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- Gahan, Chandra Sekhar
(författare)
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Possibilities to use industrial oxidic by-products as neutralising agent in bioleaching and the effect of chloride on biooxidation
- 2009
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- The cost for neutralisation is the second largest cost in a bioleaching operation for which, possibilities to replace generally used lime/limestone was tested. Industrial oxidic by-products generated form Swedish industries were investigated for neutralising capacities by chemical leaching with sulphuric acid at pH 1.5, which is the optimum pH for bioleaching operations. The by-products used for the study comprised of five different steel slags from ore and scrap based steel making, electric arc furnace (EAF) dust from scrap based steel plant, Mesalime from paper and pulp industry and three different types of ashes from combustion for energy production. All the by-products showed a good neutralising capacity, while some of them had higher capacities than the reference Ca(OH)2. Due to the good neutralising potential of the by-products obtained from the chemical leaching, attempts were made to use them as neutralising agent in batch bioleaching of pyrite in stirred tank reactor to determine their neutralising potential, eventual toxic effects on the microorganisms and pyrite oxidation. Pyrite oxidation in all the batch bioleaching was in the range of 69-80%, except the Waste ash experiment which was 59%. Neutralising capacity was high for all the by-products except Waste ash and Coal & Tyres ash compared to slaked lime. No remarkable toxic effects due to the by-products were observed except in the Waste ash experiment, which was probably due to the high content of chloride. To confirm if the chloride in the Waste ash caused any toxic effect on the bioxidation activity, batch bioleaching studies were conducted with Ca(OH)2 + NaCl as neutralizing agent with a similar chloride concentration profile obtained in the Waste ash experiment. Effect of the chloride on the biooxidation of pyrite by sudden exposure of 2 g/L, 3 g/L, and 4 g/L of chloride in the log phase of the biooxidation of pyrite was investigated. Addition of 2 g/L chloride resulted jarosite precipitation with a lower pyrite recovery than the reference experiment, whereas the addition of 3 g/L chloride temporarily chocked the microorganisms but activity was regained after a short period of adaptation. Population dynamics study conducted on the experiment with 3 g/L chloride showed the variation in the microbial species at different stages of the biooxidation of pyrite. The study with sudden exposure of 4 g/L of chloride was found to be lethal to the microbes. Out of all the by-products used in batch bioleaching studies, Mesalime and Electric Arc Furnace (EAF) dust were used as a neutralising agent in continuous biooxidation of refractory gold concentrate. The neutralising capacity of EAF dust was lower, while the Mesalime was similar to the Ca(OH)2 reference. The arsenopyrite oxidation in the experiments ranged from 85-90%, whereas the pyrite oxidation was 63-74%. In subsequent cyanidation 90% of the gold was achieved in the bioresidues from Mesalime and Ca(OH)2, while 85% of gold was recovered in bioresidue from EAF dust. A probable explanation for the low recovery of gold from the EAF dust experiment could be due to the encapsulation of the part of the gold by high elemental sulphur content present in the EAF dust. Cyanide consumption was relatively high and ranged from 8.1-9.2 kg/tonne feed after 24 hours of cyanidation. Both Mesalime and EAF dust proved to be feasible options as neutralising agents in bioleaching operations. Studies on the modelling of ferrous iron oxidation by a Leptospirillum ferriphilum-dominated culture was conducted with 9 g/L or 18 g/L ferrous iron in a chemostat. Modelling data suggested that the kinetics and yield parameters changed with the overall solution composition. The apparent Fe3+ inhibition on specific Fe2+ utilisation rate was a direct consequence of the declining biomass yield on the Fe2+ oxidation, when dilution rate was decreased. The maintenance activity contributed up to 90% of the maximum specific Fe2+ utilisation rate, which appears close to the critical dilution rate. Determination of the toxic limit of chloride were studied both in batch and chemostat conditions. Batch studies showed a toxic limit at 12 g/L chloride, while chemostat studies showed a toxic limit of 4 g/L. Modelling of the ferrous iron oxidation in chloride environment showed a decrease in maximum specific growth rate and increase in the substrate constant. The biomass concentration decreased with the increase in chloride concentration due to the toxic effect on the microorganisms. The maintenance coefficient decreased by 70% in the chloride environment.
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| 2. |
- Orrling, Diana, 1978-
(författare)
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Towards Abatement of Selected Emissions from Metals Manufacturing
- 2010
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Although the metallurgical industry has made great strides in the reduction of unwanted emissions to the atmosphere as a result of production processes, significant challenges still exist. From a global perspective, even large reductions in emissions per produced ton become immaterial when considering that the total world production of metals continues to increase. Two such particularly hazardous emissions are sulfur dioxide, primarily from copper ore roasting, and mercury, which has had increasing emissions from the steel industry in recent years. Both pollutants have severe consequences for the environment and also for human health. The primary motivations of this work have hence been: (1). to study sulfate formation on soot from sulfur dioxide emissions reacting with ozone and H2O in the vapor phase and (2). to study factors involving the behavior of mercury adsorption on metal surfaces involved in steelmaking, in order to further the understanding of select emissions from scrap-based steelmaking. Gas phase experiments were conducted to examine the heterogeneous oxidation of sulfur dioxide on soot in the presence of ozone and water vapor. The sulfur dioxide oxidation into sulfate was quantified using a particle-into-liquid sampler coupled with ion chromatography to measure the sulfate formation at atmospheric pressure. Water vapor, ozone and sulfur dioxide concentrations were controlled. Due to the ozone oxidation, multilayer adsorption of sulfur dioxide on soot, as well as sulfate formation and physisorption on secondary surface layer sites were observed. The exposure also caused the soot to become hydrophilic, due to the sulfur dioxide adsorption and also likely the formation of carboxyl groups on the surface. No significant increase in sulfate formation was observed at ozone concentrations above 1000 ppm. The effects of common surface contaminants such as oxygen and chlorine were examined on the metal surfaces, as well as the impact of changes in temperature, with controlled conditions using thermal desorption auger electron spectroscopy. It was established that low temperatures (82 K through 111 K) were conducive to mercury adsorption, wherein physisorption and subsequent lateral mercury interactions in mercury adlayers occurred. Chlorine appeared to favor mercury uptake, as determined by the increased mercury coverage at low temperatures on polycrystalline iron, copper and zinc. Oxygen, however, was found to be an inhibitor of mercury, most notably at room temperature. It was surprising to establish that no mercury adsorbed on zinc surfaces at room temperature and only on polycrystalline samples at low temperature. The mercury signal intensity increased up to the limit of the melting temperature for iron systems, on the oxidized copper surface and the polycrystalline zinc surfaces, prior to desorption from the surfaces. It is suggested that this is due to a rearrangement of mercury atoms on the surface at increasing temperatures, whereas at 85 K, mercury adhered to its initial adsorption position. In other words, mercury wet these surfaces on annealing, transitioning from an islanded surface at low temperature to a smooth layer before desorption. Based on these results, it was concluded that the mercury bond to the oxidized surface was weakened compared to clean copper. Furthermore, it is proposed that a surface phase transition occurred on polycrystalline zinc prior to desorption. No such transition was observed on iron. Activation energies of desorption were calculated for the relevant metal surfaces. It was established that clean iron had the highest activation energy of desorption. The large bond strength between mercury and iron may account for the highest desorption temperature of the iron systems. Zinc and copper had similar activation energies and desorption temperatures, which were respectively lower than that of iron. X-Ray Photoelectron and Auger Electron Spectroscopy were used to ascertain common surface contamination, i.e. chlorine, oxygen and sulfur, which affected mercury adsorption. Laser Ablation Inductively Coupled Plasma Time of Flight Mass Spectrometry was used to determine the depth of mercury adsorption on the samples. The technique also showed that the samples contained mercury in the surface layers. Accompanied by the rising demand for metals is the increase in emissions from metals manufacturing. Moreover, it is critical to minimize sulfur dioxide emissions as particulates from soot continue to be released in the atmosphere. For scrap-based steelmaking, monolayer mercury adsorption on clean iron and copper at room temperature are significant results. With the rising use of electronic devices in vehicles, the sorting of scrap becomes increasingly important. Mercury not adsorbing on zinc at room temperature is also of relevance as it disproves the theory of increased mercury adsorption with the increased use of galvanized scrap in summer conditions. However, the low temperature studies showed multilayer adsorption of mercury on iron, zinc and copper, which has relevance for the reported temporal variations of mercury deposition in arctic regions. Keywords: mercury, iron, zinc, sulfur dioxide, adsorption, pollution, thermal desorption, polycrystalline, surfaces, spectroscopy
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