Thesis (PhD)--Stellenbosch University, 1992. / ENGLISH ABSTRACT: The dissolution of gold from refractory ores is a complex kinetic problem involving a number of chemical, mass transport and mineralogical factors. In most Witwatersrand ores in South Africa more than 97 % of the gold is dissolved in cyanide medium after a residence time of about 16 hours in pachuca tanks. This high percentage may be the reason why so little fundamental research has been done into the mechanism and kinetics of the leaching process. With the increasingly lower grades of ore mined, the introduction of backfill mining, and the reduction of profit margins, it has become imperative to increase the efficiency of gold dissolution. The effects of the chemistry and particle size on the dissolution of gold in each sample of ore were studied in detail. The emphasis in this study is on the effect of the leaching behaviour of various ore constituents on the rate of gold dissolution. Interferences with the leaching of gold in contact with other minerals or metals could be attributed to the galvanic interaction (electrical conductivity) between the gold and the mineral and to the formation of a surface film on the gold surface. Sulphide minerals and their oxidation products cause the largest decrease in gold dissolution rate. Galena enhances the rate of gold dissolution owing to dissolved Pb(II)-ions. Gold in contact with conductive minerals passivates as a result of the enhanced magnitude of the cathodic cu1Tent. In all experiments the rotating disc of gold passivated so that the rate of dissolution was much slower than that predicted by a mass-transport limiting model. The various films that form on the surface of the gold and associated minerals, as well as the galvanic interaction, depend largely on the pretreatment of the ore. Pre-elimination of host minerals from the gold bearing ore increases the dissolution rate of gold, and explains the kinetics of reaction on the gold surface to a large extent. The selective destruction of the various minerals with oxidative acid leaches destroys and/or decomposes certain minerals which may form films on the gold surface by precipitation. The chemical composition of these films and precipitates depends on the mineralogy of the sample. These films may be oxides, sulphides, carbonates and cyanide complexes. The complexes can be destroyed, depending on the nature of the film, by interstage dilute acid and/or cyanide washes in an agitated vessel. The destruction of the films exposes the gold surface for cyanidation. A simple distribution function similar to the King liberation model is proposed and tested to describe the dissolution step in the multi-step leaching mechanism. For the King model, good agreement is shown with experimental results. For the liberation results obtained by leaching in this study, the trend is co1Tect, but calibration is required for a close fit. A potentially important use for the liberation model by leaching is to predict the leachable or free gold in an ore from the free gold in the complete sample. This approach for studying the leaching behaviour of different gold bearing minerals has provided reasons why some ores leach better than others. / AFRIKAANSE OPSOMMING: Die loging van goud vanuit weerbarstige ertse is 'n komplekse kinetiese probleem wat verskeie faktore soos massa-oordrag, chemiese aspekte en mineralogiese ingeweefdheid insluit. Goud ekstraksies so hoog as 97 % in sianied oplossings in Pachuca reaktore na ongeveer 16 uur logingstyd word behaal in die meeste Witwatersrand ertse in Suid-Afrika. Hierdie hoë ekstraksies mag dalk die rede wees vir die min fundamentele navorsing oor die ekstraksie van goud vanuit minerale in 'n spesifieke erts. Die dalende erts grade, die verlaging van winsgrense en die terugplaas van geloogde erts in die myn noodsaak verbeterde goud ekstraksie. Verkeie faktore nl., chemie, diffusie, partikelgrootte en oplosbaarheid van goud in elke monster erts is in hierdie studie ondersoek. Die sentrale tema was om die logingsgedrag van goud vanuit verskeie minerale in 'n erts te bepaal. Galvaniese interaksie (hou verband met elektriese geleidingsvermoeë) en film vorming is die belangrikste faktore wat die loging van goud in kontak met minerale nadelig beïnvloed. Sulfied minerale en hul oksidasie produkte speel die grootste rol in die verlaging van die tempo van goudloging. Galena verhoog die tempo van goudloging as gevolg van die Pb (II)- ione in oplossing. Goud in kontak met geleidende minerale passiveer as gevolg van die verhoogde katodiese stroomdigtheid. In alle eksperimente met die roterende skyf (goudskyf) apparaat, passiveer die goudskyf in so 'n mate dat die logingstempo baie stadiger is as wat voorspel word met die massa-oordrags model. Die onderskeie films wat vorm op die goud- en geassosieerde minerale se oppervlaktes, asook die galvaniese interaksies, is 'n funksie van die voorafbehandeling van die erts. Die selektiewe eliminering van minerale vanuit 'n gouddraende erts verhoog die tempo van goudloging drasties en dit beskryf die kinetika van goudloging op die goudoppervlak in 'n groot mate. Die selektiewe eliminering van minerale deur gebruik te maak van oksiderende suurlogings, vernietig sekere van die minerale wat films op die goudoppervlakte kan veroorsaak deur middel van presipitasie. Die chemiese samestelling van hierdie films hang af van die mineralogie van die monster. Dit bestaan meestal uit oksiedes, sulfiedes, karbonate en sianiedkomplekse en hulle kan vernietig word deur middel van inter-stadia verdunde suur-en/of sianied wasse. 'n Eenvoudige distribusiefunksie, soortgelyk aan die King bevrydingsmodel word voorgestel en eksperimenteel getoets om die logingstap in die multi-stadia logingsmeganisme te beskryf. Vir bevryding deur loging, is die neiging van King se model korrek, maar kalibrasie word benodig vir goeie passing. 'n Potensiele gebruik van die aangepaste model is om vrye of loogbare goud in 'n spesi fieke partikel grootte fraksie van 'n erts te voorspel as die vry goud in die totale fraksie bekend is. Die resultate uit hierdie studie kan gebruik word om die logingsgedrag van gouddraende minerale te voorspel en te beskryf, en dus veduidelik hoekom goud uit sekere ertse beter loog as uit ander.

Thesis (PhD)--Stellenbosch University, 2012. / ENGLISH ABSTRACT: Sulphuric acid/oxygen pressure leaching is typically employed on Base Metal Refineries (BMRs) to selectively dissolve base metals from platinum group metal (PGM) bearing nickelcopper matte. Optimal operation of this processing step requires an understanding of the system chemistry and the effects of process variables on base metal and PGM leaching behaviour. This project aimed to aid in the development of an improved understanding of the high pressure leaching system. The effects of temperature, pressure, acid concentration, and solid to liquid ratio on the leaching behaviour were determined experimentally using a two litre autoclave. For conditions comparable to that typically used at the Western Platinum Ltd. BMR, changes in the acid concentration had the largest effect on the copper leaching behaviour. Increasing the initial acid concentration from 140 g H2SO4/ℓ to 165 g H2SO4/ℓ resulted in the copper dissolution decreasing from 88.7% to 75.3% on average for the experiments performed at different temperatures (116°C, 130°C) and pressures (7 bar, 9 bar), and with different solids contents (80 g/ℓ, 130 g/ℓ). In the case of the other precious metals (OPMs), temperature was determined to be the process variable with the largest effect on the leaching kinetics. The average percentage rhodium dissolution achieved after seven hours of leaching at different conditions (pressure, acid concentration, and solids content were varied) increased from 58.3% at 116°C to 83.6% at 130°C. Similar effects were observed for ruthenium (96.2% dissolution at 130°C; 79.4% dissolution at 116°C) and iridium (81.8% dissolution at 130°C; 46.9% dissolution at 116°C). The rate of copper leaching was found to be limited by the rate of oxygen transfer from the gaseous phase to the liquid phase, while the remainder of the reactions were chemical reaction limited. The extent of OPM leaching was found to be dependent on the rate and extent of copper leaching. A set of 21 chemical reactions was proposed to describe the leaching behaviour, and the shape factors and reaction rate constants were determined by the method of least squares to minimise the error between the predicted concentrations and the experimental data. Apart from direct base metal leaching reactions, six cationic exchange reactions contribute to the leaching of copper sulphides and nickel sulphides by precipitation of OPM oxides. Three leaching reactions for each of the OPMs (one for sulphide phases, one for metallic phases, and one for oxide phases) resulted in satisfactory modelling of the system behaviour. Activation energies of -26.2 kJ/mol and -5.9 kJ/mol were calculated for the digenite acid leaching reaction and the covellite direct oxidation reaction, respectively, which confirmed that the rates of these reactions were mass transfer limited. The activation energies for the remainder of the base metal leaching reactions exceeded 30 kJ/mol. The activation energies of the reactions accounting for rhodium sulphide leaching, rhodium leaching, and rhodium oxide leaching, were calculated to be 64.2 kJ/mol, 138.5 kJ/mol, and 116.2 kJ/mol, respectively. Similar activation energies were calculated for the respective Ru and Ir leaching reactions. The rate of OPM sulphide leaching was typically an order of magnitude and three orders of magnitude larger than the rate of OPM leaching reactions and OPM oxide leaching reactions, respectively. The autoclave at the Western Platinum Ltd. BMR was modelled assuming a monosized distribution of the feed and approximating the autoclave as four ideal continuously stirred tank reactors. The steady state solution employed the sequential modular approach in MATLAB, while the dynamic simulation involved solving a set of 217 differential equations derived from mass and energy balances simultaneously in MATLAB. The model was used successfully to evaluate the effects that changes in the leaching temperature, leaching pressure, acid feed rate, and solids feed rate have on the extent of base metal and OPM leaching in the autoclave. The optimum operating conditions depend on the flow rates and compositions of the feed streams. A feed stream containing 10.3 wt% solids (825 kg solids/h) and an acid addition rate of 28.6 kg/h were considered as typical operating conditions for model-based analysis. More than 95% copper dissolution and no OPM dissolution were predicted when performing the pressure leaching at a pressure of 8 bar and a temperature of approximately 123°C. Decreasing the pressure resulted in lower copper dissolution when OPM leaching started to occur. Increasing the temperature resulted in reduced copper leaching, while decreasing the temperature resulted in a longer OPM leaching period and hence higher OPM dissolution. Model-based analysis furthermore showed that the relative amounts and relative leaching rates of digenite and covellite significantly influence the percentage copper dissolution achieved when noticeable OPM leaching start to occur. / AFRIKAANSE OPSOMMING: Swawelsuur/suurstof hoë druk loging word tipies op Basis Metaal Raffinaderye (BMRe) gebruik om basis metale selektief op te los vanuit platinum groep metaal (PGM) bevattende nikkel-koper mat. Optimale bedryf van hierdie prosesstap vereis ʼn begrip van die sisteem se chemie en die effekte wat proses veranderlikes op die logingsgedrag van basis metale en PGMe het. Hierdie projek het ten doel gehad om ʼn beter begrip van die hoë druk loging sisteem te ontwikkel. Die effekte van temperatuur, druk, suur konsentrasie, en vastestof tot vloeistof verhouding op die logingsgedrag is eksperimenteel met behulp van ʼn twee liter outoklaaf bepaal. Vir toestande vergelykbaar met dié wat tipies by die Western Platinum Bpk. BMR gebruik word, het veranderinge in die suurkonsentrasie die grootste effek op die logingsgedrag van koper gehad. Verhoging van die aanvanklike suurkonsentrasie van 140 g H2SO4/ℓ na 165 g H2SO4/ℓ het tot gevolg gehad dat die gemiddelde koper oplossing afgeneem het van 88.7% na 75.3% vir die eksperimente wat by verskillende temperature (116°C, 130°C) en drukke (7 bar, 9 bar), en met verskillende vastestof inhoud (80 g/ℓ, 130 g/ℓ), uitgevoer is. In die geval van die ander edelmetale (AEM) is bevind dat die temperatuur die prosesveranderlike met die grootste effek op die logingskinetika is. Die gemiddelde persentasie rodium oplossing wat na sewe ure se loging by verskillende toestande (druk, suurkonsentrasie, en vastestof inhoud is varieer) behaal is, het toegeneem van 58.3% by 116°C na 83.6% by 130°C. Soortgelyke effekte is waargeneem vir rutenium (96.2% oplossing by 130°C; 79.4% oplossing by 116°C) en iridium (81.8% oplossing by 130°C; 46.9% oplossing by 116°C). Dit is bevind dat die tempo van koper loging beperk is deur die tempo van suurstof oordrag vanaf die gas na die vloeistoffase, terwyl chemiese reaksies beperkend was vir die res van die reaksies. Die mate van AEM loging was afhanklik van die tempo en mate van koper loging. ʼn Stel van 21 reaksies is voorgestel om die logingsgedrag te beskryf, en die vorm faktore en reaksie tempo konstantes is bepaal deur middel van die metode van kleinste kwadrate om die fout tussen die voorspelde konsentrasies en die eksperimentele data te minimeer. Afgesien van die direkte basis metaal logingsreaksies het ses kationiese uitruilingsreaksies bygedra tot die loging van kopersulfiede en nikkelsulfiede deur presipitasie van AEM oksiede. Drie logingsreaksies vir elk van die AEMe (een vir die sulfied fase, een vir die metaal fase, en een vir die oksied fase) het bevredigende modellering van die sisteem se gedrag tot gevolg gehad. Aktiveringsenergieë van -26.2 kJ/mol en -5.9 kJ/mol is bereken vir die Cu1.8S suur logingsreaksie en die CuS direkte oksidasie reaksie, onderskeidelik, wat bevestig het dat die tempo’s van hierdie reaksies deur massa oordrag beperk is. Die aktiveringsenergieë vir die res van die basis metaal logingsreaksies het 30 kJ/mol oorskry. Die aktiveringsenergieë vir die reaksies wat die rodiumsulfied loging, rodium loging, en rodiumoksied loging beskryf is as 64.2 kJ/mol, 138.5 kJ/mol, en 116.2 kJ/mol, onderskeidelik, bereken. Soortgelyke aktiveringsenergieë is bereken vir die onderskeie Ru en Ir logingsreaksies. Die tempo van AEM sulfied loging was tipies ʼn ordegrootte en drie ordegroottes groter as die tempo van AEM logingsreaksie en AEM oksied logingsreaksies, onderskeidelik. Die outoklaaf by die Western Platinum Bpk. BMR is gemodelleer deur ʼn enkelgrootte verspreiding vir die voer te aanvaar en die outoklaaf as vier ideale kontinu geroerde tenk reaktore te benader. Die oplossing vir gestadige toestande het die sekwensiële modulêre benadering toegepas in MATLAB, terwyl die dinamiese simulasie die gelyktydige oplos van 217 differensiale vergelykings, wat vanaf massa- en energiebalanse afgelei is, in MATLAB behels het. Die model is suksesvol gebruik om die effekte wat veranderinge in die logingstemperatuur, logingsdruk, suur voertempo, en vastestof voertempo op die mate van basis metaal en AEM loging in die outoklaaf het, te bepaal. Die optimale bedryfstoestande is afhanklik van die vloeitempo’s en samestellings van die voerstrome. ʼn Voerstroom wat 10.3 massa% vastestof (825 kg vastestof per uur) bevat en ʼn suur voertempo van 28.6 kg/h is as tipiese bedryfstoestande beskou vir model-gebaseerde analises. Meer as 95% koper oplossing sonder enige AEM oplossing is voorspel wanneer die loging by ʼn druk van 8 bar en ʼn temperatuur van ongeveer 123°C uitgevoer word. ʼn Vermindering van die druk het tot gevolg gehad dat laer koper loging behaal is toe AEM loging begin plaasvind het. ʼn Verhoging in die temperatuur het laer koper loging tot gevolg gehad, terwyl laer temperature ʼn langer AEM logingsperiode en gevolglik hoër AEM loging tot gevolg het. Model-gebaseerde analises het verder getoon dat die relatiewe hoeveelhede en relatiewe tempo’s van loging van Cu1.8S en CuS ʼn beduidende invloed het op die persentasie koper wat geloog is wanneer beduidende AEM loging begin plaasvind.

Thesis (MEng)--Stellenbosch University, 2014. / ENGLISH ABSTRACT: In Base Metal Refineries (BMRs), the copper sulphate leach solution produced during the final pressure leaching stage contains impurities such as selenium and tellurium, as well as other precious metals (OPMs, namely Rh, Ru, and Ir). Se and Te are removed by precipitation with sulphur dioxide prior to electrowinning of Cu. While a small percentage of the dissolved OPMs precipitate with the Se and Te, the largest portion remains in solution and is recycled to the first stage leach. If a larger portion of the OPMs in solution can be recovered in the Se/Te precipitation stage, OPM losses and the OPM inventory of the plant can be reduced. The aim of this project was to determine operating conditions that would allow maximum OPM recovery with minimal Cu and Ni co-precipitation in the Se/Te removal section of a BMR. The effects that the operating temperature, pressure, stirring rate, reagent type, and reagent quantity have on the metal precipitation behavior and precipitate characteristics were determined experimentally. Thio-urea and sulphurous acid were evaluated as precipitation reagents for temperatures of 80°C and 160°C, stirring rates of 250 rpm and 500 rpm, and pressures equal to ambient pressure and 7 bar. 200 % and 320 % excess thio-urea and 720 % and 960 % excess sulphur dioxide were used. The precipitation of OPMs with sulphur dioxide was generally poor; the maximum percentage Rh, Ru, and Ir precipitated were 35 %, 18 %, and 20 %, respectively. It was, however, found that the OPM precipitation increased as the reagent amount was increased. Increasing the temperature further increased Rh and Ir precipitation but affected the Ru precipitation negatively. Thio-urea precipitated virtually all of the Rh contained in the solution irrespective of the values of the process variables studied. As was the case with sulphur dioxide, increasing the amount of thio-urea added resulted in increased Ru and Ir precipitation, while higher temperatures favored Ir precipitation but not Ru precipitation. The maximum percentage Ru and Ir precipitation achieved with thio-urea were 87 % and 60 %, respectively. Complete Se precipitation was observed at all process conditions, while Te precipitation increased as the operating temperature and the reagent quantity were increased. Maximum Te precipitation of 98 % and 90 % were achieved when using 320 % excess thio-urea and 960 % sulphurous acid quantities, respectively, at 160°C and a stirring rate of 250 rpm. Increasing the reagent quantity and temperature did, however, also result in increased copper and nickel precipitation. The statistical analysis of the results allowed regression models to be fitted to predict the percentage metal precipitation as a function of the investigated process variables. These models were used to define an objective function to determine the optimal operating conditions. A temperature of 80oC, a pressure of 7 bar, and 200 % excess thio-urea were proposed as the optimum operating conditions that would yield 98 % Rh, 75 % Ru, and 48 % Ir precipitation with less than 5 % Cu and Ni co-precipitation. Experimental validation tests confirmed the model predicted values and proved repeatability of the experimental data. / AFRIKAANSE OPSOMMING: Die kopersulfaat logingsoplossing wat tydens die finale drukloging stadium in Basis Metaal Raffinaderye (BMRe) produseer word, bevat onsuiwerhede soos selenium en tellurium sowel as ander edelmetale (AEMe, naamlik Rh, Ru, en Ir). Se en Te word voor Cu elektrowinning verwyder deur middel van presipitasie met swaweldioksied. Alhoewel ʼn klein persentasie van die opgeloste AEMe saam met die Se en Te presipiteer, bly die grootste gedeelte in oplossing en word gevolglik na die eerste loging stadium hersirkuleer. AEM verliese en die AEM inventaris van die aanleg kan verminder word indien ʼn groter gedeelte van die AEMe in die Se/Te presipitasie stadium herwin kan word. Die doel van hierdie projek was om bedryfstoestande te bepaal om maksimum AEM herwinning met minimale Cu en Ni kopresipitasie in die Se/Te verwyderingseksie van ʼn BMR te behaal. Die effekte wat bedryfstoestande soos temperatuur, druk, roerder tempo, tipe reagens, en hoeveelheid reagens op die metaal presipitasiegedrag en presipitaat eienskappe het, is eksperimenteel bepaal. Tio-ureum en swaweligsuur is evalueer as presipitasie reagense vir temperature van 80°C en 160°C, roerder tempo’s van 250 rpm en 500 rpm, en drukke gelyk aan omgewingsdruk en 7 bar. 200 % en 320 % oormaat tio-ureum en 720 % en 960 % oormaat swaweldioksied is gebruik. Die presipitasie van AEMe met swaweldioksied was swak in die algemeen; die maksimum persentasie Rh, Ru, en Ir presipitasie wat behaal is, is 35 %, 18 %, en 20 %, onderskeidelik. Daar is egter gevind dat die AEM presipitasie toeneem indien die hoeveelheid reagens toeneem. ʼn Toename in die temperatuur het verder tot ʼn toename in Rh en Ir presipitasie gelei, maar dit het Ru presipitasie negatief affekteer. Tio-ureum het basies al die Rh in oplossing laat presipiteer, ongeag die waardes van die ander prosesveranderlikes wat ondersoek is. Soos wat die geval vir swaweldioksied was, het ʼn toename in die hoeveelheid tio-ureum ʼn toename in die Ru en Ir presipitasie tot gevolg gehad, terwyl hoër temperature Ir presipitasie bevoordeel en Ru presipitasie benadeel het. Die maksimum persentasie Ru en Ir presipitasie wat met tio-ureum behaal is, is 87 % en 60 %, onderskeidelik. Volledige Se presipitasie is by alle proses toestande waargeneem, terwyl Te presipitasie toegeneem het soos wat die temperatuur en die hoeveelheid reagens toegeneem het. Maksimum Te presipitasie van 98 % en 90 % is behaal toe 320 % oormaat tio-ureum en 960 % oormaat swaweligsuur, onderskeidelik, by 160°C en ʼn roerder tempo van 250 rpm gebruik is. ʼn Toename in die hoeveelheid reagens en die temperatuur het egter ook meer koper en nikkel presipitasie tot gevolg gehad. Die statistiese analise van die resultate het dit moontlik gemaak om regressie modelle te pas om die persentasie metaal presipitasie as ʼn funksie van die ondersoekte veranderlikes te voorspel. Hierdie modelle is gebruik om ʼn doelfunksie te definieer ten einde die optimale bedryfstoestande te bepaal. ʼn Temperatuur van 80°C, ʼn druk van 7 bar, en 200 % oormaat tioureum is voorgestel as die optimale bedryfstoestande wat 98 % Rh, 75 % Ru, en 48 % Ir presipitasie met minder as 5 % Cu en Ni kopresipitasie tot gevolg sal hê. Eksperimentele geldigheidsbepalingtoetse het die waardes wat deur die modelle voorspel is bevestig en die herhaalbaarheid van die eksperimentele data bewys.

Thesis (MEng) -- Stellenbosch University, 2014. / ENGLISH ABSTRACT: The copper sulphate leach solutions produced during the final pressure leach stages in base metal refinery processes contain low concentrations of other precious metals (OPMs, namely Rh, Ru and Ir ) and impurities in addition to the base metals (BMs) of interest. Se and Te impurities, in particular, must be removed from the leach solution before it is fed to copper electrowinning because these species have adverse effects on electrowinning efficiency. Currently, these elements are being precipitated from the leach solution with sulphurous acid. Se precipitation is satisfactory but Te removal still proves challenging. Previous studies have shown that tellurium can either be precipitated as cuprous telluride from copper sulphate solutions by reduction with sulphurous acid alone, or by the addition of SO2 as a precipitating agent and metallic copper as an additional precipitating agent. The objective of this study was to evaluate the effects of different process variables on Te and Se recovery in order to propose operating conditions at which increased tellurium precipitation can be achieved with minimal co-precipitation of base metals of interest (notably Cu and Ni). This would also aid in the development of a better understanding of tellurium and selenium precipitation mechanisms in CuSO4-H2SO4 medium. / AFRIKKANSE OPSOMMING: Die kopersulfaat logingsoplossing wat gedurende die finale druklogingstadia in basis metaal raffinaderye produseer word bevat, behalwe vir die basis metale van belang, ook lae konsentrasies ander edelmetale (AEM, naamlik Rh, Ru, en Ir) sowel as onsuiwerhede. Se en Te onsuiwerhede, in die besonder, moet vanuit die logingsoplossing verwyder word voordat die oplossing na die koper elektrowinning gevoer word omdat hierdie spesies negatiewe effekte op die elektrowinning effektiwiteit het. Hierdie elemente word tans met swaweligsuur vanuit die logingsoplossing gepresipiteer. Se presipitasie is voldoende, maar die Te verwydering bly steeds problematies. Vorige studies het getoon dat tellurium as kuprotelluried vanuit kopersulfaat oplossings presipiteer kan word deur middel van reduksie met swaweligsuur alleen, of met die byvoeging van SO2 as presipiteermiddel en metallieke koper as addisionele presipiteermiddel. Die doelwit van hierdie studie was om die effekte van verskillende prosesveranderlikes op Te en Se presipitasie te ondersoek ten einde bedryfstoestande voor te stel wat verbeterde tellurium presipitasie toelaat met minimale kopresipitasie van basis metale van belang (hoofsaaklik Cu en Ni). Dit sal ook bydra tot die ontwikkeling van ʼn beter begrip van die tellurium en selenium presipitasie meganisme in ʼn CuSO4-H2SO4 medium.

Previous studies from laboratory experiments and a similar process at a plant in Switzerland, led to the pilot plant project at Renova AB, which will be described in this master thesis. In cooperation with Götaverken Miljö AB it was investigated if fly ash, produced at the Renova Waste-to-Energy plant in Gothenburg, could be treated with own scrubber liquids in order to recover zinc. If successful, Renova might build this tested pilot process in to a big scale. The pilot plant has a scale of 16 times smaller than a future big scale process. The goal of the project is to leach zinc from fly ash and gain a fly ash residue, which is classified as non-hazardous waste. The filtrate from the leaching campaign is treated so that the containing zinc is recovered. The zinc cake end product shall has a quality so that it can be sold to other industries or upgraded to high purity zinc metal. The evaluation of the experiments showed that the pilot plant process was successful. It was possible to leach out zinc by a maximum quote of 74%. The total recovery of zinc could be achieved by a maximum of 72%. The final zinc cake product was achieved through a precipitation and filtration campaign. This thesis evaluates, which process set-ups for zinc recovery through leaching and precipitation & filtration are the best and can be recommended for a big scale process. In addition, it briefly analyses the zinc product quality. Future studies will be necessary within: cost analysis of the process, zinc product quality and an analysis of the ash residue.

Thesis (MSc (Microbiology))--University of Stellenbosch, 2005. / Plasmid pTC-F14 is a 14.2kb promiscuous, broad-host range IncQ-like mobilizable plasmid isolated from Acidithiobacillus caldus f. At. caldus is a member of a consortium of bacteria (along with Acidithiobacillus ferrooxidans and Leptospirilum ferrooxidans) that is used industrially for decomposing metal sulphide ores and concentrates at temperatures of 40ºC or below which is now a well-established industrial process to recover metals from certain copper, uranium and gold-bearing minerals or mineral concentrates. These biomining microbes are usually obligately acidophilic, autotrophic, usually aerobic iron- or sulphur-oxidizing chemolithotrophic bacteria. Their remarkable physiology allows them to inhabit an ecological niche that is largely inorganic and differs from those environments populated by the more commonly studied non-acidophilic heterotrophic bacteria. At. caldus, is a moderately thermophilic (45 to 50ºC), highly acidophilic (pH1.5 to 2.5) sulphur-oxidizing bacterium, and its role as one of the major players in the industrial decomposition of metal sulphide ores has become evident in recent years. At. caldus f from which pTC-F14 was isolated was found to be one of two dominant organisms in a bacterial consortium undergoing pilot-scale testing for the commercial extraction of nickel from ores.

ENGLISH ABSTRACT: Leaching of nickel laterite was conducted with a solution of ammonia and ammonium carbonate in a closed vessel. The vessel used in this study was designed to leach and perform solid-liquid separation at the same time. For solid-liquid separation, stainless steel sintered metal filter media were used. The sintered metal filter medium was selected for its high strength to withstand pressure, chemical resistance to caustic solution and back flushing properties. Optimum leaching conditions were determined by varying temperature, ammonia concentration, ammonium carbonate concentration and oxygen pressure. After leaching and filtration, the pH of the leach liquor was measured and samples were analyzed for dissolved metals (Ni, Fe and Co) using atomic absorption spectrophotometry. The most significant variable effect on leaching of nickel was the ammonia concentration. The maximum dissolution of nickel from the unroasted ore was 11.90% at 4 M NH3, 100oC, 2 M (NH4)2CO3 and 2 bar O2 pressure. Optimization from the leaching data was done using response profiling and desirability in Statistica software. Optimum leaching conditions were determined to be 3 M NH3, 2 M (NH4)2CO2, 100oC and 2 bar O2 pressure. The mineralogy of the ore before and after leaching was studied to understand why nickel extraction from unroasted ore was poor. XRF analysis of solids after leaching showed that iron, silicon, and magnesium remained the same. The only metal which showed significant decrease from solids was nickel. XRD analysis of solids after and before leaching showed that most mineral phases present in the ore are not affected by the leaching solution. SEM with EDS detection was used to determine nickel distribution within the ore. The results showed that nickel is mostly associated with iron. The iron is surrounded by magnesium and silicon. Silicate minerals do not react with ammonia and ammonium carbonate solution. From filtration experiments, the filtration differential pressure had no significant effect on the filtration rate. An average filtration rate of 0.29±0.07 ml/min.cm2 was obtained. The filtration rate from these experiments was very low. The main reason was due to quick pore clogging of sintered metals. Pore clogging was found to be mainly on the surface of the filter medium. Laterites have been found to have low permeability due a lot of clay present in the ore. Rheological studies on this ore showed that the ore has shear thickening behavior. However, a very clear filtrate was obtained. After each leach and filtration experiment, the sintered metals was unblocked by back flushing with water and air. Back flushing was successful because all 18 experiments were carried out using the same sintered filter medium. The effect of roasting the ore prior to leaching was investigated using optimum conditions obtained when leaching the unroasted ore. There was a slight improvement in nickel extraction when the ore was roasted. The average percentage extraction of nickel from 3 experimental runs was 19.25%±0.19 at 100oC, 3M NH3, 2M (NH4)2CO3, and 5 bar oxygen pressure. Some part of nickel in the ore was unextractable due to association of nickel with recrystallized silicate minerals in the reduced ore. Roasting improved permeability of the ore. The filtration rate improved significantly after roasting the ore. The average filtration rate was 2.60±0.05 ml/min.cm2. Dissolution kinetics of the unroasted and roasted saprolitic laterite were investigated with regard to the effects of temperature, ammonia concentration, ammonium carbonate concentration, and oxygen pressure. For the unroasted ore, it was found that dissolution rate and degree of nickel extraction increases with increasing temperature. Increase in ammonia concentration improves the degree of nickel extraction. Nevertheless, nickel extraction does not depend entirely on ammonia concentration because even when ammonia concentration is high and ammonium carbonate concentration is zero nickel extraction is low. An increase in ammonium carbonate concentration also increases the degree of nickel extraction. Ammonium carbonate is critical for the extraction, since ammonium ions in the solution prevent hydrolysis of the nickel ammine complex. Oxygen did not have a significant effect on the degree of nickel extraction. The leaching of nickel laterite was found to be a two stage leaching process. In the first stage, the dissolution of nickel is faster but after 15 minutes, the reaction rate is reduced. The reaction rate is reduced by inert minerals which host nickel. These minerals contain iron magnesium and silicon. The fast dissolution of nickel in the first stage represents leaching of free nickel in the ore. The data for the second stage of leaching was analyzed by the shrinking core model, and the results suggested that the dissolution rate is controlled by mixture kinetics (ash layer diffusion and surface reaction control). The activation energy for the dissolution reaction was calculated as 56.5 KJ/mol. The reaction order with respect to ammonia and ammonium carbonate were determined to be 0.3 and 0.26 respectively. For the roasted ore, the highest degree of nickel extraction was obtained at 60oC, 3M NH3, 2M (NH4)2CO3, and 5 bar oxygen pressure. The percentage extraction under these conditions was 28.7%. Temperature did not have a significant effect on the leaching rate. An increase in NH3 and (NH4)2CO3 increased the final extraction of nickel but did not have any effect on leaching rate in the first stage of leaching. In the absence of ammonium carbonate, nickel extraction is almost zero. The experimental data did not give linear fit to the shrinking core models investigated for the unroasted ore. The reason for this could be due to the sampling time interval which was too far apart, or the leaching behavior of roasted nickel is complicated and cannot explained by shrinking core model alone. Leaching experiments demonstrate that for a high degree metal extraction and improved reaction kinetics with ammonia and ammonium carbonate, the solution temperature should be high (>100oC) for the unroasted ore. In order to leach at high temperature with ammonia and ammonium carbonate a closed vessel is required to prevent reagent loses. The reaction kinetics showed that the reaction is controlled mostly by ash layer diffusion; this indicates that a low degree of nickel extraction in the unroasted saprolitic laterite is due to inert minerals (ash layer) which host nickel within the ore. In order to obtain a high degree of nickel extraction, the ore needs to be roasted under reducing conditions. Roasting conditions need to be carefully controlled to ensure high dissolution of nickel. In fact optimum roasting conditions which will give maximum dissolution of nickel, must be determined before working with the bulk of the ore. / AFRIKAANSE OPSOMMING: Logingstoetse van saprolitiese lateriet met 'n oplossing van ammonia en ammonium karbonaat is gedoen in 'n druk houer. Die logingsvat vir hierdie studie is ontwikkel om die loging sowel as die vloeistof – vastestof skeiding te doen. Gesinterde metaal filter medium was gebruik vir die vloeistof – vastestof skeiding aangesien dit die volgende eienskappe vertoon; die vermoë om druk te weerstaan, die chemiese weerstand teen bytsoda oplossing, asook voordelige terugspoel eienskappe. Optimum loogkondisies is bepaal deur die temperatuur, ammoniak konsentrasie, ammonium karbonaat konsentrasie, en suurstof druk te varieer. Na loging en filtrasie is die pH van die loogvloeistof gemeet en monsters is deur atoom absorpsie spektrofotometrie geanaliseer vir opgeloste metale (Ni, Fe en Co). Die veranderlike wat die grootste effek op die loging van nikkel gehad het was die ammoniak konsentrasie. Die maksimum herwinning van nikkel van uit ongeroosterde erts was 11.9 % by 4 M NH3, 100 oC, 2 M (NH4)2CO3 en 2 bar O2 druk. Optimisering van die loogdata is gedoen deur die respons profiel te analiseer met Statistica sagteware. Optimum loogkondisies was bepaal as 3 M NH3, 2 M (NH4)2CO2, 100 oC en 2 bar O2 druk. Die mineralogie van die erts voor en na loging is bestudeer om te bepaal waarom die nikel opbrengs van ongeroosterde erts so laag was. XRF analise van die vastestof na loging het gewys dat yster, silikon en magnesium nie deur loging affekteer is nie. Slegs nikkel het 'n merkwaardige afname getoon. XRD analsiese van die vastestof voor en na loging wys dat die meeste mineraal fases teenwoordig in die erts nie deur die loogoplossing affekteer is nie. SEM met EDS deteksie is gebruik om die nikkel verspreiding in die erts te bepaal. Die resultate wys dat nikkel meestal met yster assosieer. Die yster is omring deur magnesium en silikon. Silikaat minerale reageer nie met ammoniak en ammonium karbonaat oplossing nie. In filtrasie eksperimente is daar gevind dat die filtrasie differensiële druk geen noemenswaardige effek op die filtrasie tempo gehad het nie. Die gemiddelde filtrasietempo was 0.29+0.07 ml/min.cm2. Die filtrasie tempo van hierdie eksperimente was baie laag, hoofsaaklik as gevolg van blokkasie van porieë van die sinter metaal filter medium. Dit is gevind dat blokkasie van porieë hoofsaaklik op die oppervlak van die filter medium plaasvind. Lateriedes toon 'n lae deurlaatbaarheid as gevolg van die erts se hoë klei inhoud. Rheologiese studies op hierdie erts wys dat die erts skuif verdikking (“shear thickening”) gedrag vertoon. 'n Baie helder filtraat is egter verkry. Die gesinterde metale is na elke loog en filtrasie eksperiment skoongemaak deur terugspoeling met water en lug. Hierdie procedure was suksesvol, aangesien al 18 eksperimente met dieselfde filter medium uitgevoer is. Die effek van erts roostering voor loging is ondersoek by die optimum kondisies wat verkry was vir die loging van ongeroosterde erts. Nikkel ekstraksie het effens verbeter met geroosterde erts. Die gemiddelde persentasie ekstraksie van nikkel van drie eksperimentele lopies was 19.25 % + 0.19 by 100 oC, 3 M NH3, 2 M (NH4)2CO3, en 5 bar suurstofdruk. 'n Gedeelte van die nikkel in die erts was onherwinbaar as gevolg van die assosiasie van nikkel met her-gekristaliseerde sillikaat-minerale in die gereduseerde erts. Die porositeit van die erts is verbeter deur dit te rooster. Die filtrasie tempo het merkwaardig verbeter nadat die erts gerooster is. Die gemiddelde filtrasie tempo was 2.6+0.05 ml/min.cm2. Kinetika vir die oplossing van ongeroosterde en geroosterde saprolitiese lateriet is ondersoek, met in ag geneem die effekte van temperatuur, ammonia konsentrasie, ammonium karbonaat konsentrasie en suurstofdruk. Vir ongeroosterde erts is gevind dat die oplossingstempo en graad van nikkel ekstraksie toeneem met toenemende temperatuur. Toename in ammoniak konsentrasie lei tot 'n toename in nikkel ekstraksie, maar nikkel ekstraksie is nie alleenlik afhanklik van ammoniak nie. 'n Toename in ammonium karbonaat konsentrasie lei ook tot 'n toename in nikkel ekstraksie. Ammonium karbonaat is krities vir die ekstraksie, aangesien ammonium ione in die oplossing die hidrolise van die nikkel-amien kompleks verhoed. Suurstof het nie 'n merkwaardige effek op die totale nikkel ekstraksie gehad nie. Vir die bepaling van reaksie kinetika is 100˚C gebruik as die logingstemperatuur. Die loging van saprolitiese nikkel lateriet vind in twee stadia plaas. In die eerste fase is die oplossing van nikkel vinnig, maar na 15 minute neem die reaksietempo af. Die reaksietempo word verlaag deur inerte minerale wat teenwoordig is in die nikkel erts. Hierdie minerale bevat yster, magnesium en silikon. Die vinnige oplossing van nikkel in die eerste fase verteenwoordig die loging van vry nikkel in die erts. Die data vir die tweede stadium is geanaliseer deur die krimpende kern model, en die resultate dui aan dat die oplossingstempo deur 'n gemengde meganisme beheer word (as laag diffusie en oppervlak reaksie beheer). Die aktiveringsengergie vir die oplossingsreaksie was bereken as 56.5 kJ/mol. Die reaksieorde ten opsigte van ammoniak en ammonium karbonaat is onderskeidelik bepaal as 0.3 en 0.26. Die hoogste graad van nikkel ekstraksie vir die geroosterde erts is verkry by 60oC, 3 M NH3, 2 M (NH4)2CO3, en 5 bar O2 druk. Die persentasie ekstraksie by hierdie kondisies was 28.7 %. Temperatuur het nie 'n merkwaardige effek op loogtempo gehad nie. 'n Toename in NH3 en (NH4)2CO3 het die graad van nikkel ekstraksie laat toeneem, maar het nie enige effek op die loogtempo gehad nie. In die afwesigheid van ammonium karbonaat het byna geen nikkel ekstraksie plaasgevind nie. Die eksperimentele data het nie 'n lineêre passing vir die krimpende kern model soos vir die ongeroosterde erts ondersoek gegee nie. Die rede hiervoor is dat die monsternemings interval te groot was, of dat die logings karakteristiek van geroosterde nikel gekompliseerd is en nie alleen deur die krimpende kern model voorspel kan word nie. Logings eksperimente wys dat die temperatuur hoog moet wees (> 100 oC) om 'n hoë graad van nikkel ekstraksie te verkry met die ongeroosterde erts. 'n Geslote reaktor word benodig om by 'n hoë temperatuur met ammoniak en ammonium karbonaat te loog om reagens verliese te verhoed. Die reaksie kinetika word grootliks deur aslaag diffusie beheer. Hieruit kan gesien word dat 'n lae graad van nikkel ekstraksie uit die ongeroosterde saprolitiese lateriet die gevolg is van nie-reaktiewe minerale (aslaag) waarin die nikkel binne die erts bevat word. Om 'n hoë graad van nikkel ekstraksie te verkry moet die erts onder reduserende kondisies gerooster word. Rooster kondisies moet versigtig beheer word om hoë oplossing van nikkel te verseker. Optimum rooster kondisies om maksimum nikkel oplossing te verkry, moet bepaal word voordat daar met groter hoeveelhede erts gewerk kan word.

Thesis (MScAgric (Soil Science))--University of Stellenbosch, 2008. / In order to produce table grapes of export quality economically, irrigation must be practised conservatively without adversely affecting the crop. To use water as conservatively as possible effective irrigation scheduling practices must be applied. The highest water use efficiency (WUE) is only possible if irrigation scheduling practices lower the amount of water applied, while at the same time they increase the yield. The first aim of this project is to investigate whether current irrigation practices make efficient use of water by comparing irrigation requirements determined using theoretical models with actual irrigation applied for two seasons (2005/6 and 2006/7). Secondly, the effect of cumulative irrigation on the chemical status of soil in 16 blocks was investigated to establish whether nutrient leaching as a result of differential water use may have had an influence on yield. Six blocks (three dripper and three microsprinkler blocks) were selected and irrigation requirements were determined using evaporation pan calculations, SAPWAT and Vinet and compared with actual irrigation applications. Furthermore, a yield-irrigation index (kg/m3) and an income-irrigation index (R/m3) were determined for each of the six blocks and compared. To investigate the effect of cumulative water use on the chemical status of the soils of 16 blocks, soil samples were taken and analysed for pH (1M KCl), EC (1:5); soluble cations and anions (Ca, Mg, Na, K, SO4, NO3, and Cl), ammonium acetate extractable cations (Ca, Mg, Na and K) and micro elements (Zn, Fe, Mn, Cu and B). The irrigation requirements predicted by the different irrigation scheduling methods are variable. For Vinet, the irrigation requirement determined for microsprinkler irrigation is much higher than that determined using the evaporation pan or SAPWAT approaches. Comparison of the irrigation applied to each of these blocks does not clarify whether any irrigation scheduling takes place. Results showed a relationship between the yield-irrigation index and income-irrigation index. It has not however been verified whether this relationship is statistically significant.

<p>Most of the city of Uppsala rests on postglacial clay with a varying content of sulphur. The sulphur occurs naturally in the clay in reduced form as sulphide and the clay is for that reason usually called “sulphide clay”. Excavation during construction activities gives rise to large amounts of excavation material, of which the sulphide clay is a considerable part.</p><p>When the clay is exposed to air and water, an oxidation of the sulphides occurs which may produce an acid leachate and the mobilisation of heavy metals bound in the clay or underlying material. The aim of the work has been to improve our understanding of the behaviour of sulphide clays and produce a basis for risk assessment in the future handling of excavation material with high sulphide content. After sampling had been carried out in two places, batch tests were performed to examine the long-term acidification potential of clays with different calcium carbonate content. The tests were performed with continuous air supply and during the experiment leachate water was analysed with respect to pH, alkalinity, dissolved sulphate and mobilised metals. The results from the laboratory study showed that a clay with a high calcium carbonate content and thus a high net neutralisation potential (NNP) will consume the generated acid and prevent against a lowering of the pH.</p><p>In clay lacking calcium carbonate, the pH dropped significantly and caused a mobilisation of chiefly Cd, Mn, Co, Ni, Ca and As. Regardless of the changes in pH over time, a large production of sulphur was observed as a result of the sulphide oxidation. In a risk assessment, it is suggested that the NNP should be determined by methods agreed upon to facilitate future comparisons and because different methods may give different results. A clay with a NNP<5 kg CaCO3/ton should be further analysed with respect to metal content to establish the leachate generation potential and estimate the future environmental influence of the excavation material.</p> / <p>Uppsala stad vilar till stor del på postglacial lera med varierande svavelhalt. Svavlet finns naturligt i leran i reducerad form som sulfid och leran kallas därför vanligtvis för ”sulfidlera”. Vid schaktningsarbete i samband med byggnation uppkommer stora mängder schaktmassor varav en betydande del är sulfidlera.</p><p>Då leran exponeras för luft och nederbörd sker en oxidation av sulfiderna som kan ge upphov till surt lakvatten och läckage av tungmetaller bundna i leran eller underliggande material. Syftet med arbetet har varit att öka kunskaperna om hur sulfidleror beter sig och ta fram ett underlag för riskbedömning i samband med den framtida hanteringen av sulfidhaltiga schaktmassor i Uppsala. Efter genomförd provtagning på två platser utfördes skaktest för att undersöka den långsiktiga försurningspotentialen hos lera med varierande kalkinnehåll. Testerna utfördes med kontinuerlig tillförsel av luft och löpande under försökets gång togs lakvatten ut för analys avseende pH, alkalinitet, löst sulfat och utlakade metaller.</p><p>Resultaten från den laborativa studien visade att en kalkhaltig lera med hög nettoneutralisationspotential (NNP) kan förbruka den bildade syran och därigenom genereras ingen pH-sänkning. I lera som saknar kalk sjönk pH kraftigt och föranledde läckage av framförallt Cd, Mn, Co, Ni, Ca och As.</p><p>Oavsett utvecklingen av pH observerades en stor utlakning av svavel till följd av oxidationen av sulfider. I en riskbedömning föreslås att lerans NNP bestäms enligt överenskomna metoder för att underlätta framtida jämförelser och för att olika tekniker kan ge olika resultat. En lera med NNP-värde < 5 kg CaCO3/ton bör analyseras vidare avseende metallinnehåll för att fastställa den potentiella utlakningen och bedöma schaktmassans framtida naturpåverkan.</p>

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