This study investigated the effect of excess carbon loading in the anoxic reactor on the nitrogen removal capacity of a biological pre-denitrification system for the treatment of a high ammonia leachate. The influent leachate was low in degradable organic carbon, thus an external carbon source was needed for denitrification requirements. Four different carbon sources were studied: methanol, glucose, acetate, and a waste brewer's yeast. The carbon loading was increased over the duration of the experimental period. The COD:NOx added to the anoxic reactor reached more than three times the carbon loading required to just achieve complete denitrification. All four carbon sources were found to support denitrification, but the glucose system showed erratic behaviour and ultimately failed after reaching a CODrNOx loading of about 23:1. The system using acetate appeared to require the least amount of COD:NOx (5.9:1) for complete denitrification, followed closely by methanol (6.2:1), then the yeast waste (8.5:1), and finally by glucose (9:1). Carbon breakthrough, the bleeding of carbon from the anoxic reactor into the aerobic reactor, was observed to occur just after complete denitrification was reached. The excess carbon did not appear to have any effect on denitrification, except in the case of the glucose system. The unit nitrification was found to decrease as the CODrNOx was increased, even though the ammonia removal remained at 100%. The decrease in nitrification, with respect to the COD:NOx, was most pronounced in the system that used methanol, and about equal in the other three systems. The cause of the decrease in nitrification is suspected to be due to increased ammonia assimilation by the heterotrophs rather than an inhibition of the nitrifiers. Nitrification ceased in the glucose system, but was restored within 12 days after the glucose addition was halted. The cause of the failure of the nitrogen removal process in the glucose system was not determined. Nitrite accumulation was observed in all the systems except the methanol system. The yeast waste system had nitrite accumulation in the aerobic reactor at C0D:N0x loadings over 25:1. Free ammonia inhibition of Nitrobacter is suspected to be the cause of aerobic nitrite buildup. The glucose and acetate systems had nitrite buildup in the anoxic reactor until complete denitrification was achieved. Facultative anaerobic bacteria are suspected of causing this nitrite accumulation. This theory was supported by observations in the glucose system, such as low anoxic pH; this may have been due to volatile fatty acids produced from fermentation. / Applied Science, Faculty of / Civil Engineering, Department of / Graduate

No description available.

Excess nitrate-N concentration (>10 mg L-1) in drinking water can cause significant risk to human health. Also, at very low concentration (0.035-0.1 mg P L-1), phosphorus is considered as a pollutant due to its effects of promoting algal growth and eutrophication of surface waters. This thesis’ research was conducted at two different sites. The first study was conducted at Carman on a sandy loam soil with cropping system, perennial versus annual, as the main plot and manure nutrient management system, as the subplot to measure nitrate and phosphorus leaching from hog manures. The second field experiment, located northwest of the town of Carberry, Manitoba, was conducted on a loamy sand soil. A two year rotation was employed for the annual cropping systems with a randomized complete block design. Treatments included two rates of liquid hog manure (LH-5000, LH-2500), two rates of fertilizers (F5000, F2500) corresponding to the amount of available nitrogen in the two rates of hog manure a compost treatment (Com-2500) and a control for a total of six treatments. The results from Carman site showed that while a substantial amount of nitrate-nitrogen was lost from the annual plots (40 to 60 kg ha-1 in 2010 and 23 to 60 kg ha-1 in 2011), a negligible amounts of nitrate was lost from the perennial (< 1 kg ha-1). There was no evidence of significant downward movement of phosphorus below the top 15 cm soil layer in this study. However, repeated, annual application of manure at an N-based rate resulted in increased soil test P. In Carberry, total N leaching of fertilizer amended plots was greater than in plots that received manure. Based on the results, application of liquid hog manure at the rate of 2500 gallon ac-1 was economically and environmentally more desirable and is recommended. We applied the multi-layer water balance model, VSMB, to the data that we generated in the field to gain an understanding of how well the model will simulate the loss of water that we measured from the lysimeters. The simulation study showed that the VSMB model grossly underestimated the amount of leached water, possibly due to an overestimation of evapotranspiration. / October 2015

No description available.

No description available.

The present work, where additional value-creating processes in existing combined heat and power (CHP) structures have been examined, is motivated by a political- and consumer-driven strive towards a bioeconomy and a stagnation for the existing business models in large parts of the CHP sector. The research is based on cases where the integration of flash pyrolysis for co-production of bio-oil, co-gasification for production of fuel gas and synthetic biofuels as well as leaching of extractable fuel components in existing CHP plants have been simulated. In particular, this work has focused on the CHP plants that utilize boilers of fluidized bed (FB) type, where the concept of coupling a separate FB reactor to the FB of the boiler forms an important basis for the analyses. In such dual fluidized bed (DFB) technology, heat is transferred from the boiler to the new rector that is operating with other fluidization media than air, thereby enabling other thermochemical processes than combustion to take place. The result of this work shows that broader operations at existing CHP plants have the potential to enable production of significant volumes of chemicals and/or fuels with high efficiency, while maintaining heat supply to external customers. Based on the insight that the technical preconditions for a broader operation are favourable, the motivation and ability among the incumbents in the Swedish CHP sector to participate in a transition of their operation towards a biorefinery was examined. The result of this assessment showed that the incumbents believe that a broader operation can create significant values for their own operations, the society and the environment, but that they lack both a strong motivation as well as important abilities to move into the new technological fields. If the concepts of broader production are widely implemented in the Swedish FB based CHP sector, this can substantially contribute in the transition towards a bioeconomy. / Bioeconomy has been identified to hold a great potential for reducing fossil fuel dependence and for maintaining and creating economic growth. Large parts of the combined heat and power (CHP) sector, which successfully have contributed in the transition towards a fossil free society, are at present facing stagnation. District heating actors are facing challenges due to warmer climate, better insulated buildings and competition from heat pumps. The forest industry where CHP plants supplies processes with heat is facing structural changes foremost in the graphic segments. The emerging bioeconomy and the stagnation for the existing business models in large parts of the CHP sector form the background for the examination of additional value-creating processes in the existing CHP structure presented in this thesis. The technical viability for integration of fast pyrolysis, gasification and leaching with existing CHP plants has been analysed as well as the motivation and ability of the CHP incumbents to participate in a transition towards the bioeconomy by developing their plants to biorefineries.

M.Sc. / The leaching of chalcopyrite (CuFeS2) concentrate in a ferrous iron promoted aerobic/anaerobic controlled low potential sulphate system was investigated by using the duel metabolic (aerobic ferrous iron oxidation and anaerobic ferric iron reduction) capabilities of Ferroplasma JTC 3. The experimental work conducted in this study was divided in three sections. The first section focussed on the identification and phylogenetic classification of Ferroplasma JTC 3, first identified amongst a mixed microbial population in a 55 oC pyrite concentrate-fed bioreactor operated at Johannesburg Technology Centre (BHP Billiton, JTC). Based on the 16S rDNA sequence and the phylogenetic analysis, Ferroplasma JTC 3 represents a new species member under the genus of Ferroplasma. The optimal growth temperature of Ferroplasma JTC 3 was determined at approximately 53 oC (moderate thermophile). The second section of this study focussed on the isolation, basic metabolism and growth conditions of Ferroplasma JTC 3, specifically directed towards the chalcopyrite leaching related experimental work. An important aspect of this study was to compare low potential chalcopyrite leaching (potential below 400 mV vs. Ag/AgCl) against high potential chalcopyrite bioleaching (potential above 600 mV vs. Ag/AgCl) in terms of the rate of copper extraction. Microbial growth and the rate of ferrous iron oxidation are essential in order to maintain a high potential during an extended leach period, which was typically the case in the high potential chalcopyrite leaching experiments performed during this study. Ferroplasma JTC 3 required yeast extract as sole carbon source (chemo-heterotrophic) for growth via aerobic ferrous iron oxidation. Taking into account no carbon dioxide enrichment via aeration, chemo-autotrophic growth by means of ferrous iron oxidation was poor with carbon dioxide as sole carbon source. The anaerobic metabolism of Ferroplasma JTC 3 was utilized in assisting with solution potential control during the low potential chalcopyrite leaching work. The anaerobic metabolism enabled the reduction of ferric iron (decrease redox potential) in the presence of elemental sulphur and yeast extract. Elemental sulphur was shown to be a requirement for Ferroplasma JTC 3 assisted ferric iron reduction, which was not influenced by different ferrous/ferric iron based redox potentials. The third section covers the main focus of this study, which was the low potential leaching of chalcopyrite in combination with the metabolic capabilities of Ferroplasma JTC 3. The major challenge of low potential chalcopyrite leaching in an acidic environment is maintaining the solution potential below the critical upper limit (400 mV vs. Ag/AgCl) of the low potential window for prolonged periods of time. The reason is the slow chemical oxidation of ferrous iron in the presence of oxygen, which increases the leach solution potential above the critical upper limit before complete copper dissolution is obtained. The aim of this study was to maintain a low solution potential environment in a bioreactor via a programmable electronic gas control system, capable of creating an aerobic environment until the solution potential would reach the upper low potential limit (400 mV vs. Ag/AgCl) due to ferrous iron oxidation (chemically or via Ferroplasma JTC 3) and then switch to an anaerobic environment. During the anaerobic environment, the aim was to decrease the solution potential to a lower potential set point via chalcopyrite oxidation by ferric iron (ferric iron reduction) and by employing the ferric iron reduction metabolism of Ferroplasma JTC 3. With the particular aerobic/anaerobic solution potential control system, in conjunction with the metabolic capabilities of Ferroplasma JTC 3, the solution potential could be controlled within the critical low potential region, but no chalcopyrite leaching could be obtained during the anaerobic phase. The lack of chalcopyrite leaching during the anaerobic phase was due to inability of ferric iron to act as oxidant of chalcopyrite after the mineral was pre-leached in the preceding aerobic phase. The “oxidative acid leach” mechanism was identified as the dominant leach reaction that prevailed during the aerobic low potential stage in each of the aerobic/anaerobic control experiments conducted, in which oxygen acts as oxidant of chalcopyrite (electron acceptor) in the presence of protons (H+) (acidic environment), instead of ferric iron in an acid environment. The “boundary potential”, which is the maximum solution where no electron flow occurred to the ferrous/ferric couple from “pre-leached” chalcopyrite, was identified in the region of 450 mV (Ag/AgCl). Under the experimental conditions within this study, the leaching of chalcopyrite within the aerobic phase of the aerobic/anaerobic control experiments was superior to the Ferroplasma JTC 3 mediated high potential leaching, but complete copper dissolution could not be obtained with the combined aerobic and anaerobic system. Ferric iron precipitation as a function of pH was proposed as a tool for solution potential control, instead of controlling the potential by limiting oxygen to the leach system. In controlling the solution potential via pH, almost complete copper dissolution from chalcopyrite was obtained, while maintaining the solution potential below the critical upper limit of the low potential region.

Studies were conducted into the mechanism and kinetics of the dissolution of synthetic zinc sulfide and zinc concentrate in aqueous solutions containing sulfur dioxide.Experiments at ambient temperature established that the dissolution of ZnS in aqueous solutions of sulfur dioxide proceeds via acidic non-oxidative dissolution and not by direct reaction of the sulfide with S02(aq). The non-oxidative dissolution reaction generates H2S(aq) or HS-(aq) species which are thought to rapidly react with sulfurous acid species, S02(aq) or HS03-(aq), to possibly produce initially sulfane monosulfonates as intermediates, followed by sulfane disulfonates and elemental sulfur. The formation of sulfane monosulfonates is postulated based upon inhibition observed in ZnS / S02 leaches which is not attributable to either H2S(aq) or occlusion elemental sulfur.At elevated temperatures (100oC - 200oC) the rate of ZnS dissolution in sulfurous acid is affected by the thermal decomposition of sulfurous acid, which produces sulfuric acid, which leaches the mineral non-oxidatively. Increasing the temperature increases the rate of thermal decomposition of sulfurous acid and consequently, the rate of sulfuric acid formation, increasing the rate of ZnS dissolution.The kinetics of the dissolution of ZnS in solutions of sulfuric acid and sulfur dioxide were investigated at temperatures up to 200oC. At 100oC and 150oC, the dissolution of ZnS in H2SO4 was found to obey the relationd[Zn2+]/dt = kfAs[H+] krAs[H2S(aq)]1/2[Zn2+]1/2and equilibria and rate constants for the ZnS / H2S04 reaction were obtained over the range, 100oC to 200oC. The activation energies of the forward and reverse reactions were found to be 56 +/- 11 kJ mol-1 and 45 +/- 15 kJ mol-1, respectively. The equilibrium constants were 4.99x10-4, 1.26x10-3 and 2.83x10-3 at 100oC, 150oC and 200oC, respectively.In the presence of added S02, ++ / at low ZnS pulp density (0.5 g L-1), the rate of ZnS dissolution in sulfuric acid increased due to the removal of H2S(aq) by reaction with S02(aq) or HS03-(aq). However the increase in rate was much less than that expected for the complete removal of H2S(aq). As with leaches of ZnS in sulfurous acid at ambient temperature, the inhibition was not attributable to the presence of residual H2S(aq) or to occlusion of unreacted ZnS by elemental sulfur, but is thought to be due to aqueous species that are like "H2S", in that they may react with Zn2+ to reprecipitate W.To this end, sulfane monosulfonates have again been postulated. The rate of ZnS dissolution, under conditions of low pulp density, was independent Of S02 concentration, suggesting that under these conditions the rate of the H2S / S02 reaction is also independent of the S02 concentration.At higher pulp densities (200 g L-1), similar to those expected in an industrial application, synthetic zinc sulfide leached rapidly in H2S04 / S02 solutions to approximately 60% zinc extraction, but was then inhibited by the large amounts of sulfur that formed. These caused agglomerates of zinc sulfide and elemental sulfur to form, even at temperatures below the melting point of sulfur, reducing the surface area of zinc sulfide available for reaction.Leaches of zinc concentrate at low pulp densities in H2S04 / S02 solutions and at temperatures above sulfur's meting point, were inhibited by the formation of molten sulfur. In contrast to synthetic zinc sulfide, zinc concentrate is readily wet by molten sulfur. Three surfactants orthophenylenediamine, quebracho and sodium ligninsulfonate were found to be reasonably effective in preventing molten sulfur from occluding the mineral surface. At high pulp densities, the H2S04 / S02 leach solution was unable to effect, the extraction of zinc from a zinc concentrate beyond approximately ++ / 10%.Integral S02 / H2S04 leaching of zinc concentrate was found not to be a commercial prospect. However, sidestream processing of zinc concentrate in an acid leach stage followed by reaction of generated H2S with S02 from the roasting stage to produce elemental sulfur may be viable.

Dissertation (Ph. D.)--University of Stellenbosch, 1995. / Bibliography. Also available via the Internet.

CG-4 H2S adsorbent, an iron oxide based solid, has high sulfur capacity (20-25% w/w) and thus finds favor in users eyes in North America. This product, imported from CLEAN Catalysis and Purification Technologies Development Company in Shanxi Province, China, is now being used in gas processing companies in Alberta, Canada and Texas, USA. However, due to the elemental sulfur deposition on the adsorbent, the recovered sulfur capacity by regeneration is only about 1/3 as that of fresh adsorbent. This limits the adsorbent use to be once, which results in higher operating cost due to the frequent changeover and cost for landfills. The problem of sulfur deposition is also the limitation to the utilization and regeneration of other desulfurization adsorbent or catalyst. <p>This study developed a process to recover the sulfur capacity of CG-4 adsorbent by ammonia leaching to remove elemental sulfur. The leaching was conducted in a stainless steel cylindrical reactor at room temperature and a pressure higher than the vapor pressure of liquid ammonia. The leaching process does not deleteriously change the physical strength, but improve the properties of surface area, pore volume and pore size distribution. The new regeneration process is able to recover over 90% sulfur capacity in the first adsorption-regeneration cycle. The sulfur capacity recovery declined when CG-4 had been leached for more than one time. Nonetheless, even after the third time leaching, the sulfur capacity was recovered by 60%. The conditions of leaching process were optimized in a laboratory-scale experiment. <p>Additionally, the elemental sulfur collected from leaching process has 91.5% w/w purity and can likely be used as an additive to asphalt or used as a soil amendment for agricultural applications. The separation of solid wash-offs and liquid ammonia was simply fulfilled by depressurizing the leaching vessel and vaporizing the ammonia. CG-4 adsorbent is verified capable of at least three times reuses, which results in 60% reduction in disposal amount per unit H2S being treated. This not only reduces the cost in disposal to landfills but also the cost in CG-4 adsorbent and brings the revenue from the recovered elemental sulfur. The vapor ammonia is recommended to be recycled and reused by compressing it back to liquid.