The processing of nickeliferous laterites to produce nickel metal is both complex and energy intensive. Since most laterites are found in remote regions, the capital costs for the infrastructure can exceed those for the process itself. The low temperature sulphidation of lateritic ores to produce an intermediate nickel concentrate for further processing offers a number of potential advantages, such as lower energy consumption and a relatively simple flowsheet. In this research, the sulphidation of a nickeliferous lateritic ore was investigated between the temperatures of 450-1100oC and sulphur additions of between 25-1000 kg of sulphur per tonne of ore. The experiments demonstrated that the nickel oxide within the ore can be selectively sulphidized to a nickel-iron sulphide. It was found that both the grade and the sulphidation degree largely depended upon the temperature and the sulphur additions, with temperatures above 550oC exhibiting the highest nickel sulphidation extents and grades. A DTA/TGA with mass spectrometer was used to further elucidate the nature of the phase transformations that occur upon heating of the ore, in the presence of sulphur. It was found that the Fe-Ni-S phase formed at low temperatures was submicron in nature and heating to temperatures of 1050oC-1100oC allowed for the growth of the sulphides to a d80 of up to 14 µm due to increased sulphide mobility, associated with the formation of a liquid sulphide matte with dissolved oxygen. Flotation studies conducted on 60 g samples showed that the sulphides formed respond to flotation with maximum grades of up to 6-7 wt% nickel being achieved and average grades of between 4-5 wt% nickel. Recoveries were approximately 50% on a sulphide basis and it was determined that the low nickel grades were due to the entrainment of magnetite fines. / Thesis (Ph.D, Mining Engineering) -- Queen's University, 2012-01-29 14:14:18.704

The Alto Chicama district, Central Andean Cordillera Occidental, La Libertad, northern Perú, hosts the 14 M oz, Miocene Lagunas Norte high-sulphidation epithermal Au-(Ag) deposit (Latitude 7° 56ʹ30ʺ S; Longitude 78°14ʹ50ʺ W), in addition to several important, epithermal and mesothermal precious ± base-metal vein systems and porphyry Cu-Au-(Mo) deposits and prospects. The district is underlain by lower Oligocene-to-Middle Miocene, subaerial, Calipuy Supergroup volcanic rocks, unconformably overlying Upper Jurassic – Lower Cretaceous marine sedimentary strata affected by late Eocene-early Oligocene thin-skinned fold and thrust deformation. Mineralization at Lagunas Norte is largely hosted by intensely-folded Valanginian Chimú Formation quartz arenite, but extends into overlying, weakly-deformed, Lower Miocene dacitic volcaniclastic deposits. Fold- and thrust-related deformation at the deposit, and subsequent magmatic and hydrothermal activity, were localized along a long-lived, crustal-scale cross-strike discontinuity. Hydrothermal activity at Lagunas Norte was associated with local extension within an overall regional compressive regime. Ore formation occurred during the terminal stages of andesitic-to-dacitic magmatism in the deposit area, immediately following the sector collapse of an adjacent volcanic centre, and during eruption of late-stage peripheral dacitic domes. Intense advanced-argillic alteration occurred in at least two major pulses over a ~ 0.9 m.y. period, implying repeated magma influx in a shallow subjacent chamber. The ensuing Au-(Ag)-pyrite-enargite deposition resulted from mixing of magmatic vapour with oxidized groundwaters, a process stimulated by the contiguous incision of a steep-walled valley-pediment. The local volcanic rocks record a transition from “normal arc” to higher-pressure “adakitic” magmatism, initiated during ore deposition at Lagunas Norte, but exhibited by the entire Calipuy arc in northern Perú, and interpreted to reflect the destabilization of plagioclase and stabilization of garnet in inferred lower-crustal magmas. The progressive depletion of 18O and D in meteoric water recorded in late Oligocene-to-Late Miocene hypogene and supergene minerals is in permissive agreement with major uplift from ~ 1000 m to over 3000 m a.s.l. during hydrothermal activity. Hydrothermal activity and related ore deposition at Lagunas Norte unambiguously predated, by at least 2 m.y., the impingement of the aseismic Nazca Ridge at the Perú Trench and the ensuing flattening of the subducting slab / Thesis (Ph.D, Geological Sciences & Geological Engineering) -- Queen's University, 2012-04-05 11:09:14.751

Corrosion problems of copper waffle coolers are experienced in Platinum Group Metals (PGM’s) smelting furnaces. The copper cooler wear mechanism was studied through a post-mortem analysis of the refractory corrosion products that were removed from a PGM smelter. Post-mortem samples were characterised using Scanning Electron Microscopy (SEM), X-Ray Fluorescence Spectroscopy (XRF) and X-Ray Powder Diffraction (XRD). On visual inspection of the refractory wall it was observed that at the slag-feed interface the front refractory (mag-chrome) brick was completely corroded and only the freeze lining (frozen slag) formed a barrier between the copper cooler and the feed. At the bottom section of the slag zone the front refractory brick was still intact. Base metal sulphides and element sulphur were the major phases observed at the copper cooler-freeze lining interface while at the copper cooler-front brick interface only covellite (CuS) and element sulphur were observed. It was concluded that wear proceeded through two mechanisms: Reaction of copper with base metal sulphides which infiltrated the freeze lining and gaseous attach of copper by sulphur forming covellite. Front mag-chrome refractory bricks are replaced by graphite blocks in the latest furnace wall designs. A post-mortem graphite block was analysed with SEM, XRD and Inductively Coupled Plasma (ICP) to determine the phases associated with copper cooler corrosion. Base metal sulphides were observed at the copper cooler-graphite block (cold face) interface. Good agreement was found between the phases in the graphite block and the phases in the post-mortem sample where the refractory brick was used. Laboratory experiments were carried out to determine the effect of corrosive gas composition and copper cooler surface temperature on the corrosion rate and morphology of the corrosion products. Tests were performed on copper foils at temperatures from 80°C to 140°C. Corrosive gases included H2S, S2 and S2 with HCl. It was found that when a copper foil is exposed to sulphur the sulphides that form are covellite at 80°C, covellite and yarrowite (Cu9S8) at 110°C, yarrowite and digenite (Cu1.8S) at 140°C. Linear corrosion rate behaviour was observed between 80°C and 110°C since the sulphide scales are not passivating and they poorly adhere to the copper foil. Average corrosion rates of copper foil by sulphur vapour was 54 mm/y at 80°C and 80 mm/y at 110°C, above 112°C the corrosion rate decreased to 5 mm/y. Additions of HCl enhance the corrosion rate at temperatures above the melting point of sulphur (112°C). Chalcocite (Cu2S) forms when copper is exposed to H2S. It was concluded that the corrosion rate and the morphology of the corrosion product are functions of temperature and the corrosive gas composition. Copyright / Dissertation (MSc)--University of Pretoria, 2010. / Materials Science and Metallurgical Engineering / unrestricted

Nióbio e suas ligas são utilizados atualmente em muitas aplicações industriais por oferecerem excelente resistência à degradação em diversos meios corrosivos. Estes meios incluem atmosferas gasosas em temperaturas elevadas, como as encontradas em plantas de gaseificação de carvão existentes em usinas termelétricas para geração de energia. As atmosferas encontradas nestes meios são misturas gasosas complexasque contêm, entre outros compostos, oxigênio e enxofre. Os sulfetos são compostos menos estáveis, possuem pontos de fusão mais baixos e apresentam, freqüentemente, maiores desvios de estequiometria em relação ao óxido correspondente. Apesar de existirem estudos relacionados à aplicação de metais refratários em atmosferas sulfetantes a temperaturas elevadas, o uso de compostos de nióbio ainda não foi devidamente avaliado como revestimento protetor, havendo poucos dados disponíveis na literatura. O objetivo deste trabalho foi avaliar o efeito proporcionado por um filme de nióbio, obtido por pulverização catódica,sobre o comportamento de sulfetação isotérmica das ligas Fe-20Cr e Fe-20Cr-1Y.Os testes de sulfetação foram realizados a 500, 600 e 700°C pelo período de 2h em atmosfera H2/2%H2S. A avaliação da resistência à sulfetação foi feita por meio do ganho de massa por unidade de área exposta. Observou-se que o comportamento de sulfetação a 500ºC das ligas FeCr e FeCrY sem e com revestimento é similar. Nesta condição, nenhuma das ligas sofreu escamação. A 700ºC a liga FeCr sofreu leve escamação na forma de um pó fino, enquanto que o produto de reação formado sobre a liga FeCrY escamou na forma de placas. O efeito do nióbio se torna pronunciado a 700ºC. A camada de produto de reação formada sobre as ligas revestidas é mais fina e plástica que na liga sem revestimento. O ganho de massa por unidade de área diminuiu sensivelmente para as ligas recobertas, que não sofreram escamação. / Niobium and niobium based alloys are currently used in many industrial applications because they offer excellent resistance to degradation in various corrosive environments. These media include gaseous atmospheres at high temperatures such as those found in existing coal gasifying plants in power plants for energy generation. These atmospheres are complex gas mixtures that contain sulfur and oxygen, among other compounds. Sulphides are thermodynamically less stable, have lower melting points and often have larger deviations from stoichiometry compared to the corresponding oxides. Although there are studies regarding the use of refractory metals in high temperature sulphidizing atmospheres, the use of niobium compounds has not been adequately evaluated and there is very little studies available in the literature about its use as a protective coating. The aim of this study was to evaluate the effect of a niobium film, deposited by magnetron sputtering on the isothermal sulphidation behavior of Fe-20Cr and Fe-20Cr-1Y alloys. The sulphidation tests were carried out at 500, 600 and 700° C for 2h in H2/2% H2S atmosphere. The sulphidation resistance was determined by mass gain per unit area. The sulphidation behavior of the coated and uncoated alloys was similar at 500ºC, and none of the alloys spalled. At 700ºC FeCr alloy scalled in the form of a fine powder, while the reaction product formed on the alloy FeCrY scalled in the form of plates. The effect of niobium became pronounced at 700°C. The reaction product layer formed on the coated alloy was thinner andmore plastic than that formed on the uncoated alloy. The mass gain per unit area of the coated alloys decreased significantly and they did not scaled.

Nióbio e suas ligas são utilizados atualmente em muitas aplicações industriais por oferecerem excelente resistência à degradação em diversos meios corrosivos. Estes meios incluem atmosferas gasosas em temperaturas elevadas, como as encontradas em plantas de gaseificação de carvão existentes em usinas termelétricas para geração de energia. As atmosferas encontradas nestes meios são misturas gasosas complexasque contêm, entre outros compostos, oxigênio e enxofre. Os sulfetos são compostos menos estáveis, possuem pontos de fusão mais baixos e apresentam, freqüentemente, maiores desvios de estequiometria em relação ao óxido correspondente. Apesar de existirem estudos relacionados à aplicação de metais refratários em atmosferas sulfetantes a temperaturas elevadas, o uso de compostos de nióbio ainda não foi devidamente avaliado como revestimento protetor, havendo poucos dados disponíveis na literatura. O objetivo deste trabalho foi avaliar o efeito proporcionado por um filme de nióbio, obtido por pulverização catódica,sobre o comportamento de sulfetação isotérmica das ligas Fe-20Cr e Fe-20Cr-1Y.Os testes de sulfetação foram realizados a 500, 600 e 700°C pelo período de 2h em atmosfera H2/2%H2S. A avaliação da resistência à sulfetação foi feita por meio do ganho de massa por unidade de área exposta. Observou-se que o comportamento de sulfetação a 500ºC das ligas FeCr e FeCrY sem e com revestimento é similar. Nesta condição, nenhuma das ligas sofreu escamação. A 700ºC a liga FeCr sofreu leve escamação na forma de um pó fino, enquanto que o produto de reação formado sobre a liga FeCrY escamou na forma de placas. O efeito do nióbio se torna pronunciado a 700ºC. A camada de produto de reação formada sobre as ligas revestidas é mais fina e plástica que na liga sem revestimento. O ganho de massa por unidade de área diminuiu sensivelmente para as ligas recobertas, que não sofreram escamação. / Niobium and niobium based alloys are currently used in many industrial applications because they offer excellent resistance to degradation in various corrosive environments. These media include gaseous atmospheres at high temperatures such as those found in existing coal gasifying plants in power plants for energy generation. These atmospheres are complex gas mixtures that contain sulfur and oxygen, among other compounds. Sulphides are thermodynamically less stable, have lower melting points and often have larger deviations from stoichiometry compared to the corresponding oxides. Although there are studies regarding the use of refractory metals in high temperature sulphidizing atmospheres, the use of niobium compounds has not been adequately evaluated and there is very little studies available in the literature about its use as a protective coating. The aim of this study was to evaluate the effect of a niobium film, deposited by magnetron sputtering on the isothermal sulphidation behavior of Fe-20Cr and Fe-20Cr-1Y alloys. The sulphidation tests were carried out at 500, 600 and 700° C for 2h in H2/2% H2S atmosphere. The sulphidation resistance was determined by mass gain per unit area. The sulphidation behavior of the coated and uncoated alloys was similar at 500ºC, and none of the alloys spalled. At 700ºC FeCr alloy scalled in the form of a fine powder, while the reaction product formed on the alloy FeCrY scalled in the form of plates. The effect of niobium became pronounced at 700°C. The reaction product layer formed on the coated alloy was thinner andmore plastic than that formed on the uncoated alloy. The mass gain per unit area of the coated alloys decreased significantly and they did not scaled.

This report is intended to provide the reader with an extensive background information on hydrode oxygenation (HDO) of Tall Oil Pitch (TOP), combined with results from chemical property analyses of the same. Firstly, the importance of hydrogenation and oxygen removal for a biomass-based feed material is highlighted. The chemical nature of TOP in general is described and the target for the research work is identified. It is decided to evaluate the possibility of TOP as a prospective material for achieving partial oxygen removal. The effect of catalysis on HDO behavior is assessed, and subsequently, conventional commercial catalysts are selected. Chemical analyses of the feed mixture provided data on various properties, which can then be correlated to the products from hydrogenation. Kinematic viscosity of TOP is determined, followed by acid number and saponification number tests to evaluate the free acid and total acid contents respectively. Reasoning for any deviations are highlighted and suggestions are provided to control deviation in process parameters. GC/MS analysisof the tall oil sample is also conducted to understand the presence of oxygen-containing species. Carbon residue and ash tests revealed the coking and ash forming tendency of the samples. In addition, XRF spectroscopy results indicated the metal presence in the TOP sample. Experimental trials are carried out to sulphide the catalysts prior to use in hydrogenation experiments. Catalyst sulphidation procedure is also outlined. Furthermore, the lab-scale reactor is tested for hydrogenation to determine challenges that normally arise during high-pressure working conditions. In addition to discussion of challenges regarding batch hydrogenations and sulfidations, proposals on future work in this domain is outlined, along with suggestions on an experimental pathway forward.

The kinetics for sulphidation on a Ni-20 wt. % Cr alloy at 700ºC and sulphur potentials below 10⁻⁹ atmospheres have been studied using a thermogravimetric technique. The morphology of the reaction product was studied using optical microscopy, electron probe microanalysis and X-ray techniques. The kinetics were observed to be parabolic at sulphur potentials below 5 x 10⁻¹⁰ atmospheres with rates much slower than those reported for pure chromium under similar conditions. The parabolic kinetic reaction rate constant was found to vary as a semilogarithmic function of sulphur potential. The reaction product consisted of an external scale, identified as mainly Cr₃S₄, with dissolved nickel up to 5% and a subscale with morphological break-down of the alloy/external scale interface. Approximate determinations of the diffusivity of chromium in the alloy and the scale as well as sulphur diffusivity in the alloy have been made. Tentative mechanisms have been proposed to explain the diffusion control of the reaction and the stabilization of the external scale by dissolved nickel. / Thesis / Master of Engineering (ME)

A systematic in-depth study has been undertaken to establish the corrosion mechanism of a Model 25Cr-35Ni-Fe alloy and four commercial alloys HP40Nb, AISI314, HP40Al and Alloy 800H in low oxygen, high sulphur and carbon containing environments typically found in coal gasification and fluidised bed combustion processes. A review of present knowledge of corrosion processes in purely oxidizing, sulphidizing and carburizing environments and multiple reactant carburizing/ oxidizing, carburizing/sulphizing and oxidizing/sulphidizing environments is given. The experimental programme was designed to establish the role of sulphur on the corrosion process by studying corrosion mechanisms in a sulphurfree H2-7%C0-1.5%H2o gas, a low sulphur H2-7%C0-1.5%H20-0.2%H 2 S gas (pS2_8= 10 bar), and a high sulphur H 2 -7%C0-1.5%H 2 0-0.6%H 2 S gas (pS = lO bar) at 800'C. All_21j_hree environments had a constant partiaf pressure of oxygen (po2 = 10 bar) and carbon activity (ac = 0.3). In the sulphur-free gas the Model alloy formed a thin uniform cr 2 o 3 layer which grew at a constant parabolic rate throughout the exposure period of 0 - 5000 hours. Surface working increased the growth rate and thickness of the Cr 2 o 3 layer but created a large number of cracks and pores which allowed carbon containing gaseous species to diffuse through the oxide to form carbide precipitates in the alloy substrata. Alloying additions of Si promoted the formation of an inner SiO layer which reduced the corrosion rate by cutting off the outward diffusion of Cr, Mn and Fe. Alloying additions of Mn promoted the formation of an additional outer (Mn, Fe )Cr 2o 4 layer. The 3. 5% Al content of the HP40Al was insufficient to form a complete Al 2 o3 layer. Alloy 800H was susceptible to localised internal oxidation. Adding a low level of sulphur (0.2% H 2 S) to the gas increased the corrosion rate of the Model alloy in the 1nitial stages. This rate gradually slowed down before becoming parabolic after 1000 - 2000 hours. This was due to the nucleation of sulphides in addition to oxides. The oxides and sulphides grew side by side until the oxides overgrew the sulphides to form a complete Cr 2o3 layer which cut off further ingress of sulphur from the gas. The entrapped sulphides promoted localized thickening of the oxide layer. Eventually the sulphur redistributed from the sulphides in the scale to internal sulphide precipitates in the alloy with the corrosion rate returning to that of the sulphur-fre,e gas for the rest of the exposure period (5000 hours total). In the commercial alloys the internal sulphide precipitates prevented the inner Si02 layer becoming complete. Sulphur doped the (Mn, Fe) Cr 2 0 4 outer layer ana the intermediate Cr 2o3 layer formed from the spinal layer, increasing the number of cation . vacancies and the growth rate of the scale. These factors caused a massive Cr depletion of the alloy substrata after several thousand hours. The internal carbides became unstable which led to a massive amount of internal attack and a dramatic increase (breakaway) in the corrosion rate. Due to its thickness and the presence of Si02 inner layer the external scale became susceptible to spallation. If this occurred the oxides and sulphides nucleated on the alloy surface again but sulphides. protective alloy. insufficient Cr was available for the oxides to overgrow the The sulphides therefore grew to form a fast growing nonsulphide scale which soon led to catastrophic failure of the Increasing the level of sulphur in the gas to 0.6% H2S caused oxides and sulphides to nucleate on the surface, but in this case the sulphides overgrew the oxides to form thick fast growing non-protective sulphide scales on all the alloys.

Abstract The metamorphosed Palaeoproterozoic Orivesi gold deposit in southern Finland is located within the Tampere Schist Belt, which belongs to the Svecofennian domain. The Orivesi mine, run by Outokumpu Mining Oy, was in production from 1994 to 2003, during which time a total of approximately 1.7 million tons of ore was extracted, with an Au content of 9.31 g/t, implying a total output 13.115 tons of gold in concentrate. The hydrothermal alteration halo can be divided successively into chlorite-dominant, sericite-dominant and quartz-dominant rocks from the outer zone inwards. The host rocks of the ore are quartz rocks with andalusite-rich quartz rocks. Topaz-bearing rocks also occur in the inner part of the alteration halo. In addition to Au, the elements Ag, Te, Bi, Sb, S, As, Se, Cu, Zn, Pb, Sn and Mo are enriched to varying degrees within the alteration halo. The main ore minerals include base metal sulphides, sulphosalts and tellurides. Pyrite is the most common sulphide. The sulphosalts are represented by tetrahedrite, bournonite, boulangerite and meneghinite. The most common gold, gold-silver and silver tellurides are calaverite, montbrayite, petzite, kostovite, sylvanite and hessite. Other known tellurides include tellurobismuthite, altaite, melonite, frohbergite, tsumoite, tetradymite and rucklidgeite. Gold occurs mostly in fine-grained native grains containing an average of 5% Ag. The native gold is usually of very small grain size, generally < 20 µm. Most of the gold grains in the deposit occur as intergrowths with tellurides. The adjacent hypabyssal intrusion is an obvious source of both hydrothermal fluids and metals. A comb quartz layering has been discovered in the transition zone between the intrusion and the alteration halo. The Orivesi deposit is thought to belong to the high-sulphidation epithermal type. Soon after its formation the deposit encountered deformation and metamorphism that amounted to lower amphibolite facies conditions. The subsequent retrograde metamorphism caused the reappearance of some hydrothermal minerals typical of high-sulphidation epithermal deposits.