagente estudado apresentou boas propriedades depressoras para minerais de cobre. Nos resultados das medições de ângulo de contato, pelo método de bolha cativa, foram encontrados valores maiores para a calcopirita do que para a molibdenita (até 10 graus de diferença) e medidas entre 60 e 70 graus, porém no pH ácido esta diferença diminui e os dois minerais apresentam quase o mesmo ângulo de contato 60 mais ou menos 1 grau. Nas medidas efetuadas não foi empregado o coletor final (querosene) para a molibdenita devido a sua falta de homogeneidade na emulsão para realizar as medidas de ângulo de contato. Nos testes de flotabilidade na célula PS em misturas binarias de calcopirita-molibdenita foram encontradas na faixa ácida, valores de pH nos quais há melhores relações de concentração e recuperações, na ordem de 67 por cento para a molibdenita e apenas 10 por cento para a calcopirita no produto flutuado. Os resultados usando o reagente NaSH em condições similares apresentam recuperações similares de molibdenita, mas na faixa básica do pH. Baseados nestes resultados foram avaliadas diversas variáveis e gerado um planejamento experimental para passar à escala de bancada onde foram obtidas recuperações de 84 por cento no concentrado rougher com apenas 13 por cento de cobre corroborando as boas propriedades do depressor estudado. / [en] Copper-molybdenum porphyry deposits worldwide are exploited industrially by flotation of the ores of interest into a BULK concentrate with the aid of sulfhydryl collectors of high efficiency and low selectivity. The bulk concentrate obtained should be reprocessed in order to remove those collectors employed in the bulk stage since they impair the differential flotation during the separation step in order to obtain clean high quality molybdenite concentrates at low contents of copper and iron. The bulk flotation process is conducted under oxidizing conditions in presence of sulfhydryl collectors (xanthates, etc.). In industrial practice these bulk concentrates are then separated by modification of the pulp electrochemical potential to values considered reducing, between -300 to-450 mV, with sodium hidrosulphide (NaSH) or Nokes reagent (phosphorus pentasulfide dissolved in sodium hydroxide). Addition of sodium cyanide in some cases is used to improve process efficiency. Bulk concentrates produced are however a very small portion of the processed mineral (only 1/50 of the total ore milled), these industrial processes produce waste effluents and hazardous gases such as H2S and HCN if not adequately controlled. This dissertation seeks to assess the reagent pseudo glycol tiourea acid (PGA) and thioglycolic acid (TGA) as an alternative to industrial processing for the selective separation of minerals of copper and molybdenum. On the evaluation of this depressant were used contact angle measurements, zeta potential, flotation tests in Partridge-Smith cell (PS), FTIR and bench scale flotation testing cell with an experimental design. The reagent studied showed good depressant properties for copper minerals according to the results presented. Within the results of the contact angle measurements with the captive bubble technique were found greater contact angles for chalcopyrite than for molybdenite (up to 10 degrees difference) and values between 60 and 70 degrees, however in acidic pH this difference decreases and both minerals have almost the same contact angle as of 60 more or less 1 degree. Though on the contact angle measured values it was not employed the final collector (kerosene) for molybdenite due to lack of homogeneity on emulsions to make the contact angle measurements. On floatability tests (on PS cell) with binary mixtures of chalcopyrite-molybdenite were found pH values on the acidic range, at which good concentration ratios and recoveries in the order of 67 percent of molybdenite with only 10 percent of the chalcopyrite were obtained. The results using NaSH reagent under similar conditions gave similar recoveries for molybdenite, however it was found in the basic pH range. Based on the results, several variables were evaluated and an experimental design employed on bench scale flotation tests, the results showed recoveries of 84 percent were obtained in the rougher concentrate with 13 percent copper corroborating the good properties of this depressant.

Neste trabalho foram abordados aspectos da cadeia do molibdênio e da molibdenita nos mercados internacional e nacional, mostrando as ocorrências e suas principais aplicações. Atualmente, no Brasil, a única opção de aproveitamento econômico desse bem mineral é o minério de molibdenita gerado como coproduto ou subproduto da mineração artesanal de esmeraldas, na região de Campo Formoso e Pindobaçu, BA. A caracterização tecnológica de minérios, produtos e do processo utilizado na recuperação da molibdenita de Campo Formoso mostrou que entraves de natureza tecnológica, com destaque relacionado ao concentrado produzido, geram produtos de baixo teor e, consequentemente, de pequeno valor econômico. Isto é devido, principalmente, à presença de outros minerais hidrofóbicos, como o talco, com propriedades físico-químicas semelhantes às da molibdenita e que são co-flotados no processo de beneficiamento. Detectado o problema, e após uma revisão bibliográfica sobre o assunto, realizou-se um estudo fundamental, em escala de laboratório, sobre a separação molibdenita/talco por flotação, com a utilização de diferentes depressores empregados, usualmente, em operações de tratamento de minérios. Dentre os depressores utilizados, a dextrina e o quebracho promoveram janelas de separabilidade entre os minerais molibdenita e talco de 63 e 68%, respectivamente. Os resultados alcançados nesses estudos fundamentais motivaram um aumento de escala, passando dos testes de microflotação em célula Partridge & Smith, para testes de flotação em bancada em célula Denver, com as dosagens dos reagentes calculadas em termos de gramas de reagente por tonelada de alimentação à flotação (concentrado de molibdenita). Na flotação em escala de bancada, os melhores resultados foram obtidos com uso da dextrina como depressor da molibdenita, na dosagem de 100 g/t, para um circuito com cinco etapas de limpeza, foi possível obter um concentrado de molibdenita com 93,4% de MoS2, o qual encontra-se dentro dos requisitos exigidos pelo comércio internacional. / In this scientific and technological contribution, the aspects of the molybdenum and molybdenite chain in the domestic and international markets were discussed, showing the occurrences and their main applications. Currently, in Brazil the only option for the economic exploitation of this mineral resource is the molybdenite as a co-product or by-product of emeralds small-scale mining, at the region of Campo Formoso and Pindobaçu, BA. The technological characterization of ores, products and the process used in the recovery of molybdenite from Campo Formoso has shown that barriers of technological nature, with emphasis on the produced concentrate, generate products of low molybdenite grade and, therefore, of low economic value. This is due to the presence, in particular, of other hydrophobic minerals, such as talc, with physical-chemical properties similar to those of molybdenite and are co-floated in the beneficiation process. Once detected the problem, and after an extensive literature survey on the subject, a fundamental study was carried out, in lab-scale, to separate molybdenite from talc by froth flotation, by testing different depressants conventionally used in actual mineral processing operations. Among the tested depressants, dextrin and quebracho promoted separation gaps between the molybdenite and talc minerals of 63 and 68%, respectively. The achieved results in that fundamental study has motivated an scale up from micro-flotation tests, in Partridge & Smith cell, to bench scale flotation tests in a Denver cell, reagents additions were calculated according to the ore (molybdenite concentrate) throughput into the industrial flotation circuits. In the bench scale flotation tests, the best results, in terms of molybdenite recovery, were reached by using dextrin as molybdenite depressant, at a dosage of 100 g.t-1, for a circuit with five cleaner steps. It was possible to get a molybdenite concentrate with 93.4% of MoS2, which is within the requirements of the international trade.

La microscopie à force atomique (AFM) dynamique est née il y a maintenant presque quinze ans (Albrecht, 1991). Depuis la première image en résolution atomique (F. J. Giessibl, 1995), les avancées de cette technique de champ proche permettent aujourd'hui de manipuler des atomes à température ambiante (Oyabu, 2005) sur des surfaces conductrices ou isolantes. La compréhension du fonctionnement de cette machine complexe et l'optimisation des réglages des nombreux asservissements est un des objectifs de ce travail de thèse. A cette fin, un formalisme analytique provenant des méthodes de l'Automatique non linéaire (J. Ch. Gille, 1956) sera introduit pour traiter de façon naturelle les blocs de régulation de la machine mais aussi pour traiter l'interaction pointe-surface comme une fonction de transfert. Un outil numérique de simulation confirmera notre approche théorique. Dans un deuxième temps, le rôle capital de la sonde et sa caractérisation seront traités à travers une méthode expérimentale simple et originale. Cette méthode se base sur l'étude des changements des propriétés de résonance de la sonde oscillante sur des surfaces isolantes et conductrices. Les forces conservatives à longue portée du type électrostatique et van der Waals seront quantifiées. Les forces à courte portée essentiellement chimiques seront mises en évidence en mesurant la dissipation de la sonde oscillante en fonction de sa distance avec la surface. Nous finirons cette étude en montrant expérimentalement, sur un sytème MoS2/îlots d'or/molécules d'octanedithiol, la grande versatilité de ce microscope. En effet, cet appareil d'observation par sa complexité apparente laisse beaucoup de degrés de liberté à l'utilisateur pour aborder l'étude d'un tel système physicochimique. Des perspectives seront données pour améliorer la stabilité et le pouvoir de résolution des pointes qui permettraient de rendre pérenne cette technique de champ proche.

Neste trabalho foram abordados aspectos da cadeia do molibdênio e da molibdenita nos mercados internacional e nacional, mostrando as ocorrências e suas principais aplicações. Atualmente, no Brasil, a única opção de aproveitamento econômico desse bem mineral é o minério de molibdenita gerado como coproduto ou subproduto da mineração artesanal de esmeraldas, na região de Campo Formoso e Pindobaçu, BA. A caracterização tecnológica de minérios, produtos e do processo utilizado na recuperação da molibdenita de Campo Formoso mostrou que entraves de natureza tecnológica, com destaque relacionado ao concentrado produzido, geram produtos de baixo teor e, consequentemente, de pequeno valor econômico. Isto é devido, principalmente, à presença de outros minerais hidrofóbicos, como o talco, com propriedades físico-químicas semelhantes às da molibdenita e que são co-flotados no processo de beneficiamento. Detectado o problema, e após uma revisão bibliográfica sobre o assunto, realizou-se um estudo fundamental, em escala de laboratório, sobre a separação molibdenita/talco por flotação, com a utilização de diferentes depressores empregados, usualmente, em operações de tratamento de minérios. Dentre os depressores utilizados, a dextrina e o quebracho promoveram janelas de separabilidade entre os minerais molibdenita e talco de 63 e 68%, respectivamente. Os resultados alcançados nesses estudos fundamentais motivaram um aumento de escala, passando dos testes de microflotação em célula Partridge & Smith, para testes de flotação em bancada em célula Denver, com as dosagens dos reagentes calculadas em termos de gramas de reagente por tonelada de alimentação à flotação (concentrado de molibdenita). Na flotação em escala de bancada, os melhores resultados foram obtidos com uso da dextrina como depressor da molibdenita, na dosagem de 100 g/t, para um circuito com cinco etapas de limpeza, foi possível obter um concentrado de molibdenita com 93,4% de MoS2, o qual encontra-se dentro dos requisitos exigidos pelo comércio internacional. / In this scientific and technological contribution, the aspects of the molybdenum and molybdenite chain in the domestic and international markets were discussed, showing the occurrences and their main applications. Currently, in Brazil the only option for the economic exploitation of this mineral resource is the molybdenite as a co-product or by-product of emeralds small-scale mining, at the region of Campo Formoso and Pindobaçu, BA. The technological characterization of ores, products and the process used in the recovery of molybdenite from Campo Formoso has shown that barriers of technological nature, with emphasis on the produced concentrate, generate products of low molybdenite grade and, therefore, of low economic value. This is due to the presence, in particular, of other hydrophobic minerals, such as talc, with physical-chemical properties similar to those of molybdenite and are co-floated in the beneficiation process. Once detected the problem, and after an extensive literature survey on the subject, a fundamental study was carried out, in lab-scale, to separate molybdenite from talc by froth flotation, by testing different depressants conventionally used in actual mineral processing operations. Among the tested depressants, dextrin and quebracho promoted separation gaps between the molybdenite and talc minerals of 63 and 68%, respectively. The achieved results in that fundamental study has motivated an scale up from micro-flotation tests, in Partridge & Smith cell, to bench scale flotation tests in a Denver cell, reagents additions were calculated according to the ore (molybdenite concentrate) throughput into the industrial flotation circuits. In the bench scale flotation tests, the best results, in terms of molybdenite recovery, were reached by using dextrin as molybdenite depressant, at a dosage of 100 g.t-1, for a circuit with five cleaner steps. It was possible to get a molybdenite concentrate with 93.4% of MoS2, which is within the requirements of the international trade.