Thesis (MScIng)--University of Stellenbosch, 2007. / ENGLISH ABSTRACT: Due to economic and environmental constraints mining operations are placed under increasing pressure to effectively manage and operate tailings disposal operations. Restrictions imposed on water usage and tailings operations footprint have led to higher density and wider particle size distribution slurries conveyed to tailings areas. One means of efficiently disposing the tailings is co-disposal. In this method a concentrated fine vehicle slurry is used to convey a coarser fraction. This produces a higher density of tailings, with a number of advantages both upstream and downstream of the tailings process. Limited research has been conducted on the effect of coarse particles on the non-Newtonian rheological properties of these slurries. This lack of information complicates the design and reliable operation of these systems. This project aims at gaining a clearer understanding as to the mechanisms involved in the addition of coarse particles to a fine clay slurry vehicle; and to provide a means of estimating the measured slurry rheological properties. A number of experiments were designed to test the slurry (both Kaolin only, and Kaolin-coarse particle mixtures) rheological properties using a Couette viscometer (for the dynamic flow properties of yield stress and plastic viscosity) and a vane instrument (for the static yield stress measurements). The slurries were prepared in varying Kaolin clay solids concentrations with reverse osmosis water. Glass beads and two types of industrial sand were used as the coarse fractions. All of the coarse particles had a similar size but varied significantly in shape. Slurry pH and temperature readings were monitored throughout the tests. Tests were done initially on clay only slurries. The rheological properties of these slurries were repeatable, and no noticeable variations of properties with time were observed. The yield stress (both static and dynamic) and plastic viscosity data were well correlated with established relationships. Coarse particles were added to the clay only slurries, and then removed. The remaining clay only slurry exhibited the same rheological properties as the initial clay only slurry. The presence of coarse particles increased all the measured rheological properties (i.e. dynamic yield stress, Bingham viscosity, and static vane yield stress) in a fashion resembling the effect of adding clay to a clay only slurry. In addition, the change in measured rheological property by addition of coarse particle was independent of the clay fraction in the clay slurry. Furthermore, with both the clay only slurries and clay and coarse sand slurries, a constant linear relationship existed between the static and dynamic yield stress. Several correlations from the literature were found to provide reasonable prediction of the rheological property variations observed. These empirical and semi-empirical models however did little to explain the mechanisms involved in coarse particle addition. A new correlation has been proposed, Residual Clay Concentration, which predicts the change in rheological property based on an additional clay concentration, which in turn is a linear function of the coarse particle concentration. The accuracy of this model further strengthens the belief that the coarse particle acts in a similar fashion to a floc. By means of a case study example the importance of selecting an appropriate model for design was illustrated. The Residual Clay Concentration method provided the most conservative results. This combined with its theoretical basis strengthens the models recommendation for use in design. / AFRIKAANSE OPSOMMING: As gevolg van ekonomiese en omgewings beperkinge word mynwese nywerhede onder toenemende druk geplaas om doeltreffende afvalstroom bestuur en operasie toe te pas. Beperkinge geplaas op water gebruik en afvalstroom area-groote ly tot hoër digthede en wyer partikel-grooteverspreidings van flodders vervoer na afval areas. Een manier om van die afval doeltreffend ontslae te raak en te berg is deur medeberging. In die metode word ‘n gekonsentreerde fyn flodder gebruik as draer van ‘n growwer partikel-fraksie. Dit ly tot ‘n hoër digtheid flodder, met verskeie voordele in beide die op – en afstroom prosesse. Beperkte navorsing is gedoen op die effek van growwe partikels op die nie-Newoniese rheolgiese eienskappe van hierdie flodders. Hierdie tekort aan informasie maak die effektiewe, betroubare bedryf en operasie van die sisteme meer ingewikkeld. Hierdie projek is daarheen gemik om ‘n beter begrip te ontwikkel met betrekking tot die meganismes betrokke in die byvoeging van growwe partikels aan ‘n fyn klei-agtige flodder draer; en om ‘n manier te voorsien wat die rheologiese eienskappe kan beraam. Verskeie eksperimente was ontwerp om die flodders (beide slegs Kaolien, en Kaoliengrowwe partikel mengsels) se rheologiese eienskappe te toets deur die gebruik van ‘n Couette-viskometer. Die Couette viskometer was gebruik om die dinamiese eienskappe (van grens-spanning, en plastiese viskositet) te meet. ‘n Vaan apparaat is gebruik om die eienskap van statiese grens-spanning te meet. Die flodders was voorberei in verskeie Kaolien konsentrasies met tru-osmosis water. Glas krale en twee tipes industriële sand is gebruik as die growwe fraksies. Al die growwe partikels het soortgelyke groottes gehad, maar het grootliks verskil in vorm. Die flodder pH en temperatuur lesings is deurentyd nagegaan. Toetse was aanvanklik gedoen op die klei-alleenlike flodders. Die gemete reologiese eienskappe van die flodders was herhaalbaar, en geen opmerkbare veranderinge van die eienskappe met betrekking tot tyd is gemeet nie. Die grens-spanning (beide statiese en dinamiese) en plastiese viskositeit is goed gekorrelleer met gevestigde verhoudinge. Growwe partikels is aan die klei-alleenlike flodders bygevoeg, en daarnae verwyder. Die oorblywende klei-alleenlike flodder het dieselfde gemete rheologiese eienskappe getoon as die oorspronklike klei-allenlike flodder. Die teenwoordigheid van growwe partikels het na ‘n toename van al die gamete rheologiese eienskappe gelei wat fisies baie soortgelyk is aan die byvoeging van klei tot ‘n klei-alleenlike flodder. Verder, met beide die klei-alleenlike en klei-growwe partikel flodders het ‘n konstante liniëre funksie tussen die statiese en dinamiese grens-spannings bestaan. Verskeie verhoudings uit die literatuur het goeie korrelasie bewerkstellig met die waargenome rheologie veranderinge. Hierdie empiriese en semi-empiriese modelle doen egter min om die megansimes betrokke in die toevoeging van growwe partikels te verduidelik. ‘n Nuwe korrelasie is voorgestel, naamlik die Residu Klei Konsentrasie. Hierdie model voorspel die verandering in reologiese eienskappe gebaseer op ‘n addisionele klei konsentrasie, wat ‘n liniëre funkise is van die growwe partikel konsentrasie. Die goeie korrelasie gesien met die model versterk die idée dat die growwe partikel in ‘n soortgelyke manier as ‘n flok gedra in die teenwoordigheid van ander flokke. Deur middel van ‘n tipiese industriële voorbeeld is die belangrikheid in die keuse van die regte korrelasie geillustreer. Die Residu Klei Konsentrasie metode het die mees konservatiewe resultate gelewer. Hierdie feit gekombineerd met die model se soliede teoreitiese beginsels versterk dit as voorgestelde korrelasie vir ontwerp.

Thesis (MScEng (Process Engineering))--Stellenbosch University, 2008. / Please refer to full text to view abstract.

Thesis (MScEng (Process Engineering))--Stellenbosch University, 2010. / ENGLISH ABSTRACT: Recently, improved technologies have been developed for the biobutanol fermentation process: higher butanol concentrations and productivities are achieved during fermentation, and separation and purification techniques are less energy intensive. This may result in an economically viable process when compared to the petrochemical pathway for butanol production. The objective of this study is to develop process models to compare different possible process designs for biobutanol production from sugarcane molasses. Some of the best improved strains, which include Clostridium acetobutylicum PCSIR-10 and Clostridium beijerinckii BA101, produce total solvent concentrations of up to 24 g/L. Among the novel technologies for fermentation and downstream processing, fedbatch fermentation with in situ product recovery by gas-stripping, followed by either liquid-liquid extraction or adsorption, appears to be the most promising techniques for current industrial application. Incorporating these technologies into a biorefinery concept will contribute toward the development of an economically viable process. In this study three process routes are developed. The first two process routes incorporate well established industrial technologies: Process Route 1 consist of batch fermentation and steam stripping distillation, while in Process Route 2, some of the distillation columns is replaced with a liquid-liquid extraction column. The third process route incorporates fed-batch fermentation and gas-stripping, an unproven technology on industrial scale. Process modelling in ASPEN PLUS® and economic analyses in ASPEN Icarus® are performed to determine the economic feasibility of these biobutanol production process designs. Process Route 3 proved to be the only profitable design in current economic conditions. For the latter process, the first order estimate of the total project capital cost is $187 345 000.00 (IRR: 35.96%). Improved fermentation strains currently available are not sufficient to attain a profitable process design without implementation of advanced processing techniques. Gas stripping is shown to be the single most effective process step (of those evaluated in this study) which can be employed on an industrial scale to improve process economics of biobutanol production. / AFRIKAANSE OPSOMMING: Onlangse verbeteringe in die tegnologie vir die vervaardiging van butanol via die fermentasie roete het tot gevolg dat: hoër butanol konsentrasies en produktiwiteit verkry kan word tydens die fermentasie proses, en energie verbruik tydens skeiding-en suiweringsprosesse laer is. Hierdie verbeteringe kan daartoe lei dat biobutanol op ʼn ekonomiese vlak kan kompeteer met die petrochemiese vervaardigings proses vir butanol. Die doelwit van die studie is om proses modelle te ontwikkel waarmee verskillende proses ontwerpe vir die vervaardiging van biobutanol vanaf suikerriet melasse vergelyk kan word. Verbeterde fermentasie organismes, wat insluit Clostridium acetobutylicum PCSIR-10 en Clostridium beijerinckii BA101, het die vermoë om ABE konsentrasies so hoog as 24 g/L te produseer. Wat nuwe tegnologie vir fermentasie en skeidingprosesse behels, wil dit voorkom of wisselvoer fermentasie met gelyktydige verwydering van produkte deur gasstroping, gevolg deur of vloeistof-vloeistof ekstraksie of adsorpsie, van die mees belowende tegnieke is om tans in die nywerheid te implementeer. Deur hierdie tegnologie in ʼn bioraffinadery konsep te inkorporeer sal bydra tot die ontwikkeling van ʼn ekonomies lewensvatbare proses. Drie prosesserings roetes word in die studie ontwikkel. Die eerste twee maak gebruik van goed gevestigde industriële tegnologie: Proses Roete 1 implementeer enkellading fermentasie en stoom stroping distillasie, terwyl in Proses Roete 2 van die distilasiekolomme vervang word met ʼn vloeistof-vloeistof ekstraksiekolom. Die derde proses roete maak gebruik van wisselvoer fermentasie met gelyktydige verwydering van produkte deur gas stroping. Die tegnologie is nog nie in die nywerheid bewys of gevestig nie. Om die ekonomiese uitvoerbaarheid van die proses ontwerpe te bepaal word proses modellering uitgevoer in ASPEN PLUS® en ekonomiese analises in ASPEN Icarus® gedoen. Proses Roete 3 is die enigste ontwerp wat winsgewend is in huidige ekonomiese toestande. Die eerste orde koste beraming van die laasgenoemde projek se totale kapitale koste is $187 345 000.00 (opbrengskoers: 35.96%). Die verbeterde fermentasie organismes wat tans beskikbaar is, is nie voldoende om ʼn proses winsgewend te maak nie; gevorderde proses tegnologie moet geïmplementeer word. Gasstroping is bewys as die mees effektiewe proses stap (getoets in die studie) wat op industriële skaal geïmplementeer kan word om die winsgewendheid van die biobutanol proses te verbeter. / Centre for Renewable and Sustainable Energy Studies

Thesis (MScEng (Chemical Engineering))--University of Stellenbosch, 2001. / 304 leaves single sided printed,preliminary pages i-xxii and numberd pages 1-282. Includes bibliography,list of figures and tables, used a Bizhub 250 Scanner to pdf format (OCR) 57pages contain figures in color.Digitized at 300 dpi 24-bit Color to pdf format (OCR),used a Hp Scanjet 8250 / ENGLISH ABSTRACT: Ecosystems and natural water sources are constantly under threat from pollutants and all efforts should be made to minimise polluting factors. In the last decade growing concern has been expressed with regard to the environmental threat posed by wastewater produced by wineries and distilleries. Research into winery wastewater commenced in the early nineties mainly in Australia and France. These investigations characterised winery wastewater, indicating a large diversity in quality and quantity between wastewaters emanating from wineries. Owed to changes in South African legislation, in conjunction with an augmented environmental awareness, the need for an environmental assessment of wineries became apparent. In South Africa, research of this nature had not yet been conducted. Previous research on winery wastewater treatment employed mostly biological technologies, with success but also shortfalls. In South Africa the majority of wineries are located in the Western Cape Province, several within the same water catchment area. Wineries may produce approximately 1 to 10 litres of wastewater per litre of wine produced, which are turbid and acidic and typically contain high levels of organic compounds (thus oxygen deficient), and suspended material. Usually these wastewaters are irrigated onto land, in close proximity to natural water resources. The pollution of water tables and down-stream water sources may occur. The quantification, qualification and treatment of this type of wastewater are addressed in this study. Winery wastewater produced from the predominantly red wine producing Rupert and Rothschild Vignerons, served as case study for a two-year wastewater audit strategy. The most common analyses performed on winery wastewater include the Chemical Oxygen Demand (COD), suspended solids (SS), pH and turbidity. A thorough analysis in the form of a comprehensive audit was performed on the water and vinification processes. This allowed for an accurate determination of contamination sources and properties. The audit entailed a designed sampling protocol, the format of which was tailored as an initial environmental assessment for the development of an Environmental Management System (EMS) unique to Rupert and Rothschild Vignerons. The EMS includes projected future objectives for wastewater quality (COD, SS, pH, turbidity), as well as an environmental policy. In order to reach the proposed quality objectives, a suitable wastewater treatment system must be installed. The efficiency of the treatment system present at Rupert and Rothschild Vignerons was evaluated and piloted the investigation of physico-chemical treatment technologies. Research into the applicability of induced sedimentation (coagulation) and chemical oxidation (ozone) was the first of its kind for winery wastewater as substrate, and provided an interesting dimension in the sense of pragmatic and economic feasibility. Dissolved and suspended particles present in winery wastewater do not settle by gravity alone, thus requiring sedimentation agents (coagulants). Benchscale experiments were conducted employing four types of pre-polymerised metal salt coagulants (polyaluminium chloride). Successful sedimentation of turbidity inducing compounds (up to 98 %) and suspended solid fractions (up to 92%) was achieved. These coagulants are highly suitable for the treatment of winery wastewater since the investigation showed that they are effective over a broad pH and dosage range. In addition, rapid sedimentation rates were observed, favouring thickener design economy. Ozone is a potent oxidising agent, and has been reported to increase the biodegradability of dissolved organic compounds and result in the decolouring of wastewaters. Ozonation is highly pH dependent, with hydroxyl radical activity dominating at alkaline pH. In the majority of gas-liquid contacting systems, the kinetics of the heterogeneous reaction is not limited by the chemical reaction rate, but by the transport of ozone to the liquid phase. To compensate, the ozone concentration in the gas phase is increased. Coupled to the primary investigation on the applicability of ozone treatment for winery wastewater, thus emerged a secondary investigation into an enhanced mass transfer system, realised by the use of impinging stream technology. The ozone transfer in a conventional bubble-column was compared to that of an impinging-stream jet-reactor. The latter significantly improved the ozone transfer to the winery wastewater, resulting in the rate-limiting step being the chemical reaction rate. Ozonation resulted in the increased biodegradability of the winery wastewater, and complete colour and odour elimination. Concerning jet-reactors, the principal importance lies in the substantial reduction in the initial ozone concentration requirement, thereby rendering the process more economically feasible. Following the investigation of the wastewater dynamics, the determination of eco-toxicology during irrigation should be conducted in future. When considering induced sedimentation, further studies should be directed towards ascertaining the most economic yet efficient dosage of the coagulant. Similarly, a study concerning the economic viability of ozone efficiency should be realised in terms of the energy requirements for both ozone generation and the operation of jet-reactors. Although the jet reactor poses a benefit for enhanced mass transfer, the essential criterion concerning residence time in the reactor must be addressed for positive results. Since no single solution exists for the treatment of winery wastewaters, the application of the considered technology must be carefully selected and incorporated in a treatment design; the two foremost criteria for selection being efficiency and economy. / AFRIKAANSE OPSOMMING: Ekologiese stelsels en natuurlike waterbronne word gedurig bedreig deur besoedeling, dus moet ten aile tye gepoog word om besoedeling te minimiseer of te voorkom. Gedurende die laaste dekade is al hoe meer kommer uitgespreek oor die besoedeling van afloop water afkomstig van wyn en spiritualiee-vervaardiging. Navorsing aangaande wynafloopwater het ontstaan in die vroee negentigs, hoofsaaklik in Australie en Frankryk. Hierdie navorsing het gelei tot die karakterisering van wynafloopwater, en die uiteenlopendheid van hierdie water aangaande die kwaliteit en kwantiteit tussen kelders, is aangetoon. As gevolg van veranderinge in die SuidAfrikaanse wetgewing, asook 'n groeiende bewuswording van omgewingsake, het die noodsaaklikheid van omgewings impak-studies vir wynkelders na vore getree. Tot op hede is navorsing van hierdie aard nog nie in Suid Afrika gedoen nie. Vorige navorsing op die behandeling van wynafloopwater het meestal biologiese tegnologiee behels, met 'n mate van sukses maar ook met tekortkominge. Die meederheid wynkelders in Suid Afrika is in die Wes-Kaap gelee, baie binne dieselfde opvanggebied. Wynkelders kan tussen 1 tot 10 liter afloop water produseer per liter wyn geproduseer. Hierdie afloop het tipies 'n hoe konsentrasie organiese stowwe (is dus arm aan suurstof), is troebel en suur, en bevat gesuspendeerde materiaal. Gewoonlik word die wynafloop water besproei in die nabyheid van natuurlike waterbronne. Die besoedeling van watertafels en waterbronne kan dus plaasvind. Die kwantifisering, kwalifisering en behandeling van wynafloopwater word ondersoek in hierdie tesis. Die wynafloopwater van die hoofsaaklik rooiwyn produserende Rupert en Rothschild Vignerons, het gedien as proefstudie tydens 'n twee-jaar wynafloopwateroudit. 'n Deeglike analise in die formaat van 'n veelomvattende oudit is uitgevoer op die wynmaakproses en die waterafvoerstrome. 'n Akkurate bepaling van die oorsprong van waterkontaminasie, asook die eienskappe daarvan is bewerkstellig. Die oudit behels 'n spesifiek ontwerpte monsternemingprotokol, waarvan die formaat geformuleer is om te dien as 'n beginpunt vir die ontwikkeling van 'n Omgewingsbestuurstelsel (08S), uniek vir Rupert en Rothschild Vignerons. Hierdie 08S sluit toekomstige doelstellings vir die kwaliteit (chemiese suurstofbehoefte, gesuspendeerde vaste stowwe, pH, turbiditeit) van wynafloopwater in, asook 'n omgewingsbeleid. Die installering van 'n waterbehandelingsisteem moet geskied om te voldoen aan hierdie voorgestelde doelstellings. Die effektiwiteit van die huidige behandeling sisteem teenwoordig by Rupert en Rothschild Vignerons is geevalueer en het gelei tot navorsing oor fisieschemiese behandelingstegnologiee. Navorsing aangaande die toepassing van geinduseerde sedimentasie (koagulasie) en chemiese oksidasie (osoon), is vir die eerste keer toegepas op wynafloopwater, en het interessante gevolge in 'n pragmatiese en ekonomiese sin. Opgelosde en gesuspendeerde partikels teenwoordig in wynafloopwater sak nie onder normale gravitasie uit nie, en dus word die toediening van sedimentasie-induserende middels benodig. Eksperimente is in die laboratorium uitgevoer met vier verskillende gepolimeriseerde metaalsoutkoagulante (poli-aluminiumchloriedes). Dit het gelei tot die effektiewe sedimentering van stowwe wat troebelheid (turbiditeit) veroorsaak (tot 98 %) en ook gesuspendeerde stowwe (tot 92 %). Dit is gevind dat hierdie tipe koagulante hoogs geskik is vir die behandeling van wynafloop water, aangesien hulle effektief is by 'n wye pH- en doseringsreeks. Die uitsaktempo is vinnig, wat dus die ontwerp van 'n uitsaktenk (verdikker) ekonomies maak. Osoon is 'n sterk oksideermiddel, terwyl talle verslae aandui dat dit die biologiese ontbinding van opgelosde stowwe verhoog en die ontkleuring van afloopwaters tot. gevolg het. Osonering is pH afhanklik; by alkaliese pH oorheers die werking van hidroksielradikale. In die meerderheid gasvloeistofkontaksisteme word die kinetika van die heterogene chemiese reaksie nie beperk deur die intrinsieke reaksietempo nie, maar deur die vervoer van osoon na die vloeistoffase. Om te kompenseer hiervoor, word die osoon konsentrasie in die gasfase verhoog. Gekoppel aan die primere ondersoek aangaande die toepasbaarheid van osoonbehandeling op wynafloopwater, het 'n tweede ondersoek onstaan aangaande verhoogde massa-oordragssisteme deur die gebruik van hoeintensiteit spuitreaktore. Die osoonoordrag in konvensionele borrelkolomme is vergelyk met die van 'n hoe intensiteit spuitreaktor. Laasgenoemde het die osoonoordrag na die wynafloopwater aansienlik verhoog, met die gevolg dat die chemiese reaksie die beperking op die reaksie tempo geplaas het. Osonering het die biodegradasie van die wynafloop water verhoog, asook die kleur en reuk verwyder. By die spuit-reaktor Ie die belangrikheid daarin by die aansienlike veriaging in die aanvanklike behoefte aan osoonkonsentrasie, derhalwe is hierdie oordragsisteem meer ekonomies. Na afloop van die ondersoek op die dinamika van wynafloopwater, moet die ekotoksisiteit gedurende besproeiing bepaal word vir toekomstige doeleindes. Indien ge"induseerde sedimentasie verlang word, kan verdere studie gedoen word om die mees ekonomiese dosis van die koagulant te bepaal. Ooreenstemmend, moet die ekonomiese lewensvatbaarheid van die osoon effektiwiteit bepaal word ten opsigte van die energiebehoefte van beide die osoongenerasie en die werking van die hoe-intensiteit spuitreaktor. Alhoewel die spuitreaktor verhoogde massa-oordrag bewerkstellig, moet die effek van die residensietyd in die reaktor inag geneem word word ten einde positiewe resultate te verkry. Geen enkele oplossing bestaan vir die behandeling van wynafloop water nie, derhalwe moet die toepassing van die beoogde sisteem versigtig gekies word en ingesluit word in die ontwerp van 'n behandelingsisteem; die twee vernaamste maatstawwe is ondermeer effektiwiteit en ekonomiese aspekte.

Thesis (MScEng (Process Engineering))--University of Stellenbosch, 2010. / Thesis submitted in partial fulfilment of the requirements for the degree of MASTER OF SCIENCE IN ENGINEERING (MINERAL PROCESSING) in the Department of Processing Engineering at the University of Stellenbosch / ENGLISH ABSTRACT: This work evaluates the use of inverse least squares (ILS) and classical least squares (CLS) models for calibration of a diffuse reflectance spectrophotometer for on-line monitoring of the aqueous phase in a flotation cells. Both models use a Beer's law for the quantification of the metals. The formulated statistical models are compared to a proprietary Blue Cube model in terms of prediction ability to determine the potential applicability of the models. A diffuse reflectance spectrophotometry was used for simultaneous analysis of copper (Cu), cobalt (Co) and zinc (Zn) in the solutions. The laboratory set-up of Blue Cube instrument was used for the experimental analysis. The concentrations and matrix compositions of the samples are simulated according to Skorpion zinc mine plant conditions. The calibration samples were prepared using a simplex-centroid mixture design with the triplicates of the centroid run. The unknown or test samples were prepared randomly within the same concentration of the calibration samples. The effects of temperature and nickel concentration on absorption of the metals were evaluated in the following range, 20 - 80 °C and 125 - 400 ppm, respectively. The statistical models (ILS and CLS) were calibrated from visible and near infrared (VNIR) spectra data of the calibration samples. A modified Beer's method was used as a preprocessing technique to convert the raw data into absorbance values. The manual wavelength selection procedure was used to select the wavelengths to be used in both models. The quality of the models was evaluated based on Rª and % root mean squared error (RMSE) values with 0.90 and 10% used as the guideline for the respective statistical parameters. Both ILS and CLS models showed good results for all three metals (Cu, Co and Zn) during their calibration steps. It was further shown that both models give worse predictions for Zn as compared to other metals due to its low relative intensity in the mixture. The derivative orders of absorbance spectra that were used to enhance the prediction results of Zn had no positive effect but they rather lowered accuracy of predictions. An increase in temperature was found to increase the intensities of the absorption spectra of all the metals while an increase in nickel concentration decreases the prediction ability of model. The developed statistical models were compared to a Blue Cube model in terms of prediction ability using analysis of variance (ANOVA) test. The ANOVA results revealed that there is no statistical difference between the developed models and Blue Cube model since the F-values for all the metals were below the critical F-value. Furthermore, the partial least squares (PLS) model shows an increased accuracy results for prediction of zinc metal as compared to both the ILS and CLS models. Finally, good comparisons of the statistical models results with atomic absorption spectroscopy (AAS) analyses were establish for the unknown samples. The study demonstrates that chemometric models (ILS and CLS) developed here can be used for quantification of several metals in real hydrometallurgical solutions as samples were simulated according to a plant conditions. However, in order to have confidence in the results of the models, a factorial-mixture design must be used to study the effect of temperature and nickel concentration. Moreover the models must be further tested and validated on the real samples from a plant. / AFRIKAANSE OPSOMMING: Hierdie werkstuk evalueer die gebruik van inverse kleinste kwadraatmetodes (IKK) en klassieke kleinste kwadraatmetodes (KKK) vir die kalibrasie van 'n diffuse reflektansiespektrofotometer vir die aanlyn monitering van die waterige fase in flottasieselle. Beer se wet word vir die kwantifisering van metale vir albei modelle gebruik. Die omskrewe data-gebaseerde modelle is op grond van voorspellingsvermoë vergelyk met'n. Blue Cube model, sodat die moontlike toepaslikheid van hierdie modelle bepaal kan word. 'n Diffuse reflectantie spektrofotometrie is ingespan vir die gelyktydige analise van koper (Cu), kobalt (Co) en sink (Zn) in oplossing. Eksperimentele analises is met behulp van 'n laboratoriumopstelling met 'n Blue Cube instrument uitgevoer. Die konsentrasies en matriks-samestellings van monsters is gesimuleer om Skorpion sinkmyn aanlegkondisies na te boots. Kalibrasie monsters is voorberei volgens . simpleks-sentroïed mengselontwerp met drievoudige sentroïede lopies. Onbekende (toets) monsters is ewekansig voorberei binne dieselfde konsentrasie spesifikasies as die kalibrasie monsters. Die invloed van temperatuur en nikkelkonsenstrasie op die absorpsie van die metale is in die bestek van 20 - 80 °C en 125 - 400 dpm, onderskeidelik, bepaal. Die data-gebaseerde modelle (IKK en KKK) is met sigbare en naby infrarooi (SNIR) spektra data van die kalibrasie monsters gekalibreer. 'n Gewysigde Beer metode is vir data voorbereiding benut om rou data na absorbansie waardes om te skakel. Die handgolflengte-seleksieprosedure is vir beide modelle gebruik om die golflengtes te kies. Die kwaliteit van die modelle is op grond van Rª en % wortel gemiddelde kwadratiese fout (WGKF) geevalueer, met waardes van 0.90 en 10% (onderskeidelik) as riglyne vir hierdie statistiese parameters. Beide IKK en KKK modelle het vir hul kalibrasie stappe vir al drie metale (Cu, Co en Zn) goeie resultate getoon. Dit is verder getoon dat albei modelle die slegste voorspellings lewer vir Zn (vergeleke met die ander metale) as gevolg van Zn se lae relatiewe intensiteit in die mengsel. Afgeleide ordes van absorbansie spektra is gebruik om die Zn voorspellings te versterk, maar het geen positiewe effek gehad nie; inteendeel, voorspellingakkuraatheid is verlaag. ʼn Verhoging in temperatuur het die intensiteite van die absorpsie spektra van alle metale verhoog, terwyl ʼn verhoging in nikkelkonsentrasie die voorspellingakkuraatheid van die modelle verlaag het. Die ontwikkelde data-gebaseerde modelle is met ʼn Blue Cube model vergelyk in terme van voorspellingsvermoë met behulp van variansie-analise (ANOVA). Die ANOVA resultate toon dat daar geen statistiese verskil tussen die ontwikkelde modelle en die Blue Cube model is nie, aangesien die F-waardes vir al die metale onder die kritiese F-waarde is. Die gedeeltelike kleinste kwadraatmodel (GKK) toon verder verhoogde voorspellingakkuraat-heid vir sinkmetaal tenoor beide die IKK en KKK modelle. Ten slotte, goeie ooreenstemming van die data-gebaseerde modelresultate met atoomabsorpsie spektroskopie (AAS) analise is vir die onbekende monsters gevind. Hierdie werkstuk toon dat die chemometriese modelle (IKK en KKK) wat hier ontwikkel is, gebruik kan word vir die kwantifisering van verskeie metale in werklike hidrometallurgiese oplossings, aangesien monsters gesimuleer is volgens aanlegkondisies. Om egter verdere vertroue te hê in die modelresultate, sal ʼn faktoriaal-mengselontwerp toegepas moet word om die effek van temperatuur en nikkelkonsentrasie te ondersoek. Voorts moet die modelle verder getoets en gevalideer word op werklike monsters van ʼn aanleg.

Thesis (MScEng (Process Engineering))--University of Stellenbosch, 2010. / ENGLISH ABSTRACT: Previous work has shown that microwave heating of mineral ores induces micro cracks within the ore structure, which can be attributed to the difference in the adsorption of microwaves amongst the different mineral phases. This reduces the energy required during subsequent grinding and enhances the liberation of valuable minerals. In order to design microwave applicators for this purpose, knowledge of the effective dielectric properties of the crushed ore is required. Of particular interest is the effective complex permittivity of the bulk crushed ore. The measurement of the effective permittivity of a large volume of crushed ore is most readily accomplished using the waveguide measurement technique. In this method a representative sample of the material is placed in a defined and fixed volume in a standard size rectangular section metallic waveguide. The magnitude and phase angle of the transmitted and reflected low power microwaves through and from the sample are measured. The complex permittivity can be extracted from these so-called scattering, or Sij parameters. In this study the effective complex permittivities for two porphyry copper ores and a copper carbonatite ore were determined as a function of particle size distribution (-26.5+2mm) using two sizes of waveguide (WR284 and WR340). The sample holders incorporate dielectric windows for the location of the material under test. The extraction of dielectric properties from Sij parameter measurements is problematic using standard algorithms in such cases. Accordingly a new Database Extraction (DBE) Algorithm has been developed. In this method, a database of scattering parameters is established through electromagnetic modelling of the measurement system. A search algorithm is used to determine the effective complex permittivity of the modelled load whose scattering parameters provide the best fit to the experimental data. The goodness of the experimental fit of the simulated to the measured Sij parameters is determined by a root mean squared deviation minimisation metric. Results show that the method can be used successfully to determine an effective complex permittivity for a bulk volume of the crushed material. It is concluded that the dielectric property extraction over the full operational frequency interval (2.3-3 GHz) is preferred as it has a larger degree of extraction confidence and hence reliability. Results show that with increasing particle size, the experimental fit between the simulated and measured Sij parameters becomes increasingly poor, as wall effect become more prominent. The effect is most prominent for the smaller WR284 waveguide size. It is shown that for a waveguide size of similar size to the particle size, the Sij parameter fitting is poorer compared to when a larger waveguide size is used. The extracted complex permittivity reproducibility between repeated dielectric property measurements is improved for the WR340 waveguide size, as the extractions in the WR284 waveguide is dominated by the combined particle size and wall-effects of the sample holder. Ore mineralogy is identified as a key parameter that influences the dielectric properties of the crushed ore. For ores with a dominant microwave absorbent mineral phase, the dielectric constant and loss factor is found to be larger, compared with ores with a more dominant microwave transparent gangue mineral phase. / AFRIKAANSE OPSOMMING: Navorsing toon dat die verhitting van mineraal erts, met mikrogolwe, mikroskaal frakture in die mineraalstruktuur teweeg bring weens die verskil in die adsorpsie van mikrogolwe in die verskillende mineraalfases. Gevolglik verminder die energievereiste vir die vergruising van die erts en verbeter die vrystelling van waardevolle minerale wat vasgevang is in die mineraalmatriks. Vir die ontwerp van mikrogolfapplikators vir dié doel, word die effektiewe diëlektriese eienskappe van die vergruisde erts benodig. Van spesifieke belang is die effektiewe komplekse permittiwiteit van die erts. Die effektiewe permittiwiteit van `n vergruisde materiaal monster word met behulp van die golfgeleier tegniek gemeet. Vir dié tegniek word `n verteenwoordigende monster van die materiaal in `n rigiede volume in `n standaard grootte reghoekige golfgeleier geplaas. Die grootte en fasehoek komponente van die deurgelate en weerkaatste mikrogolwe deur en van die oppervlak van die materiaal word gemeet. Die komplekse permittiwiteit van die vergruisde materiaal kan geëkstrakteer word vanaf hierdie sogenaamde verspreide, of Sij parameters. In hierdie studie word die effektiewe permitiwiteit van twee porforie koper ertse en `n koper karbonatiet erts bepaal as funksie van partikel grootte (-26.5+2 mm) deur gebruik te maak van twee standaard grootte golfgeleiers. Die monster houers inkorporeer diëlektriese vensters om die vergruisde materiaal monster in posisie te hou. In so `n geval is die ekstraksie van die diëlektriese eienskappe vanuit die Sij parameter metings problematies. Gevolglik is ‘n nuwe Databasis Ekstraksie Algoritme ontwikkel wat `n databasis van verspreide parameters opstel deur die elektromagnetiese simulasie van die metingsisteem. `n Soek-algoritme word gebruik om die effektiewe komplekse permitiwiteit van die gesimuleerde monster te bepaal wat die beste ooreenstem met dié van die gemete eksperimentele Sij parameter data. Die mate van ooreenstemming tussen die parameters, word bepaal aan die hand van die minimaliserings prosedure. Resultate toon dat dié metode geskik is vir die bepaling van die effektiewe komplekse permitiwiteit van die vergruisde monster. Dit word vasgestel dat die betroubaarheid van die geëkstraeerde Sij parameters, en gevolglik die diëlektriese eienskappe van die erts, toeneem indien die algoritme oor `n groter frekwensie band uitgevoer word. Resultate toon verder dat met toenemende partikel grootte, die mate waartoe die absolute grootte en fasehoek komponente van die gesimuleerde en gemete Sij parameters ooreenstem, versleg. Dit word toegeskryf aan wand-effekte. Hierdie verskynsel is veral opmerklik vir die kleiner grootte golfgeleier. Dit word getoon dat vir metings waar die golfgeleier dieselfde orde grootte geometriese afmetings het as die vergruisde erts self, die passing tussen die gesimuleerde en gemete Sij parameters swakker is, wanneer dit vergelyk word met metings waar dit nie die geval is nie. Die reproduseerbaarheid van die geëkstraeerde diëlektriese eienskap waardes verbeter vir lesings wat uitgevoer word in `n groter grootte golfgeleier. Laasgenoemde word toegeskryf aan die meer dominante wand-effekte wat kenmerklik is vir `n kleiner golfgeleier. Erts mineralogie word geïdentifiseer as `n sleutel parameter wat die diëlektriese eienskappe van die vergruisde materiaal beïnvloed. Beide die diëlektriese konstante en verliesfaktor is groter vir ertse met `n oorheersende mikrogolf absorberende mineraalfase.

Thesis (PhD)--Stellenbosch University, 2014. / ENGLISH ABSTRACT: Data on the process performance at different operating conditions are required to determine the feasibility of a separation process. Such data can be experimentally measured, but due to the time and costs associated with pilot plant scale experiments, the use of predictive process models are often preferred. The main aim of this project is to establish a working process model in Aspen Plus® that can be used to predict the separation performance of a supercritical fluid fractionation process aimed at the separation of mixtures of detergent range alkanes and alcohol isomers where similar boiling points or low relative volatilities can occur. Currently, an azeotropic distillation process is employed for the separation of detergent range alkanes and alcohols. Although this process shows good separation performance, some concerns regarding the operating conditions are raised: the preferred entrainer, diethylene glycol, is toxic to humans; very low operating pressures of 0.016 – 0.031 MPa and high temperatures of 473 K are required; additional processing units and materials are required to remove the entrainer from the product streams. An alternative process, supercritical fluid fractionation, is proposed in this work after previous studies have reported that this process have potential for the separation of alkanes and alcohols. The supercritical fluid fractionation process addresses the concerns of the azeotropic distillation process in the following ways: a non-toxic solvent, CO2, is used as the separating agent; mild temperatures of 344 K is proposed, but at the cost of the low operating pressures of the azeotropic process; and a single process unit and no additional material is required to separate the solvent from the product streams. A process model was developed in Aspen Plus® to evaluate the separation performance of the newly proposed supercritical fluid fractionation process and compare it to the current azeotropic distillation process. The development of the process model included the development of an accurate thermodynamic model in Aspen Plus®. After thorough evaluation of a number of cubic equations of state, the RK-ASPEN model was found to be superior in its representation and prediction of phase transition pressures for multi-component mixtures of detergent range alkanes and alcohols in the temperature range 318 – 348 K. Phase transition pressures could be predicted with an error of less than 6 % with the inclusion of regressed polar parameters and binary solute-solvent interaction parameters for two multi-component mixtures: CO2 + (20 % n-dodecane + 70 % 1-decanol + 10 % 3,7-dimethyl-1-octanol) and CO2 + (25 % n-decane + 25 % 1-decanol + 25 % 3,7-dimethyl-1-octanol + 25 % 2,6-dimethyl-2-octanol). Polar parameters were regressed from pure component vapour pressure data predicted with correlations available in Aspen Plus®. Binary interaction parameters were regressed from experimental bubble and dew point data. Binary bubble and dew point data were measured for a number of systems containing ethane or CO2 and a C10-alkane or C10-alcohol isomer at temperatures between 308 K and 353 K, and compositions ranging between 0.01 and 0.7 mass fraction solute. A comparison between the phase equilibrium data measured for these systems revealed that the structure of the molecule, and not only the molecular weight, influences its solubility in the supercritical solvent. The phase transition pressures of n-decane, 2-methylnonane, 3-methylnonane and 4-methylnonane did not differ significantly in CO2 or ethane, and these compounds will in all likelihood not be separated in a supercritical fluid fractionation process. The phase transition pressures measured for the C10-alcohol isomers decreased in both CO2 and ethane in the following order: 1-decanol, 3,7-dimethyl-1-octanol, 2-decanol, 2,6-dimethyl-2-octanol and 3,7-dimethyl-3-octanol. The position of the hydroxyl group and the number, length and position of the side branches, all influence the solubility behaviour and phase transition pressures of the isomeric alcohols in the supercritical solvent. Since the use of ethane did not show any significant benefits with regard to selectivity, the use of the less harmful and less expensive solvent, CO2, in further investigations was justified. The RK-ASPEN thermodynamic model, with the inclusion of the regressed polar and binary solute-solvent interaction parameters, was implemented in the process model and the separation performance of the process was simulated at different operating conditions for the CO2 + (25 % n-decane + 25 % 1-decanol + 25 % 3,7-dimethyl-1-octanol + 25 % 2,6-dimethyl-2-octanol) mixture. A comparison to experimental pilot plant data revealed that the model cannot be used to predict the separation performance at low fractionation temperatures (316 K) due to shortcomings in the thermodynamic model. However, the performance of the process at high fractionation temperatures (344 K) could be predicted well, with an error of 10 – 36 %. Simulations for the CO2 + (25 % n-decane + 25 % 1-decanol + 25 % 3,7-dimethyl-1-octanol + 25 % 2,6-dimethyl-2-octanol) and CO2 + (20 % n-dodecane + 70 % 1-decanol + 10 % 3,7-dimethyl-1-octanol) mixtures showed that the composition of the feed mixture have a significant effect on the location and size of the operating window and optimum operating conditions. The optimum operating conditions were defined as the conditions where an acceptable selectivity ratio and alcohol recovery occurred simultaneously. Since the selectivity ratio and alcohol recovery have opposing optimization approaches, a number of possible optimum operating conditions exist, based on the product specifications. When an alcohol and an alkane with similar phase behaviour exist in a mixture, a distinct minimum selectivity ratio will occur at a point within the extract-to-feed ratio limits of the process. When the alkanes and alcohols present in a mixture do not have similar or overlapping phase transition pressures, the minimum selectivity ratio will typically cover a small range of extract-to-feed ratios at the high end limit of the extract-to-feed ratio range. To summarize: A process model was established in Aspen Plus® that can be used to determine the feasibility and separation performance of a supercritical fractionation process for a feed mixture of detergent range alkane and alcohol isomers. The model was used to prove that an SFF process is a feasible alternative process to consider for the removal of alkanes from mixtures of detergent range alcohol isomers, even where overlapping boiling points or low relative volatilities occur. During the development of the process model, the following significant novel contributions were made: · New phase equilibrium data were measured for C10-alkane and C10-alcohol isomers in supercritical ethane, as published in The Journal of Supercritical Fluids 58 (2011) 330 – 342. · New phase equilibrium data were measured for C10-alkane and C10-alcohol isomers in supercritical CO2, as published in The Journal of Supercritical Fluids 59 (2011) 14 – 26. · A thermodynamic model was developed in Aspen Plus® that can accurately predict the phase transition pressures of binary, ternary and multi-component mixtures of detergent range alkanes and alcohols in supercritical CO2, as published in The Journal of Supercritical Fluids 84 (2013) 132 – 145. · A process model was developed in Aspen Plus® that can be used to predict the separation performance of a supercritical fluid fractionation process for the separation of mixtures of detergent range alkanes and alcohols. · Experimental and simulated results indicated that a supercritical fluid fractionation process can be implemented successfully to separate an alkane from a mixture of alcohol isomers, as was shown for two mixtures: CO2 + (25 % n-decane + 25 % 1-decanol + 25 % 3,7-dimethyl-1-octanol + 25 % 2,6-dimethyl-2-octanol) and CO2 + (20 % n-dodecane + 70 % 1-decanol + 10 % 3,7-dimethyl-1-octanol). / AFRIKAANSE OPSOMMING: Data oor die omvang van skeiding by verskillende bedryfstoestande word benodig om die lewensvatbaarheid van ’n skeidingsproses te bepaal. Sulke data kan eksperimenteel gemeet word, maar as gevolg van die tyd en kostes geassosieer met eksperimente op loodsaanlegskaal, word die gebruik van prosesmodelle verkies. Die hoofdoel van hierdie projek is om ’n werkende prosesmodel, wat daarop gemik is om C8 – C20 alkane en alkohol isomere te skei, in Aspen Plus® tot stand te bring om die omvang van die skeiding van ’n superkritiese fraksioneringsproses te meet. Tans word azeotropiese distillasie gebruik vir die skeiding van C8 – C20 alkane en alkoholisomere. Alhoewel goeie skeiding met hierdie proses bewerkstellig word, is daar sekere eienskappe van die proses wat aandag vereis: die voorgestelde skeidingsagent, dietileen glikol, is giftig vir mense; baie lae bedryfsdrukke van 0.016 – 0.031 MPa en hoë temperature van 473 K word benodig; addisionele proseseenhede en materiaal is nodig om die skeidingsagent van die produkte te verwyder. Die gebruik van ’n alternatiewe proses - superkritiese fraksionering - word in hierdie werk voorgestel nadat vorige studies getoon het dat hierdie proses die potensiaal het om alkane en alkohole te skei. Die superkritiese fraksioneringsproses spreek al die kommerwekkende eienskappe van azeotropiese distillasie aan soos volg: ’n veilige oplosmiddel, CO2, word as die skeidingsagent gebruik; gemiddelde temperature van 344 K word voorgestel, maar ten koste van lae bedryfsdrukke; ’n enkele proseseenheid en geen addisionele materiaal word benodig om die oplosmiddel van die produkte te skei nie. ’n Prosesmodel is in Aspen Plus® ontwikkel om die omvang van die skeiding wat deur die voorgestelde superkritiese fraksioneringsproses teweeggebring is, te evalueer en te vergelyk met die azeotropiese distillasieproses wat tans in gebruik is. Die ontwikkeling van die prosesmodel sluit die ontwikkeling van ’n akkurate termodinamiese model in Aspen Plus® in. Na deeglike evaluasie van ’n aantal kubiese toestandsvergelykings is gevind dat die RK-ASPEN-model die faseoorgangsdrukke van multi-komponentmengsels van C8 – C20 alkane en alkohole die beste voorspel binne die temperatuurbereik van 318 – 348 K. Faseoorgangsdrukke kon voorspel word met ’n fout van minder as 6 % met die insluiting van voorafbepaalde polêre parameters en binêre interaksie-parameters vir twee multi-komponentmengsels: CO2 + (20 % n-dodekaan + 70 % 1-dekanol + 10 % 3,7-dimetiel-1-oktanol) and CO2 + (25 % n-dekaan + 25 % 1-dekanol + 25 % 3,7-dimetiel-1-oktanol + 25 % 2,6-dimetiel-2-oktanol). Polêre parameters is bepaal met dampdruk data, wat voorspel is met korrelasies in Aspen Plus®. Binêre interaksieparameters is van eksperimentele faseoorgangsdata bepaal. Binêre faseoorgangsdata is vir ’n aantal sisteme wat uit etaan of CO2 en ’n C10-alkaan- of C10-alkohol-isomeer bestaan, gemeet by temperature tussen 308 K en 353 K en samestellings van tussen 0.01 en 0.7 massafraksie van die opgeloste stof. ’n Vergelyking tussen die gemete fase-ewewigsdata het onthul dat die struktuur van die molekuul, en nie net die molekulêre massa nie, die oplosbaarheid van die stof in die superkritiese oplosmiddel beïnvloed. Die faseoorgangsdrukke van n-dekaan, 2-metielnonaan, 3-metielnonaan en 4-metielnonaan het geen skynbare verskille getoon in etaan of CO2 nie en dus sal hierdie stowwe in alle waarkynlikheid nie met ’n superkritiese fraksioneringsproses geskei kan word nie. Die faseoorgangsdrukke wat vir die C10-alkohol gemeet is, het in beide etaan en CO2 afgeneem in die volgende volgorde: 1-dekanol, 3,7-dimetiel-1-oktanol, 2-dekanol, 2,6-dimetiel-2-oktanol en 3,7-dimetiel-3-oktanol. Die posisie van die hidroksielgroep en die aantal, lengte en posisie van die sytakke beïnvloed die oplosbaarheidsgedrag van die alkohol-isomere in die superkritiese oplosmiddel. Aangesien die gebruik van etaan nie enige voordele ten opsigte van selektiwiteit inhou nie, is die gebruik van die minder skadelike en goedkoper oplosmiddel, CO2, vir verdere ondersoeke geregverdig. Die ontwikkelde termodinamiese model, met die insluiting van die polêre parameters en binêre interaksieparameters, is in die prosesmodel ingesluit en die omvang van die skeiding van die proses is gesimuleer by verskillende bedryfstoestande vir die CO2 + (25 % n-dekaan + 25 % 1-dekanol + 25 % 3,7-dimetiel-1-oktanol + 25 % 2,6-dimetiel-2-oktanol) mengsel. ’n Vergelyking tussen die gesimuleerde data en die eksperimentele loodsaanlegdata het onthul dat die model nie die omvang van die skeiding kan voorspel by lae fraksioneringstemperature (316 K) nie as gevolg van die tekortkominge in die termodinamiese model. Die omvang van die skeiding by hoë temperature (344 K) kon egter goed voorspel word met ’n fout van 10 – 36 %. Simulasies van die CO2 + (25 % n-dekaan + 25 % 1-dekanol + 25 % 3,7-dimetiel-1-oktanol + 25 % 2,6-dimetiel-2-oktanol) en CO2 + (20 % n-dodekaan + 70 % 1-dekanol + 10 % 3,7-dimetiel-1-oktanol) mengsels het getoon dat die samestelling van die voermengsel ’n beduidende effek op die grootte van die bedryfsvenster en optimum bedryfstoestande het. Die optimum bedryfstoestande word gedefinieer as die toestande waar ’n aanvaarbare selektiwiteitsverhouding en alkoholherwinning terselfdertyd voorkom. Aangesien die selektiwiteitsverhouding en alkoholherwinning teenstrydige optimeringsbenaderings het, bestaan daar ’n aantal optimum bedryfstoestande gebaseer op die produkspesifikasies. Wanneer ’n alkohol en ’n alkaan met ooreenstemmende fasegedrag saam in ’n mengsel voorkom, bestaan daar ’n duidelike minimum selektiwiteitsverhouding by ’n punt binne die ekstrak-tot-voer-verhoudingslimiete van die proses. Wanneer die alkane en alkohole in ’n mengsel nie ooreenstemmende fasegedrag toon nie, sal die minimum selektiwiteitsverhouding oor ’n reeks ekstrak-tot-voer-verhoudings voorkom, tipies by die hoë limiet van die ekstrak-tot-voer-verhoudingsreeks. Om op te som: ’n Prosesmodel is in Aspen Plus® tot stand gebring wat die lewensvatbaarheid en omvang van die moontlike skeiding van ’n superkritiese fraksioneringsproses vir voermengsels van C8 – C20 alkane en alkohol-isomere kan voorspel. Die model is gebruik om te bewys dat ’n superkritiese proses ’n lewensvatbare alternatiewe proses is om te oorweeg vir die verwydering van alkane uit mengsels van alkohol-isomere, self waar ooreenstemmende kookpunte of lae relatiewe vlugtigheid tussen komponente voorkom. Tydens die ontwikkeling van die prosesmodel is die volgende beduidende nuwe bydraes gemaak: · Nuwe fase-ewewigsdata is gemeet vir C10-alkaan- en C10-alkohol-isomere in superkritiese etaan, soos gepubliseer in The Journal of Supercritical Fluids 58 (2011) 330 – 342. · Nuwe fase-ewewigsdata is gemeet vir C10-alkaan and C10-alkohol isomere in superkritiese CO2, soos gepubliseer in The Journal of Supercritical Fluids 59 (2011) 14 – 26. · ’n Termodinamiese model is ontwikkel in Aspen Plus® wat die faseoorgangsdrukke van binêre, ternêre en multi-komponent mengsels van C8 – C20 alkane en alkohol-isomere in superkritiese CO2 akkuraat kan voorspel, soos gepubliseer in The Journal of Supercritical Fluids 84 (2013) 132 – 145. · ’n Prosesmodel is ontwikkel in Aspen Plus® wat die omvang van die moontlike skeiding van ’n superkritiese fraksioneringsproses, gemik op die skeiding van mengsels van C8 – C20 alkane en alkohol-isomere, kan voorspel. · Eksperimentele en gesimuleerde resultate toon aan dat ’n superkritiese fraksioneringsproses suksesvol geïmplementeer kan word vir die skeiding van ’n alkaan vanuit ’n mengsel van alkohol-isomere, soos bewys vir twee mengsels: CO2 + (25 % n-dekaan + 25 % 1-dekanol + 25 % 3,7-dimetiel-1-oktanol + 25 % 2,6-dimetiel-2-oktanol) en CO2 + (20 % n-dodekaan + 70 % 1-dekanol + 10 % 3,7-dimetiel-1-oktanol).

Thesis (PhD)--Stellenbosch University, 2014. / ENGLISH ABSTRACT: The reactive absorption rate of CO2 into non-aqueous solvents containing the primary amine, mono-ethanolamine (MEA) is recognised as a suitable method for measuring the effective interfacial mass transfer area of separation column internals such as random and structured packing. Currently, this method is used under conditions where the concentration of MEA in the liquid film is unaffected by the reaction and the liquid phase reaction is, therefore, assumed to obey pseudo first order kinetics with respect to CO2. Under pseudo first order conditions, the effect of surface depletion and renewal rates are not accounted for. Previous research indicated that the effective area available for mass transfer is also dependent upon the rate of surface renewal achieved within the liquid film. In order to study the effect of surface depletion and renewal rates on the effective area, a method utilising a fast reaction with appreciable depletion of the liquid phase reagent is required. The homogeneous liquid phase reaction kinetics of CO2 with MEA n-Propanol as alcoholic solvent was investigated in this study. A novel, in-situ Fourier Transform Infra-Red (FTIR) method of analysis was developed to collect real time concentration data from reaction initiation to equilibrium. The reaction was studied in a semi-batch reactor set-up at ambient conditions (T = 25°C, 30°C and 35°C, P = 1 atm (abs)). The concentration ranges investigated were [MEA]:[CO2] = 5:1 and 10:1. The concentration range investigated represents conditions of significant MEA conversion. The reaction kinetic study confirmed the findings of previous research that the reaction of CO2 with MEA is best described by the zwitterion reactive intermediate reaction mechanism. Power rate law and pseudo steady state hypothesis kinetic models (proposed in literature) were found to be insufficient at describing the reaction kinetics accurately. Two fundamentally derived rate expressions (based on the zwitterion reaction mechanism) provided a good quality model fit of the experimental data for the conditions investigated. The rate constants of the full fundamental model were independent of concentration and showed an Arrhenius temperature dependence. The shortened fundamental model rate constants showed a possible concentration dependence, which raises doubt about its applicability. The specific absorption rates (mol/m2.s) of CO2 into solutions of MEA/n-Propanol (0.2 M and 0.08 M, T = 25°C and 30°C, P = ±103 kPa) were investigated on a wetted wall experimental setup. The experimental conditions were designed for a fast reaction in the liquid film to occur with a degree of depletion of MEA in the liquid film. Both interfacial depletion and renewal of MEA may be considered to occur. The gas phase resistance to mass transfer was determined to be negligible. An increase in liquid turbulence caused an increase in the specific absorption rate of CO2 which indicated that an increase in liquid turbulence causes an increase in effective mass transfer area. Image analysis of the wetted wall gas-liquid interface confirmed the increase in wave motion on the surface with an increase in liquid turbulence. The increase in wave motion causes an increase in both interfacial and effective area. A numerical solution strategy based on a concentration diffusion equation incorporating the fundamentally derived rate expressions of this study is proposed for calculating the effective area under conditions where surface depletion and renewal rates are significant. It is recommended that the reaction kinetics of CO2 with MEA in solvents of varying liquid properties is determined and the numerical technique proposed in this study used to calculate effective area from absorption rates into these liquids. From the absorption data an effective area correlation as a function of liquid properties may be derived in future. / AFRIKAANSE OPSOMMING: Die reaktiewe absorpsie van CO2 in nie-waterige oplossings van die primêre amien, monoetanolamien (MEA) word erken as ‘n geskikte metode om die effektiewe massaoordragsarea van gepakte skeidingskolomme te bepaal. Tans word die metode gebruik onder vinnige pseudo eerste orde reaksietoestande met betrekking tot CO2. Die pseudo eersteorde aanname beteken dat die konsentrasie van MEA in die vloeistoffilm onbeduidend beïnvloed word deur die reaksie en effektief konstant bly. Onder pseudo eerste orde toestande word oppervlakverarming- en oppervlakvernuwingseffekte nie in ag geneem nie, juis as gevolg van die konstante konsentrasie van MEA in die vloeistoffilm. Daar is voorheen bevind dat oppervlakverarming en oppervlakvernuwing ‘n beduidende invloed het op die beskikbare effektiewe massaoordragsarea. Hierdie invloed kan slegs bestudeer word met ‘n vinnige reaksie in die vloeistoffilm wat gepaard gaan met beduidende oppervlakverarming van die vloeistoffase reagens. Die homogene vloeistoffase reaksiekinetika van CO2 met MEA in die alkohol oplosmiddel, n- Propanol, is in hierdie studie ondersoek. ‘n Nuwe, in-situ Fourier Transform Infra-Rooi (FTIR) metode van analiese is ontwikkel in hierdie ondersoek. Die reaksie is ondersoek in ‘n semienkelladings reaktor met MEA wat gevoer is tot die reaktor om met die opgeloste CO2 te reageer. Die FTIR metode meet spesiekonsentrasie as ‘n funksie van tyd sodat die konsentrasieprofiele van CO2, MEA en een van die soutprodukte van die reaksie gebruik kan word om verskillende reaksiesnelheidsvergelykings te modelleer. Die reaksie is ondersoek onder matige toestande (T = 25°C, 30°C and 35°C, P = 1 atm (abs)). Die konsentrasiebereik van die ondersoek was [MEA]:[CO2] = 5:1 en 10:1. Hierdie bereik is spesifiek gebruik sodat daar beduidende omsetting van MEA kon plaasvind. Die reaksiekinetieka studie het, ter ondersteuning van bestaande teorie, bevind dat die reaksie van CO2 met MEA in nie-waterige oplosmiddels soos alkohole, beskyf word deur ‘n zwitterioon reaksiemeganisme. Die bestaande reaksiesnelheids modelle (eksponensiële wet en pseudo gestadigde toestand hipotese) kon nie die eksperimentele data met genoegsame akuraatheid beskryf nie. Twee nuwe reaksiesnelheidsvergelykings, afgelei vanaf eerste beginsels en gebaseer op die zwitterioon meganisme, word voorgestel. Hierdie volle fundamentele model het goeie passings op die eksperimentele data getoon oor die volledige temperatuur en konsentrasiebereik van hierdie studie. Die reaksiekonstantes van die fundamentele model was onafhanklik van konsentrasie en tipe oplosmiddel en het ‘n Arrhenius temperatuurafhanklikheid. Die verkorte fundamentele model se reaksiekonstantes het ‘n moontlike konsentrasieafhanlikheid gewys. Dit plaas onsekerheid op die fundamentele basis van hierdie model en kan dus slegs as ‘n eerste benadering beskou word. Die spesifieke absorpsietempos (mol/m2.s) van CO2 in MEA/n-Propanol oplossings (0.2 M en 0.08 M MEA, T = 25°C and 30°C, P = ±103 kPa) is ondersoek met ‘n benatte wand (‘wetted wall’) eksperimentele opstelling. Die eksperimentele toestande is gekies sodat daar ‘n vinnige reaksie in die vloeistoffilm plaasgevind het, met beide beduidende en nie-beduidende MEA omsetting. Die doel met hierdie eksperimentele ontwerp was om die invloed van intervlakverarming en intervlakvernuwing op die spesifieke absorpsietempo te ondersoek. Gas fase weerstand was nie-beduidend onder die eksperimentele toestande nie. Beide intervlakverarming en intervlakvernuwing gebeur gelyktydig en is waargeneem vanuit die eksperimentele data. ‘n Beeldverwerkingstudie van die gas-vloeistof intervlak van die benatte wand het bevind dat daar ‘n toename in golfaksie op die vloeistof oppervlak is vir ‘n toename in vloeistof turbulensie. Hierdie golfaksie dra by tot oppervlakvernuwing en ‘n toename in effektiewe massaoordragsarea. ‘n Numeriese metode word voorgestel om die effektiewe area van beide die benatte wand en gepakte kolomme te bepaal vanaf reaktiewe absorpsietempos. Die metode gebruik die fundamentele reaksiesnelheidsvergelykings, bepaal in hierdie studie, in a konsentrasie diffusievergelyking sodat oppervlakverarming en vernuwing in ag geneem kan word. Daar word voorgestel dat die reaksiekinetika van CO2 met MEA in oplossings met verskillende fisiese eienskappe (digtheid, oppervlakspanning en viskositeit) bepaal word sodat die numeriese metode gebruik kan word om ‘n effektiewe area korrelasie as ‘n funksie van hierdie eienskappe te bepaal.

Thesis (MScEng)--Stellenbosch University, 2012 / ENGLISH ABSTRACT: Through many years of research, a number of production schemes have been developed for converting lignocellulosic biomass into transport fuels. These technologies have been assessed through a number of techno-economic studies for application in a particular context in terms of the technical and economic feasibility. However, previous studies using these methods have tended to lack vigour in various aspects. Either the energy efficiency of the processes were not maximised through adequate heat integration, or a competing technology which existed was not considered. From an economic perspective, the financial models would often lack the vigour to account for the risk and uncertainty that is inherent in the market prices of the commodities. This phenomenon is especially relevant for the biofuel industry that faces the full fledge of uncertainties experienced by the agricultural sector and the energy sector. Furthermore, from an environmental perspective, the techno-economic studies had often ignored the environmental impacts that are associated with biofuel production. Thus, a comparative study could have favoured an option due to its economic feasibility, while it could have had serious environmental consequences. The aim of this study was to address these issues in a South African context, where biofuels could be produced from sugarcane bagasse. The first step would be to modify an existing simulation model for a bioethanol scenario that operates with a Separate Hydrolysis and Fermentation (SHF process) configuration into a second processing scenario that operates with a Simultaneous Saccharification and Fermentation (SSF process) configuration using reliable experimental data. The second step was to ensure that the maximum energy efficiency of each scenario was realised by carrying out pinch point analysis as a heat integration step. In contrast to these biological models is the thermochemical model that converts bagasse to gasoline and diesel via gasification, Fischer-Tropsch synthesis and refining (GFT process). While there were no significant advances in technology concerning this type of process, the energy efficiency was to be maximised with pinch point analysis. The GFT process obtained the highest energy efficiency of 50.6%. Without the affects of pinch point technology, the efficiency dropped to 46%, which thus emphasises the importance of heat integration. The SSF had an efficiency of 42.8%, which was superior to that of the SHF at 39.3%. This resulted from a higher conversion of biomass to ethanol in the SSF scenario. Comparing the SHF model to an identical model found in literature that did not have pinch point retrofits, this study showed lower efficiency. This arose because the previous study did not account for the energy demands of the cold utility systems such as the cooling tower operation, which has been shown in this study to account for 40% of the electrical energy needs. The economic viability of all three processes was assessed with Monte Carlo Simulations to account for the risks that the fluctuations in commodity prices and financial indices pose. This was accomplished by projecting the fluctuations of these parameters from samples of a historical database that has been transformed into a probability distribution function. The consequences were measured in terms of the Net Present Value (NPV) and Internal Rate of Return (IRR) for a large number of simulations. The results of these variables were aggregated and were then assessed by testing the probability that the NPV<0, and that the IRR recedes below the interest rate of 12.64%. The investment was thus deemed unfeasible if these probabilities were greater than 20%. Both biological models were deemed profitable in terms of this standard. The probabilities were 13% for the SSF and 14% for the SHF. The GFT process however was deemed completely unfeasible because the probability that the NPV<0 was 78%. Given that the GFT process had the highest energy efficiency, this result arises mainly because the capital investment of 140,000USD/MWHHV of biomass energy input is to enormous for any payback to be expected. The environmental footprint of each process was measured using Life Cycle Assessments (LCAs). LCAs are a scientifically intricate way of quantifying and qualifying the effects of a product or process within a specified boundary. The impacts are assessed on a range of environmental issues, such as Global Warming, Acidification, Eutrophication and Human toxicity. Furthermore, if the project under concern has multiple output products, then the impacts are distributed between the output products in proportion to the revenue that each generates. The impacts were either relative to the flow of feedstock, which was 600MW of bagasse, or to the functional unit, which was the amount of fuel required to power a standard vehicle for a distance of 1 kilometre. In either case, the GFT scenario was the least burdening on the environmental. This was expected because the GFT process had the highest energy efficiency and the process itself lacked the use of processing chemicals. Relative to the feedstock flow, the SSF was the most environmentally burdening scenario due to the intensive use of processing chemicals. Relative to the functional unit, the SHF was the most severe due to its low energy efficiency. Thus, the following conclusions were drawn from the study:  The GFT is the most energy and environmentally efficient process, but it showed no sign of economic feasibility. iv  There is no significant difference in the economic and environmental evaluation of the SSF and SHF process, even though the SSF is considered to be a newer and more efficient process. The major cause of this is because the setup of the SSF model was not optimised. / AFRIKAANSE OPSOMMING: Deur baie jare van navorsing is ‘n aantal produksie-skemas vir die omskakeling van lignosellulose biomassa na vloeibarebrandstof ontwikkel. Hierdie tegnologië is geassesseer ten opsigte van die tegniese en ekonomiese haalbaarheid deur middel van tegno-ekonomiese studies in bepaalde tekste. Tog het hierdie vorige studies besliste beperkings gehad. Of die energie-doeltreffendheid van die proses is nie gemaksimeer deur voldoende hitte-integrasie nie, of 'n mededingende tegnologie wat bestaan is nie oorweeg nie. Vanuit 'n ekonomiese perspektief, was die finansiële modelle dikwels nie die omvattend genoeg om rekening te hou met die risiko en onsekerheid wat inherent is in die markpryse van die kommoditeite nie. Hierdie verskynsel is veral relevant vir die biobrandstof bedryf wat die volle omvang van onsekerhede ervaar waaraan die landbousektor en die energiesektoronderhewig is. Verder het die tegno-ekonomiese studies dikwels die omgewingsimpakte wat verband hou met biobrandstofproduksie geïgnoreer. Dus kon ‘n opsie deur die ekonomiese haalbaarheid bevoordeel word, ten spyte van die ernstige omgewingsimpakte wat dit kon inhou. Die doel van hierdie studie was om hierdie kwessies aan te spreek in 'n Suid-Afrikaanse konteks, waar biobrandstof uit suikerriet bagasse geproduseer kan word. Die eerste stap was om 'n bestaande simulasiemodel vir 'n bio-scenario wat met Afsonderlike Hidroliese en Fermentasie (SHF proses) stappe werk, te modifiseer vir 'n tweede verwerking scenario wat met 'n gelyktydige Versuikering en Fermentasie (SSF proses) konfigurasie werk. Die verandering is gedoen deur die gebruik van betroubare eksperimentele data. Die tweede stap was om te verseker dat elke scenario die maksimum energie-doeltreffendheid het, deur 'n hitte-integrasie stap, wat gebruik maak van “pinch-point” analise. In teenstelling met hierdie biologiese modelle, is daar die thermochemiese roete waar petrol en diesel van bagasse vervaardig word via vergassing, Fischer-Tropsch-sintese en rafinering (GFT proses). Daar was geen betekenisvolle vooruitgang in tegnologie vir hierdie proses nie, maar die energie-doeltreffendheid is gemaksimeer word deur energie-integrasie. Die GFT proses toon die hoogste energie-doeltreffendheid van 50,6%. Sonder die invloed van energie-integrasie het die doeltreffendheid gedaal tot 46%, wat dus die belangrikheid van hitte-integrasie beklemtoon. Die SSF het 'n effektiwiteit van 42,8% gehad, wat beter was as dié 39,3% van die SHF opsie. Hierdie hoër effektiwiteit wasas gevolg van die hoër omskakeling van biomassa na etanol in die SSF scenario. Die energie doeltreffendheid vir die SHF-model was laer as met 'n identiese model (sonder energie-integrasie) wat in die literatuur gevind wat is. Dit het ontstaan omdat die vorige studie nie 'n volledig voorsiening gemaak het met die energie-eise van die verkillingstelselsnie, wat tot 40% van die elektriese energie behoeftes kan uitmaak. Die ekonomiese lewensvatbaarheid van al drie prosesse is bepaal met Monte Carlo simulasies om die risiko's wat die fluktuasies in kommoditeitspryse en finansiële indekse inhou, in berekening te bring. Hierdie is bereik deur die projeksie van die fluktuasies van hierdie parameters aan die hand van 'n historiese databasis wat omskep is in 'n waarskynlikheid verspreiding funksie. Die gevolge is gemeet in terme van die netto huidige waarde (NHW) en Interne Opbrengskoers (IOK) vir 'n groot aantal simulasies. Die resultate van hierdie veranderlikes is saamgevoeg en daarna, deur die toets van die waarskynlikheid dat die NPV <0, en dat die IRR laer as die rentekoers van 12,64% daal, beoordeel. Die belegging is dus nie realiseerbaar geag as die waarskynlikhede meer as 20% was nie. Beide biologieseprosesse kan as winsgewend beskou word in terme van bostaande norme. Die waarskynlikhede was 13% vir die SSF en 14% vir die SHF. Aangesien die NHW van die GFT-proses onder 0 met ‘n waarskynlikheid van 78% is, is die opsie as nie-winsgewend beskou. Gegewe dat die GFT-proses die hoogste energie-doeltreffendheid het, is die resultaat hoofsaaklik omdat die kapitale belegging van 140,000 USD / MWHHV-biomassa energie-inset te groot is, om enige terugbetaling te verwag. Die omgewingsvoetspoor van elke proses is bepaal deur die gebruik van Lewens Siklus Analises (“Life Cycle Assessments”) (LCAS). LCAS is 'n wetenskaplike metodeom die effek van ‘n produk of proses binne bepaalde grense beide kwalitatief en kwantitatief te bepaal. Die impakte word beoordeel vir 'n verskeidenheid van omgewingskwessies, soos aardverwarming, versuring, eutrofikasie en menslike toksisiteit. Voorts, indien die projek onder die saak verskeie afvoer produkte het, word die impakte tussen die afvoer produkte verdeel, in verhouding tot die inkomste wat elkeen genereer. Die impak was met of relatief tot die vloei van roumateriaal (600MW van bagasse), of tot die funksionele eenheid, wat die hoeveelheid van brandstof is om 'n standaard voertuig aan te dryf oor 'n afstand van 1 kilometer. In al die gevalle het die GFT scenario die laagste belading op die omgewing geplaas. Hierdie is te verwagte omdat die GFT proses die hoogste energie-doeltreffendheid het en die proses self nie enige addisionele chemikalieë vereis nie. Relatief tot die roumateriaal vloei, het die SSF die grootse belading op die omgewing geplaas as gevolg van die intensiewe gebruik van verwerkte chemikalieë. Relatief tot die funksionele eenheid, was die SHF die swakste as gevolg van sy lae energie-doeltreffendheid.