Isolamento do tungstênio da volframita da mina de Igarapé Manteiga (Rondônia - Brasil) por lixiviação ácida

We report results of the efficiency of tungsten extraction from wolframite concentrate (containing 61.5 wt % WO3) from the Igarapé Manteiga mine (state of Rondônia, Brazil) through acid leaching with strong mineral acids at 100 ºC and 400 rpm for 2-4 h. HCl yielded insoluble matter containing the highest WO3 content (90 wt %). This solid was dissolved in concentrated NH3(aq) at 25 ºC and the insoluble matter filtrated. The filtrate was slowly evaporated. 70 wt % of the tungsten present in the starting concentrate material was recovered as ammonium paratungstate (APT).

Harvinaisten metallien talteenotto epäorgaanisista jätevirroista

Taloudellisesti tärkeiden metallien varannot ja tuotanto eivät ole jakautuneet tasaisesti. Maantieteelliset alueet, joilla ei ole omia varantoja ovat riippuvaisia muualta tuoduista raaka-aineista. Euroopan komissio ja USA:n energiaministeriö ovat luokitelleet tietyt metallit kriittisiksi niiden taloudellisen merkittävyyden ja saatavuuteen liittyvien epävarmuustekijöiden johdosta. Tällaisten metallien saatavuutta voitaisiin mahdollisesti parantaa lisäämällä niiden talteenottoa jätteistä. Tutkimuksessa kartoitettiin Euroopan komission kriittiseksi luokittelemien metallien pitoisuuksia eräissä jätevirroissa. Kartoitetut jätteet olivat teollisissa poltto-prosesseissa syntyneitä polttojätteitä, prosessiteollisuuden jätesakkoja ja sähkö- ja elektroniikkajätteitä. Kartoituksen perusteella valittiin lupaavimmat jätteet ja suoritettiin niille talteenottokokeita. Talteenottokokeita suoritettiin kolmelle jätteelle. Yhdestä jätesakasta liuotettiin indiumia rikki- ja suolahapoilla. Kahden eri polttojätteen seoksesta liuotettiin galliumia rikkihapolla. Käytettyjen loisteputkien käsittelyprosessista peräisin olleesta sakasta liuotettiin maametalleja rikki- ja suolahapoilla sekä rikki- ja typpihapon seoksella. Indium liukeni heikosti (korkeintaan 25 %) huoneenlämmössä rikkihapolla. Suolahapolla se liukeni paremmin (68 %). Polttojätteen liuotuskokeissa galliumin talteenottoasteen todettiin riippuvan käytetyn liuottimen määrästä. Loisteputkijätesakasta liukeni yttriumia ja europiumia kaikilla käytetyillä happoliuoksilla noin 70–100 %. Käytetyillä happokonsentraatioilla ei havaittu suuria eroja yttriumin ja europiumin liukoisuuksissa. Näitä metalleja voitaisiin mahdollisesti ottaa talteen tämän tyyppisestä sakasta liuottamalla ne happoliuoksella ja saostamalla oksalaattina. Tarvittaessa liuokset voitaisiin puhdistaa tai metallit erottaa toisistaan neste–nesteuutolla, joka on tärkein maametallien tuotantoon käytetty hydrometallurginen menetelmä.

Estudo comparativo entre a pirólise do polietileno de baixa densidade, utilizando vermiculita modificada e SBA-15

Catalytic processes are widely present in everyday life. This results in large number of studies seeking materials that may combine the low cost catalytic efficiency. Based on this assumption, the clays have long been used as catalysts, with its huge availability, diversity and possibility of improving their properties from structural changes, primarily responsible for this great use. Among the natural clays, vermiculite due to their characteristic properties (high cation exchange capacity and expansion), is suitable for various applications including as catalysts and catalyst supports. In this work, the acid leaching of clay vermiculite was performed, coming from Santa Luzia-PB, with nitric acid (2, 3 and 4 mol / L) and subsequent calcination of the materials obtained. The materials were named as Vx/400, where x is the acid concentration employed and 400 used in calcination temperature. The effectiveness of changes made was determined by XRD techniques, FT-IR, EDS, TG/DTG, nitrogen physisorption and DTP of n-butylamine. Acid leaching has improved some properties of the clay - specific area and acidity - but the control of the acid concentration used is of vital importance, since the highest concentration caused the partial destruction of vermiculite entailing a decline in their properties. For analysis of the catalytic activity of the modified clay was made a comparative study with the SBA -15 mesoporous materials, synthesized via hydrothermal method, using the pyrolysis of low density polyethylene (LDPE). The results showed that the acid plays a fundamental role in the conversion of the polymer into smaller molecules, the material V3/400 was more selective for the source monomer (ethylene) due to their increased acidity, which promotes more breaks bonds in the polymeric chain, while materials and V0/400 V2/400, lower acidity, showed higher selectivity to light hydrocarbons, the range of fuel (41.96 and 41.23%, respectively), due to less breakage and secondary condensation reactions chains; already V4/400 SBA-15/550 and resulted in lower percentages of light hydrocarbons and the partial destruction of the structure and low acidity, respectively, responsible for the inefficiency of materials

Recuperação de níquel e outros metais a partir de diferentes fontes (rejeitos minerais de processo industrial e pentlandita '(Ni,Fe)IND. 9' 'S IND. 8' ) mediante lixiviação ácida e bacteriana

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Estudo hidrometalúrgico de compostos de titânio proveniente do resíduo do processo Bayer

Estudos realizados no resíduo do processo Bayer, lama vermelha, para reciclagem desse material têm sido intensificados por suas características físico-químicas. O resíduo é constituído por inúmeros óxidos, destes se destaca o óxido de ferro em teores acima de 30% em peso e óxido de titânio em concentrações acima de 5% em peso. Este trabalho estuda a possibilidade de extrair óxido de ferro, objetivando a concentração de compostos de titânio. A extração foi realizada através do processo de calcinação da lama vermelha a 900°C seguida de lixiviação ácida com concentração de H2SO4 a 20% e 30% em volume a 60°C, 80°C e 90°C, com retirada de uma alíquota a cada 30 minutos. Durante o processo de lixiviação, foi observada extração intensa dos compostos de ferro, resultando no aumento da concentração de titânio na lama vermelha, verificado em todos os experimentos, com destaque para os que foram realizados a 90°C e H2SO4 a 30% em v/v, onde houve extração de 95% de ferro e concentração de até 14% de titânio considerando o balanço de massa global. Diante dos dados obtidos, a lama vermelha torna-se um material interessante para ser utilizado como fonte alternativa para obtenção de minerais de titânio, os quais são encontrados na natureza com um percentual em torno de 8%.

Poly(2,5-bibenzimidazole) Membranes: Physico-Chemical Characterization Focused on Fuel Cell Applications

Membranes of Poly(2,5-benzimidazole) (ABPBI), prepared by polycondensation in polyphosphoric acid, were characterized from the fuel cell application point of view: mechanical properties of the membranes for different acid doping levels, thermal stability, permeability for the different gases/vapors susceptible of use in the cell (hydrogen, oxygen, methanol and ethanol), electro-osmotic water drag coefficient, oxidation stability to hydroxyl radicals, phosphoric acid leaching rate and, finally, in-plane membrane conductivity. ABPBI membranes presented an excellent thermal stability, above 500 degrees C in oxygen, suitable mechanical properties for high phosphoric acid doping levels, a low methanol and ethanol limiting permeation currents, and oxygen permeability compared to Nafion membranes, and a low phosphoric acid leaching rate when exposed to water vapor. On the contrary, hydrogen permeation current was higher than that of Nafion, and the chemical stability was very limited. Membrane conductivity achieved 0.07 S cm(-1) after equilibration with a humid environment. Fuel cell tests showed reasonable good performances, with a maximum power peak of 170 mW cm(-2) for H-2/air at 170 degrees C operating under a humidified hydrogen stream, 39.9 mW cm(-2) for CH3OH/O-2 at 200 degrees C for a methanol/water weight ratio of 1: 2, and 31.5 mW cm(-2) for CH3CH2OH/O-2 at the same conditions than for methanol. (C) 2012 The Electrochemical Society. [DOI: 10.1149/2.014207jes] All rights reserved.

HCl gas gettering of 3d transition metals for crystalline silicon solar cell concepts

In order to reduce the costs of crystalline silicon solar cells, low-cost silicon materials like upgraded metallurgical grade (UMG) silicon are investigated for the application in the photovoltaic (PV) industry. Conventional high-purity silicon is made by cost-intensive methods, based on the so-called Siemens process, which uses the reaction to form chlorosilanes and subsequent several distillation steps before the deposition of high-purity silicon on slim high-purity silicon rods. UMG silicon in contrast is gained from metallurgical silicon by a rather inexpensive physicochemical purification (e.g., acid leaching and/or segregation). However, this type of silicon usually contains much higher concentrations of impurities, especially 3d transition metals like Ti, Fe, and Cu. These metals are extremely detrimental in the electrically active part of silicon solar cells, as they form recombination centers for charge carriers in the silicon band gap. This is why simple purification techniques like gettering, which can be applied between or during solar cell process steps, will play an important role for such low-cost silicon materials. Gettering in general describes a process, whereby impurities are moved to a place or turned into a state, where they are less detrimental to the solar cell. Hydrogen chloride (HCl) gas gettering in particular is a promising simple and cheap gettering technique, which is based on the reaction of HCl gas with transition metals to form volatile metal chloride species at high temperatures.rnThe aim of this thesis was to find the optimum process parameters for HCl gas gettering of 3d transition metals in low-cost silicon to improve the cell efficiency of solar cells for two different cell concepts, the standard wafer cell concept and the epitaxial wafer equivalent (EpiWE) cell concept. Whereas the former is based on a wafer which is the electrically active part of the solar cell, the latter uses an electrically inactive low-cost silicon substrate with an active layer of epitaxially grown silicon on top. Low-cost silicon materials with different impurity grades were used for HCl gas gettering experiments with the variation of process parameters like the temperature, the gettering time, and the HCl gas concentration. Subsequently, the multicrystalline silicon neighboring wafers with and without gettering were compared by element analysis techniques like neutron activation analysis (NAA). It was demonstrated that HCl gas gettering is an effective purification technique for silicon wafers, which is able to reduce some 3d transition metal concentrations by over 90%. Solar cells were processed for both concepts which could demonstrate a significant increase of the solar cell efficiency by HCl gas gettering. The efficiency of EpiWE cells could be increased by HCl gas gettering by approximately 25% relative to cells without gettering. First process simulations were performed based on a simple model for HCl gas gettering processes, which could be used to make qualitative predictions.

Isotope geochemistry of Ninetyeast Ridge basalts

The Ninetyeast Ridge lavas have Sr and Nd isotopic ratios intermediate between those of Indian Ocean MORBs and those of the very enriched Kerguelen hot spot. In an Nd-Sr isotope diagram, they also plot close to the fields of St. Paul Island lavas and of the early magmatism on Kerguelen Archipelago. The Ninetyeast Ridge lavas were generated by mixing among at least three components: a depleted, MORB-type component, such as the one erupted today on the Southeast Indian Ridge; a very enriched, high- Sr/ Sr, low-epsilon-Nd, OIB-type component (the Kerguelen hot spot); and an OIB-type component comparable to that sampled from the St. Paul (and Amsterdam) lavas. The Ninetyeast Ridge lavas show a typical Dupal anomaly signature and Pb, Sr, and Nd isotopic systematics indicate that the Kerguelen hot spot was involved in the ridge's formation as the Indian plate moved northward. The different sites cored during ODP Leg 121 show a trend in their isotopic compositions, from less radiogenic Pb/ Pb ratios and intermediate 87Sr/86Sr and 143Nd/**Nd ratios in the oldest lavas (Site 758) toward more radiogenic 206Pb/204Pb, higher epsilon-Nd, and lower 87Sr/86Sr values in the youngest lavas (Site 756). The lavas from Site 757 have 206Pb/204Pb ratios intermediate between those of the lavas from Sites 756 and 758 and higher 87Sr/86Sr and lower epsilon-Nd values. The relative proportions of the hot spot(s) and MORB component have evolved with time, reflecting differences of tectonic setting: the relative proportion of the Kerguelen hot spot component appears lower in the younger Site 756 lavas than in the older lavas from Sites 757 and 758. Site 756 coincides with the beginning of rifting at the Southeast Indian Ridge, about 43 Ma ago. The formation of the early Kerguelen Archipelago lavas may have drained most of the plume-derived material toward the Antarctic plate. Alternatively, the proximity of the spreading-ridge axis may account for the isotopic similarity of the Site 756 lavas to young lavas erupted on the Southeast Indian Ridge, from 33? to 37?S. The older lavas of Ninetyeast Ridge may have formed when the hot spot and ridge axis did not exactly coincide. The involvement of the third component, a St. Paul hot spot, in the genesis of the Ninetyeast Ridge lavas, especially for the Site 756 lavas, is clearly indicated by Sr, Pb, and Nd isotope systematics and also by trace element ratios. These data, together with those from the Kerguelen Plateau, indicate that the Kerguelen hot spot has been active more or less continuously in the South Indian Ocean for at least 115 Ma. This could indicate that the plume, and by inference the Dupal anomaly, is deep seated in origin.

Strontium and Oxygen isotope compositions from DSDP Holes 54-424A, 54-424B and 70-509B

Strontium and O isotope compositions of green clay minerals from sediment cores of three boreholes drilled into (sites 424A and 509B) and close to a hydrothermal mound (site 424B) near the Galapagos Spreading Center (DSDP Legs 54 and 70) were determined. The green clays consist mostly of a transition from Fesmectite (nontronite) to glauconite. 87Sr/86Sr ratios were measured on clay size-fractions after gentle acid leaching and on the recovered leachates from different samples. The 87Sr/86Sr ratios of the clay residues from both the 424A and B sites are well below the modern seawater value, which points consistently to precipitation from hydrothermal fluids that contained variable amounts of seawater, even away from mound. However, most of the clay residues from mound site 509B have 87Sr/86Sr ratios significantly above the seawater value, suggesting the occurrence of a detrital component together with the new authigenic particles. The clay minerals of the hydrothermal mound are mixed with detrital components, and that of the sample taken outside but near the mound as a reference for the surrounding oceanic environment, yields a hydrothermal signature. Crystallization temperatures of the clays range from 32 to 63 °C assuming a d18O value of +2.2 per mil for the mineralizing fluids. Hydrothermal fluids generated in the underlying oceanic crust, mixed in varied proportions with ambient seawater and migrated into beds of the mound in a sequence of recurrent processes that ultimately resulted in the formation of the observed clay minerals. No significant temperature differences were detected for crystallization of the K-rich glauconite and K-depleted nontronite. The 87Sr/86Sr ratios of the Sr leached off the clay particles are near the value of modern seawater, inferring a progressive replacement of the hydrothermal fluids by seawater in the pore space of the mound sediments.

Diurnal and seasonal measurements of seawater chemistry, temperature and PAR in Hurricane Hole, U.S. Virgin Islands - 2010-2012

Risk analyses indicate that more than 90% of the world's reefs will be threatened by climate change and local anthropogenic impacts by the year 2030 under "business-as-usual" climate scenarios. Increasing temperatures and solar radiation cause coral bleaching that has resulted in extensive coral mortality. Increasing carbon dioxide reduces seawater pH, slows coral growth, and may cause loss of reef structure. Management strategies include establishment of marine protected areas with environmental conditions that promote reef resiliency. However, few resilient reefs have been identified, and resiliency factors are poorly defined. Here we characterize the first natural, non-reef coral refuge from thermal stress and ocean acidification and identify resiliency factors for mangrove-coral habitats. We measured diurnal and seasonal variations in temperature, salinity, photosynthetically active radiation (PAR), and seawater chemistry; characterized substrate parameters; and examined water circulation patterns in mangrove communities where scleractinian corals are growing attached to and under mangrove prop roots in Hurricane Hole, St. John, US Virgin Islands. Additionally, we inventoried the coral species and quantified incidences of coral bleaching, mortality, and recovery for two major reef-building corals, Colpophyllia natans and Diploria labyrinthiformis, growing in mangrove-shaded and exposed (unshaded) areas. Over 30 species of scleractinian corals were growing in association with mangroves. Corals were thriving in low-light (more than 70% attenuation of incident PAR) from mangrove shading and at higher temperatures than nearby reef tract corals. A higher percentage of C. natans colonies were living shaded by mangroves, and no shaded colonies were bleached. Fewer D. labyrinthiformis colonies were shaded by mangroves, however more unshaded colonies were bleached. A combination of substrate and habitat heterogeneity, proximity of different habitat types, hydrographic conditions, and biological influences on seawater chemistry generate chemical conditions that buffer against ocean acidification. This previously undocumented refuge for corals provides evidence for adaptation of coastal organisms and ecosystem transition due to recent climate change. Identifying and protecting other natural, non-reef coral refuges is critical for sustaining corals and other reef species into the future.

Avaliação da influência do efeito de ultrassom na lixiviação de metais de placas de circuito impresso obsoletas.

Os equipamentos elétricos e eletrônicos (EEE) possuem uma grande importância na sociedade contemporânea, e estão presentes no cotidiano das pessoas de forma ubíqua. Com o aumento no consumo de EEE juntamente com a obsolescência precoce, surge um novo tipo de resíduo, chamado de Resíduos de Equipamentos Elétricos e Eletrônicos (REEE). Os REEE não devem ser descartados em aterros, pelo risco de contaminação e pelo desperdício de material. Assim, a reciclagem se faz necessária. As placas de circuito impresso (PCI) estão presentes na grande maioria do REEE e contem a maior variedade de metais, incluindo metais valiosos como Au, Ag, Pt e Cu. A complexidade torna a reciclagem destas placas muito difícil. Rotas hidrometalúrgicas tem surgido como uma alternativa mais limpa para o tratamento de PCI, em detrimento aos processos pirometalúrgicos. Nas rotas hidrometalúrgicas, os metais são extraídos pela lixiviação realizada por ácidos ou bases. O efeito ultrassônico tem sido empregado na síntese de novas substâncias e também em alguns casos no tratamento de resíduos. O processo central no uso de ultrassom é a cavitação acústica, capaz de produzir microbolhas na solução com temperatura da ordem de 5000 K e pressão de 500 atm localmente. Além disto, a implosão das bolhas de cavitação em meio heterogêneo causa um jato de solução na superfície, que pode alcançar velocidade de 100 m.s-1. Assim, esta tese tem como objetivo a investigação do efeito do ultrassom sobre PCI obsoletas. Dois efeitos foram investigados: o efeito da cominuição das PCI promovido pela cavitação e a influência da cavitação na lixiviação com ácido sulfúrico de Fe, Al e Ni. Os parâmetros investigados na cominuição foram: tipo de placa, granulometria da placa moída e potência de ultrassom. Os parâmetros de lixiviação avaliados foram: razão sólido-líquido (S/L), concentração de ácido e potência de ultrassom. Também foram realizados ensaios de lixiviação sonicados com meio oxidante. Foi feita a análise cinética para se determinar qual é o controle da reação de lixiviação.

Reciclagem de resíduos eletroeletrônicos: um estudo cinético da lixiviação ácida de ferro de placas de circuito impresso de microcomputadores.

O aumento no consumo mundial de novos aparelhos eletroeletrônicos aliado à redução no tempo de vida útil destes equipamentos tem como principal consequência ao meio ambiente a geração de resíduos. No Brasil, com a instituição da Política Nacional de Resíduos Sólidos, criou-se a obrigatoriedade legal da responsabilidade dos fabricantes pela logística reversa dos equipamentos eletroeletrônicos, incentivando pesquisas para o desenvolvimento dos métodos de reciclagem e tratamento dos materiais descartados. O processo de lixiviação foi avaliado como alternativa à etapa de separação magnética presente nas atuais rotas hidrometalúrgicas para recuperação de metais valiosos de placas de circuito impresso. Para avaliar a composição das placas, foi realizado ensaio de dissolução em água régia. As amostras foram moídas e submetidas a ensaios de lixiviação com ácido sulfúrico nas concentrações de 1 e 2mol/L, às temperaturas de 75ºC, 85ºC e 95ºC, durante 24 horas. Com ácido sulfúrico 2mol/L a 95ºC, o tempo necessário para se obter 100% de extração do ferro foi de 2 horas. Nestas condições, não foi detectada a presença de cobre dissolvido. A cinética da reação é controlada por reação química e obedece a equação .=1(1)3. A energia de ativação aparente do processo equivale a 90kJ/mol.

Estudo cinético da lixiviação de metais de placas de circuito impresso obsoletas.

O processo tradicional de recuperação de metais de resíduos de equipamentos eletroeletrônicos (REEE) geralmente envolve processamento pirometalúrgico. Entretanto, o uso desta tecnologia para processar placas de circuito impresso (PCI) obsoletas pode levar à liberação de dioxinas e furanos, devido à decomposição térmica de retardantes de chama e resinas poliméricas presentes no substrato das placas. Portanto, este trabalho propõe uma rota hidrometalúrgica para recuperação de metais. O comportamento dos metais, com destaque para cobre, zinco e níquel, durante a lixiviação ácida, foi estudado em três temperaturas diferentes (35ºC, 65ºC e 75ºC), com e sem adição de um agente oxidante (peróxido de hidrogênio H2O2). A cinética de dissolução ácida desses metais foi estudada baseada na análise química por ICP-OES (Espectrometria de emissão ótica por plasma acoplado indutivamente) e EDX (Espectroscopia de fluorescência de raios-X por energia dispersiva). O balanço de massa e a análise química indicaram que a etapa de lixiviação sem adição de oxidante é pouco eficaz na extração dos metais, sendo responsável pela dissolução de menos do que 6% do total extraído. A 65ºC e H2SO4 1 mol/L, com adição de 5 mL de H2O2 (30%) a cada quinze minutos e densidade de polpa de 1 g / 10 mL, 98,1% do cobre, 99,9% do zinco e 99,0% do níquel foram extraídos após 4 horas. A cinética de dissolução desses metais é controlada pela etapa da reação química, seguindo, dependendo da temperatura, a equação 1 (1 XB)1/3 = k1.t ou a equação ln (1 XB) = k4.t.

Isotopic geochemistry of lavas at DSDP Holes 81-553 and 81-555

It is demonstrated by K-Ar analyses that the age of reversely magnetized basalts, which immediately predate magnetic Anomaly 24B, is 53.5 ± 1.9 m.y. Samples from deep levels appear to be grossly contaminated by an extraneous argon component with a uniform argon-40/argon-36 ratio 440. This component is thought to have been derived from fluids circulating in the lava pile during burial. The age result corroborates the assignment previously made to Anomaly 24B by Hailwood et al. (1979) and Lowrie and Alvarez (1981). It additionally suggests that lava extrusion formed part of a much larger magmatic event, which affected wide areas of the North Atlantic margins around the Paleocene/Eocene boundary, and can therefore probably be considered a good estimate of the age of this boundary. Initial 143Nd/144Nd ratios lie in the very restricted range 0.512920 ± 19 to 0.513026 ± 24 and initial 8 7Sr/86Sr ratios from ca. 0.703 to ca. 0.705. Acid leaching reduces the latter range to 0.70264 ± 4 to 0.70384 ± 4, suggesting that the higher 87Sr/86Sr ratios resulted from interaction with seawater. The array of data for treated samples is closely conformable on a 143Nd/144Nd-87Sr/86Sr diagram with the main oceanic mantle array and with previously published fields for Atlantic Ocean basalts. No evidence for any continental crustal contamination has been found. This suggests, but does not prove, that continental crust played no part in the genesis of these rocks.