Dissertation (PhD(Eng))--University of Stellenbosch, 2001. / ENGLISH ABSTRACT: Coal pyrolysis liquors are a major source of phenolic compounds. The separation of the phenolic compounds from the neutral oils and nitrogen bases also present in the pyrolysis liquors is difficult due to low relative volatilities and the formation of azeotropes. The desired phenolic recovery and phenolic product purity of 99.5 % can therefore not be achieved by means of conventional separation processes. Alternative processes such as liquid-liquid extraction with various low-boiling solvents, mixtures of high-boiling solvents and extractive distillation have been investigated. Disadvantages of these processes include the high solvent ratios required, low recovery of the higher substituted phenolic compounds, inability to treat a wide-boiling feedstock in one process step and complex post-purification of the phenolic product. A solvent system consisting of a selective solvent, water as a co-solvent, and hexane as a countersolvent, is proposed. An industrial heavy naphtha stream was analysed and the most prevalent phenolic compounds, neutral oils and nitrogen bases identified. Three synthetic feed streams were compiled to represent the industrial stream, namely: 1. phenol + benzonitrile + aniline + mesitylene + 5-et-2-me-pyridine 2. m-cresol + o-tolunitrile + o-toluidine + pseudocumene + undecane + indene 3. 2,4-xylenol + 3,5-xylenol + 3,4-xylenol + indane + dodecane + naphthalene The stream containing phenol was used as a basis for solvent selection, with emphasis on the separation of phenol from benzonitrile. A variety of molecules containing hydroxyl and ether functional groups were identified as potential solvents by means of computer-aided molecular design using a genetic algorithm. Of the commercially available solvents tested on batch extraction scale, triethylene glycol achieved the highest phenol-benzonitrile, phenol-aniline and phenol-5-et-2-me-pyridine separation factors as well as the highest phenol recovery. It was concluded from the solvent selection process that effective solvents for the problem under investigation were those containing hydroxyl groups positioned on the molecule backbone in such a way as to facilitate hydrogen bonding with more than one phenolic molecule at a time. Two commercially unavailable solvents, 1,3-(ethoxy-2- hydroxy)-propane-2-01 and 1,3-(diethoxy-4-hydroxy)-propane-2-01 were therefore synthesised from ethylene glycol and diethylene glycol respectively. The molecular structures of these two solvents are analogous to that of triethylene glycol, and contain an additional hydroxyl group. The performance of the synthesised solvents was evaluated and compared to that of triethylene glycol on the basis of m-cresol-otolunitrile, 2,4-xylenol - o-tolunitrile, and 2,4-xylenol - o-toluidine separation factors and phenolic recoveries achieved by means of batch extraction tests. 1,3-(Diethoxy-4- hydroxy)-propane-2-01 yielded higher phenolic recoveries, but lower separation factors than did triethylene glycol. Triethylene glycol was therefore selected for further process development as it is commercially available. A series of batch extractions were carried out on each of the synthetic feed streams using the proposed solvent system. For phenol and m-cresol, recoveries in excess of 99% were obtained in a single stage. Recoveries in excess of 98% were obtained for the xylenol isomers. It was found that the recoveries of the xylenol isomers were more sensitive to changes in the solvent ratios. The separation of phenolic compounds from paraffins, naphthalene, indene, indane and the alkyl-substituted benzenes was trivial using the proposed solvent system. Highly satisfactory separation of the phenolic compounds from pyridines and aromatic nitriles was achieved. The separation of phenol from aniline, although satisfactory, was not as good. The optimum solvent to feed, water to solvent and hexane to feed ratios were identified as being 3.0, 5.0 and 0.25 respectively. Binary interaction parameters for the NRTL equation were obtained by regression of the equilibrium data from the batch extraction tests. The NRTL model fitted the equilibrium data satisfactorily. The proposed solvent system was tested on pilot plant scale. The performance of the extraction column was optimised using a synthetic feed stream consisting of m-cresol, p-cresol, aniline and o-tolunitrile. The optimum solvent ratios and operating parameters were then implemented in further tests on an industrial heavy naphtha stream. A phenolic product purity of 99.75% was achieved for this stream. The corresponding phenolic recovery was in excess of 91 %. The proposed separation process, including solvent recovery was simulated using the NRTL model with the experimentally determined interaction parameters. A single stream consisting of all the components used in the batch extraction tests was specified as the feed stream to the simulated process. A final simulated phenolic product purity of 99.5% and recovery in excess of 94% was obtained after solvent recovery. The optimum solvent to feed, hexane to feed and water to solvent ratios were determined as being 3.0, 5.0 and 0.25 in both the pilot plant tests and the simulated extraction process. It can be concluded that the proposed separation process is successful in recovering high purity phenolic compounds from tar liquors. Further development of the process has commenced in industry. / AFRIKAANSE OPSOMMING: Die pirolise van steenkool is 'n belangrike bron van fenoliese verbindings. Die skeiding van die fenoliese komponente vanuit die neutrale olies ook teenwoordig in die pirolise mengsel word bemoeilik deur lae relatiewe vlugtighede en die vorming van aseotrope. Dit is dus nie moontlik om die gewenste hoë fenoliese herwinning en fenoliese produk suiwerheid van 99.5% d.m.v. konvensionele distilleerprosesse te behaal nie. Alternatiewe prosesse soos ekstraktiewe distillasie en vloeistof-vloeistof ekstraksie met verskeie laagkokende oplosmiddels en mengsels van hoogkokende oplosmiddels is al ondersoek. Die hoë oplosmiddel verhoudings wat benodig word, lae herwinning van die hoërgesubstitueerde fenoliese verbindings, onvermoë om in een prosesstap 'n prosesstroom met In wye kookgebied te behandel en die ingewikkelde suiwering van die fenoliese produk tel onder die nadele van hierdie prosesse. 'n Oplosmiddelsisteem wat In selektiewe oplosmiddel, water as polêre oplosmiddel en heksaan as teenoplosmiddel bevat is as 'n alternatiewe proses voorgestel. 'n Industriële swaar nafta prosesstroom is ge-analiseer en die fenoliese verbindings, neutrale olies en stikstofbasisse met die hoogste konsentrasies daarin geïdentifiseer. Drie sintetiese strome is op grond van hierdie analise saamgestelom die industriële stroom te verteenwoordig: 1. fenol + benzonitriel + anilien + mesitileen + 5-et-2-me-piridien 2. m-kresol + o-tolunitriel +o-toluïdien + pseudokumeen + undekaan + indeen 3. 2,4-xilenol + 3,5-xilenol + 3,4-xilenol + indaan + dodekaan + naftaleen Die fenolbevattende stroom is as basis vir oplosmiddelkeuring gebruik, met die klem op die skeiding van fenol vanuit benzonitriel. Verskeie molekules wat hidroksie- en eter funksionele groepe bevat is as potensiële oplosmiddels uitgeken d.m.v. rekenaargesteunde molekulêre ontwerp met In genetiese algoritme. Hierdie oplosmiddels is d.m.v. enkellading ekstraksie toetse geëvalueer. Die kommersieel beskikbare oplosmiddel wat die hoogste fenol-benzonitriel, fenol-anilien en fenol-5-et-2-me-piridien skeidingsfaktore, sowel as die hoogste fenol herwinning op enkellading ekstraksie toetsvlak gelewer het, was triëtileenglikol. Vanuit die proses vir die keuse van 'n oplosmiddel was dit duidelik dat, vir hierdie skeidingsprobleem, die mees effektiewe oplosmiddels dié is met hidroksiel groepe wat so geposisioneer is in die oplosmiddel molekuul dat dit waterstofbindings kan vorm met meer as een fenoliese molekuul. Twee oplosmiddels wat nie kommersiëel beskikbaar is nie, 1,3-(etoksie-2-hidroksie)-propaan-2-01 en 1,3-(diëtoksie-4-hidroksie)-propaan-2- ol, is gesintetiseer vanuit etileenglikol en diëtileenglikol onderskeidelik. Die molekulêre strukture van hierdie twee oplosmiddels is analoog aan dié van triëtileenglikol en bevat 'n addisionele hidroksielgroep. Die effektiwiteit van die gesintetiseerde oplosmiddels is geëvalueer en met dié van triëtileenglikol vergelyk op grond van rn-kresol-o-tolunltriel, 2,4-xilenol - o-tolunitriel en 2,4-xilenol - o-toluïdien skeidingsfaktore en fenoliese herwinning behaal d.m.v. enkellading ekstraksie toetse. Hoër fenoliese herwinning en laer skeidingsfaktore is behaal met 1,3-(diëtoksie-4-hidroksie)-propaan-2-01as met triëtileenglikol. Triëtileenglikol is dus gekies vir verdere prosesontwikkeling aangesien dit kommersiëel beskikbaar is. Enkellading ekstraksie toetse is op elk van die sintetiese voerstrome uitgevoer met die voorgestelde oplosmiddelsisteem. Fenol- en m-kresol herwinning van meer as 99% en xilenol herwinning van meer as 98% is behaal. Die skeiding van fenoliese verbindings vanuit paraffiene, naftaleen, indeen, indaan en die alkielgesubstitueerde benseenverbindings is triviaal met die voorgestelde oplosmiddelsisteem. Hoogs aanvaarbare skeiding van fenoliese verbindings van die piridiene en aromatiese nitriele is vermag. Die skeiding van fenol en anilien is nie so goed nie, maar is nog steeds aanvaarbaar. Die optimum oplosmiddel tot voer, water tot oplosmiddel en heksaan tot voer is as 3.0, 5.0 en 0.25 vasgestel. Binêre interaksie parameters vir die NRTL vergelyking is verkry d.m.v. regressie van die ewewigsdata wat deur die enkelladingstoetse gegenereer is. Die NRTL model het die ewewigsdata goed gepas. Die voorgestelde oplosmiddelsisteem is op loodsaanlegvlak getoets. Die werking van die ekstraksie kolom is ge-optimeer met In sintetiese voerstroom wat uit m-kresol, pkresol, anilien en o-tolunitriel bestaan. Die optimum oplosmiddel verhoudings en bedryfstoestande is verder toegepas op 'n industriële swaar naftastroom. 'n Fenoliese suiwerheid van 99.75% is behaal met hierdie stroom. Die ooreenkomstige fenoliese herwinning was groter as 91%. Die voorgestelde skeidingsproses, insluitende oplosmiddelherwinning is gesimuleer met die NRTL model wat op die eksperimentele data gepas is. 'n Enkele stroom wat bestaan het uit al die komponente wat in die enkelladingstoetse gebruik is, is as die voerstroom tot die gesimuleerde proses gespesifiseer. 'n Finale gesimuleerde fenoliese produksuiwerheid van 99.5% en herwinning groter as 94% is na oplosmiddelherwinning behaal. Die optimum oplosmiddel tot voer, heksaan tot voer en water tot oplosmiddel verhoudings is vasgestel as 3.0, 5.0 en 0.25 onderskeidelik vir beide die gesimuleerde proses en die loodsaanleg toetse. Die voorgestelde skeidingsproses kan dus 'n hoogs suiwer fenoliese produk uit pirolisestrome herwin. Verdere ontwikkeling van die proses is in die industrie begin.

Thesis (PhD)--University of Stellenbosch, 2002. / ENGLISH ABSTRACT: The availability of vast deposits of high-grade ore bodies are rapidly becoming something of the past in the modern mining and metallurgical scenario. Apart from the lower grade content of these ore bodies, complex mineralogy are an even greater obstacle in the recovery of valuable metal species. The development of new technology to deal with these type of ore bodies is therefore critical and worth investigating, as the world's easily exploitable high grade ore deposits are decreasing. Valuable species can be recovered from sparingly soluble solids, which slightly dissociate to give traces of the valuable ions in solution, with the use of ion-exchange resins in a slurry mixture. A dissociation equilibrium exists between the dissolved ions in solution and the solid ore body. Jf the dissolved ions are removed from the solution by ion-exchange, the solid / liquid dissociation equilibrium is continually displaced. According to Le Chatelier's principle further dissolution of the sparingly soluble solid is required to restore the equilibrium concentration of the valuable species in solution. It is possible to recover valuable metal species from metal precipitates, such as metal sulphides, by contacting a slurry of the precipitate with a suitable ion-exchange resin. The resulting ion exchange reaction between the valuable metal species and counter ions creates electrolyte solutions that may facilitate the further dissolution of the metal precipitate. These counter ion electrolyte solutions may easily become significantly concentrated. This occurs in the event of a Resin-in-Leach (RIL) mixture that results in a continuous ion-exchange reaction taking place due to the continually changing electrolyte composition of the mixture, which significantly changes the activities and hence the solubility of the valuable metal species in solution. Complete dissolution and liberation of the metal precipitate can often be achieved provided that a sufficient amount of a suitable high capacity ion-exchange resin is used in a properly engineered Resin-in- Leach (RIL) circuit. The simultaneous dissolution and adsorption of various base metal precipitates were tested. Various interactions that take place in the slurry at molecular level as well as the effects of various variables on the "adsorption by dissolution process" are discussed through the development of fundamental thermodynamic models. These thermodynamic mathematical models are developed for the three phase system that exists in a Resin-in- Leach mixture, i.e. the solid ore body, the electrolyte solution and the ion-exchange resin, and can be used for possible other applications such as the recovery of rare earths from low grade ores in the minerals processing industry. A typical example of an industrial process for the recovery of rare earth species is the percolation leaching of rare earths from low-grade kaolinitic ores, which continually shifts the solid / liquid dissociation equilibrium condition. The rare earth content of these ores is usually between 0.05%and 0.3 %, which is very low by any modern industrial extraction and refining standards. / AFRIKAANSE OPSOMMING: Die beskikbaarheid van ryk mineraal ertsneerslae is spoedig besig om iets van die verlede te word in die huidige mineraalontginning en metallurgiese veredelings industrie. Afgesien van die lae graad van die huidige mineraal ertsneerslae, blyk die komplekse mineralogiese samestelling van hierdie neerslae In veel groter struikelblok te wees in die herwinning en veredeling van die edelmetale teenwoordig in hierdie ertse. Die ontwikkeling van nuwe veredelings en ekstratiewe tegnologie vir die herwinning van edel metale, vanuit hierdie lae graad mineraal ertsneerslae, word dus benodig wat verdere navorsing in hierdie gebied regverdig. Dit is wel moontlik om metaal spesies afkomstig van ertse met 'n baie lae oplosbaarheid in waterige oplossings te herwin met ioon-uitruilings harse vanweë die feit dat die metaal spesies wel teen baie lae konsentrasies in die waterige oplossings teenwoordig is. Die metaal spesies los op in die waterige oplossings volgens hulle karakteristieke oplossings termodinamika. Indien die opgeloste metaal spesies vanuit die waterige oplossing verwyder word, sal die vaste stof / vloeistof ewewigs balans weer herstel word deurdat die vaste stof verder saloplos as gevolg van Le Chatelier se beginsel. Dit is dus moontlik om metaalagtige spesies, soos metaal sulfiedes, te herwin deur 'n waterige oplossing wat die metaal erts bevat in kontak te bring met 'n ioon-uitruilings hars. Die daaropvolgende ioon-uitruilings reaksie tussen die metaalagtige spesies en die spesies teenswoordig op die ioon-uitruilingshars het tot gevolg dat die elektrolitiese samestelling van die waterige oplossing verander. Dit is die gevolg van die migrasie van spesies aanvanklik teenswoordig op die hars wat in die waterige fase eindig. Die veranderende samestelling van die waterige oplossing mag verder tot gevolg hê dat die oplosbaarheid van die metaalagtige spesie verder verhoog mag word. Die gevolg van bogenoemde reaksies is dat die waterige oplossing ionies sterk gekonsentreerd kan word soos meer en meer spesies aanvanklik teenswoordig op die hars migreer na die oplossing. Die ioniese verandering van die waterige oplossing van 'n suiwer waterige fase tot 'n ionies sterk gekonsentreerde oplossing vind plaas tydens die oplos van erste in 'n hars-inpulp (HIP) oplossing. Die nuwe ioniese aktiwiteit in die oplossing kan die oplosbaarheid van die vaste stof drasties verander. Die volledige oplossing van 'n bepaalde kwantiteit van die vaste stof kan bereik word deur die genoegsame toevoeging van 'n geskikte hars tot die waterige oplossing wat die vaste stofbevat. Die gelyktydige oplossing en absorpsie van die metaalagtige vastestowwe vanuit waterige oplossings met behulp van ioon-uitruilings harse is eksperimenteel getoets vir die doeleindes van hierdie werkstuk. Verskeie interaksies wat op molekulêre vlak in die pulp plaasvind asook die adsorpsie proses van die spesies vanuit die waterige oplossing op die harse word bespreek en gemodelleer. Wiskundige modelle wat die termodinamika van die verskillende fases wiskundig verteenwoordig is ontwikkel vanaf bestaande termodinamiese beginsels. Die drie verskillende fases wat in ag geneem is, is die waterige fase met opgeloste metaal spesies, die vaste stof fase wat as die erts in bostaande paragrawe beskryf is en die ioon-uitruilings fase wat 'n komplekse vastestof en water fase gekombineerd is. Die doel van die werkstuk is om die basis te skep vir die ontwikkeling van modelle wat gebruik kan word om die herwinning van skaars-aarde mertale vanuit lae oplosbare erstse te modelleer en beskryf. 'n Tipiese industriële voorbeeld is die herwinning van skaars-aarde metale van lae-graadse kalkagtige erste deur gebruik te maak van perkolerende logings reaksies wat geduring die vastestof / vloeistof ewewig versteur. Die konsentrasie van die skaars-aarde metale in hierde erts gesteentes kan wissel vanaf so laag as 0.05% tot 0.3% per massa. Hierdie konsentrasies is uiters laag gesien vanuit enige industriële herwinnings proses oogpunt.

Thesis (MScEng)--University of Stellenbosch, 2001. / ENGLISH ABSTRACT: The hydrodynamics of a hollow fibre membrane module for the ultrafiltration of potable water were investigated. The purpose was to use a hydrodynamic model to predict the permeate flux for modules of various dimensions. Various models were considered, but most of them could not account for important effects such as macroscopic radial gradients and wet fibre expansion, found in hollow-fibre membrane modules. The Porous Medium Model was found to be a suitable model and it was used together with a finite element software package, Fastflo, to solve for the pressure distributions inside the membrane modules and predict permeate flux. The permeability of the membranes was obtained using a combination of numerical and experimental procedures and was found to be 2.3 x 10-13m. A cost analysis was performed to find the most economical module dimensions (outer diameter and length) for any required product flow rate. It was assumed that the cost of the fibres and module housing comprised the capital cost, while the operating cost consisted of the pumping energy. A capital recovery factor of 0.3 was used to convert capital costs to a yearly cost. It was found that the optimum module dimensions are an outer diameter of between 90mm and 160mm and a length of 0.6m. Finally the pressure distributions on the lumen and shell sides during both cross-flow filtration and backwash were examined. Shade plots proved useful for identifying possible areas of stagnant flow, as well as indicating where backwash is the most effective. / AFRIKAANSE OPSOMMING: Die hidrodinamika binne-in 'n holvesel membraanmodule vir die ultrafiltrasie van drinkwater is ondersoek. Die doel was om 'n hidrodinamiese model te gebruik om die permeaatvloed vir modules van verskeie dimensies te voorspel. Verskillende modelle is oorweeg, maar die meeste kon nie belangrike faktore soos makroskopiese radiale drukqradiente of nat veselverlenging in ag neem nie. Die Poreuse Medium Model was die mees geskikte model en is gebruik saam met Fastf/o, 'n sagteware pakket wat gegrond is op die eindige element metode, om vergelykings vir die drukverspreiding binne-in die module op te los en permeaatvloed te voorspel. Die permeabiliteit van die membrane is verkry met behulp van numeriese en eksperimentele prosedures en 'n waarde van 2.3 x 10-13 m is bepaal. Hierna is 'n koste-analise uitgevoer om die mees ekonomiese module afmetings (Iengte en buitedeursnit) te bepaal vir 'n gegewe produk vloeitempo. Daar is aanvaar dat kapitaalkoste bestaan uit die koste van vesels en module-omhulsel, terwyl bedryfskoste bereken is deur die hoeveelheid energie benodig om die pomp aan te dryf. 'n Kapitaalherwinningsfaktor van 0.3 is gebruik om kapitaalkoste om te skakel na 'n jaarlikse koste. Die optimum module afmetings is 'n lengte van 0.6m en 'n buite-deursnit van tussen 90mm en 160mm. Laastens is die drukverspreidings tydens beide kruisvloeifiltrasie en die terugspoelproses ondersoek. Areas van stagnante vloei kan deur middel van skadu-grafieke geYdentifiseer word, terwyl dit ook moontlik is om die terugspoelproses te optimeer.

Thesis (MIng)--University of Stellenbosch, 2000. / ENGLISH ABSTRACT: Fouling is readily acknowledged as one of the most critical problems limiting the wider application of membranes in liquid separation processes. A better understanding of fouling layer formation and its monitoring is needed in order to improve on existing cleaning techniques. Plant operation can be optimised if fouling can be monitored by noninvasion means either on the plant itself or on an attached monitoring device. The overall scope of this research was to develop a non-destructive, real-time, in situ visualisation technique or device for concentration polarisation and fouling layer monitoring. Ultrasonic-time-domain-reflectometry (UTDR) was employed as a visualisation technique to provide real-time characterisation of the fouling layer. A 24 cm-long rectangular flat sheet aluminium cell was designed and used as separation device for a desalination system. The experimental results obtained using this module confirmed that there are an excellent correspondence between the flux decline behaviour and the UTDR response from the membrane. The ultrasonic technique could effectively detect fouling layer initiation and growth on the membrane in real-time. In addition to the measurement of fouling, the ultrasonic technique was also successfully employed for monitoring membrane cleaning. Since no real-time permeation data is available during cleaning operations in industrial applications, a UTDR monitoring device may prove to be a very valuable technique in optimising cleaning strategies. The technique was further tested on an 8-inch diameter spiral wrap industrial module and good results were obtained. Stagnant zones, as well as flux flow behaviour inside the module could be determined. However, more research IS needed to fully understand the complex phenomena inside a spiral wrap module. Overall, the UTDR technique and its use in monitoring devices have a major impact in the membrane industry due to its extremely powerful capabilities. / AFRIKAANSE OPSOMMING: Membraan-bevuiling of -verstopping is die grootste struikelblok wat die algemene aanwending van membrane vir verskillende watersuiweringsprosesse negatief beinvloed. 'n Beter begrip van membraan-bevuiling, asook beter metingsmetodes daarvan is nodig om op bestaande skoonmaaktegnieke te verbeter. Die hoofdoel van hierdie studie was die ontwikkeling van 'n nie-destruktiewe-in-lyn visuele tegniek vir die meting van konsentrasie polarisasie en membraan-bevuiling. Deur gebruik te maak van ultrasoniese klank golwe, is 'n tegniek ontwikkel wat 'n direkte visuele aanduiding kon gee van die toestand van membraan-bevuiling binnein die module. 'n Reghoekige aluminium-module, 24 cm lank, is ontwerp en gebou waarbinne die membraan geplaas is vir die skeidingsproses. Resultate dui daarop dat daar 'n uitstekende verband bestaan tussen die afname in permeaatvloei en die ultrasoniese eggo vanaf die membraan. Die ultrasoniese tegniek kon die vorming van en toename in membraan-bevuiling doeltreffend karakteriseer. In teenstelling hiermee, is die tegniek ook suksesvol aangewend om die skoonmaak-proses van membrane te ondersoek. Met min of geen data beskikbaar vir die skoonmaak-proses van membrane in die industriële sektor, het die tegniek enorme potensiaal in die optimisering van bestaande skoonmaak-tegnieke. Die tegniek is verder aangewend op 'n industriële 8-duim deursnee spiraal-module en goeie resultate is verkry. Stagnante sones asook vloed-vloei-patrone binne-in die module kon suksesvol bepaal word. Baie navorsing is egter nog nodig om die ingewikkelde data wat gegenereer word tydens die ondersoek van 'n spiraal-module ten volle te verstaan. Die enorme potensiaal en moontlikhede van die ultrasoniese tegniek kan die begin wees van 'n revolusie in die membraan-industrie.

Thesis (MScEng)--University of Stellenbosch, 2002. / ENGLISH ABSTRACT: Flotation was introduced early in the zo" century as a separation process for extracting valuable minerals from grinded ore. Today flotation is a dominant mineral concentration method and is used for almost all sulphide minerals and also for nonsulphide metallic minerals, industrial minerals, and coal. Automation and control has become a basic requirement in flotation plants. Effective control of pulp levels plays a very important role in stabilising the flotation process and therefore requires careful attention. This thesis presents a de-coupled level controller that has been developed for the control of levels in cascaded flow processes, including multi-tank cascaded flotation processes. The controller was developed on a two tank cascaded pilot plant using water as a flow medium. A simulation model was constructed for the cascaded flow process. The simulation model made it possible to develop and evaluate a decoupled level controller in a simulation environment. Finally independent loop PIO control and integrated PIO control loops with feed-forward de-coupling were compared through simulation, as control strategies for the pilot plant. / AFRIKAANSE OPSOMMING: Flotasie is vroeg in die 20ste eeu bekend gestel as 'n skeidingsproses om waardevolle minerale te onttrek uit fyngemaalde erts. Vandag is flotasie die dominante proses om minerale te konsentrasie en word gebruik vir byna aile sulfied minerale sowel as nie-sulfied metaal minerale, industriele minerale and steenkool. Outomatisasie en beheer het 'n basiese vereiste geword in flotasie aanlegte. Die effektiewe beheer van pulpvlakke speel 'n baie belangrike rol in die stabilisering van die flotasie proses en verdien om hierdie rede deeglike aandag. Hierdie tesis stel 'n ontkoppelde vlakbeheerstelsel voor wat ontwikkel is vir die beheer van vlakke in kaskade vloei prosesse byvoorbeeld multi-tenk flotasie prosesse. Die beheerstelsel is ontwikkel op 'n twee-tenk kaskade toetsaanleg met water as vloeimedium. 'n Volledige simulasiemodel is ontwikkel wat dit moontlik gemaak het om die vlakbeheerstelsel te ontwerp, toets en verfyn in 'n simulasie omgewing. Verder is die verskil tussen onafhanklike enkellus PID beheerders en ontkoppelde PID beheerlusse ondersoek en word in die tesis geillustreer.

Properties of polymers in thin films are distinct from those in the bulk due to the significant effects of free or substrate surfaces. The presence of a free surface allows an increased mobility of polymer chains in the near surface region, therefore, a lower glass transition temperature (T_g). With this lower surface T_g, a surface-specific crystallization phenomenon occurring at temperatures much lower than the bulk crystallization temperature (T_c) in polymers including PET, PEN and PVOH has previously been observed. However, whether or not this surface-specific crystallization is a phenomenon observable in all crystallizable polymers is still a question. Similarly, due to this greater mobility, phase separation may also be able to take place in the near-surface region of a polymer blend at a temperature much lower than the bulk phase separation temperature. Yet, no such investigation on polymer blends has been carried out. In addition, it is interesting to study the thin-film behaviours of a block copolymer that undergoes both phase separation and crystallization and compare these with corresponding bulk behaviour. In this thesis, the thin-film crystallization behaviour of polyamide 12 (PA12) in spin-cast films is presented together with some investigation of crystallization of polyamide 6 (PA6) and polystyrene. Polystyrene and poly(methyl methacrylate) (PS/PMMA) systems are used to illustrate the phase behaviours specific to the near-surface region. Finally, the microstructural evolution in high hard block content thermoplastic polyurethane (TPU) thin films on annealing has also been investigated. These TPUs have hard segments (HS) extended by 2 methyl 1,3 propanediol (2M13PD) or 1,5 pentanediol (15PD). With its flexible chains, PA12 crystallizes during spin coating forming as-spin-cast crystals with morphology that varies with solvent evaporation rate and film thickness. Despite the as spin-cast crystals, the free surface allows secondary surface crystallization of PA12 at an annealing temperature (T_a) roughly 20°C below the bulk T_c. The secondary surface crystals were indicated to exist in the most stable crystalline phase of PA12. Similar secondary surface crystallization has also been observed in the PA6 films but at a higher T_a due to the higher T_g of PA6. In addition, surface-specific crystals have been observed in PS (semicrystalline, likely due to some stereoregularity of composition), a polymer with bulky side groups. The PS surface crystals are, however, flat-on oriented showing the important effect of side groups on the morphology or growth shape of surface crystals. The discovery of these surface crystals supports the universality of surface specific crystallization. Using fast solvent quenching, it is possible to "freeze in" a structure containing both PS and PMMA in the near surface region. On annealing, surface-specific phase behaviours (observable as pits, undulations and aggregations) confined to the near-surface region take place first at temperatures around or just below the bulk polymer T_g, while bulk vertical phase separation and dewetting of PS to PMMA, forming holes, network structures and islands, occur at temperatures well above T_g. This surface specific phenomenon, being a result of the free surface, should be applicable to other phase separation systems with a free surface as well. An increase in the crystallinity of PS was found to promote the phase separation process, but the free surface effect is independent of the interplay between the crystallization and phase separation. Rather than having a two-phase morphology, as was previously observed in melt-quenched bulk samples, 2M13PD extended TPU spin-cast films showed a single-phase morphology as-spin-cast. However, the HS ordering, the formation of mesophase, the melting of HS ordered regions, and microphase mixing observed in thin films are consistent with the bulk results but with slightly different transition temperatures due to spatial confinement. With a more flexible chain extender, e.g. 15PD, the hard and soft phase separation is more limited. The thin film investigations have allowed a better understanding of the microstructural evolution in these high hard block content TPUs on annealing by imaging the morphology directly. A thin-film specific phenomenon: formation of large multilayer flat-on crystals, was also observed in these TPU thin films. These crystals are initially developed from preformed aggregations and are believed to be induced by the significant substrate effect in thin films and the free surface effect.

The overall aim of this study was to investigate the association between family structure in childhood and mental health problems in young adulthood. A prospective cohort study was conducted with 481,777 individuals with complete follow-up information, which was obtained from national registers in Sweden. Individuals who were living with only one biological parent at age 17 were compared with those who grew up with two parents with regard to retrieval of prescribed psychotropic drugs at age 35. The association was examined by Cox regression analyses with equal survival time for all individuals included in the analyses. The results demonstrated a higher risk for retrieval of psychotropic medicines among the individuals who grew up with only one parent, with hazard ratio of 1,21 (95%CI: 1,19-1,23). The multivariate analyses showed that a part of the association was explained by familial and individual factors, namely parents’ country of origin, area of residence, parents’ and the individual’s educational attainment, receipt of social benefits and parents’ history of psychiatric disorder. The results indicated that the increased risk of mental health problems among individuals who grew up with only one parent might be accounted for by various psychological, social and economic factors associated to parental separation.

Thesis (MScEng (Process Engineering))--Stellenbosch University, 2008. / Nitriles are precursors of important amides and organic acids (e.g. acrylamide, nicotinamide, mandelic acid and acrylic acid) which are used, inter alia, as food additives, in plasticisers, detergents, make-up, medicine and as chemical intermediates in the production of various important polymers. Traditionally, chemical processes are used to convert nitriles to amides and organic acids but these processes are non-specific causing various by-products to form. Chemical processes are also environmentally unfriendly and require harsh conditions. Nitrile conversions through an enzymatic route, on the other hand, have the distinct advantages of excellent chemo-, regio- and stereo selectivities, mild process conditions and reduced downstream processing costs. The enzymatic process is mediated via an initial nitrilase catalysed conversion to amide, followed by an amidase catalysed conversion to acid. This research focused on the latter part of the enzymatic transformation of nitriles, which is the amidase catalysed biotransformation of an amide to an acid, specifically with respect to the development of a membrane immobilised amidase continuous process which has the major advantage of enzyme retention coupled with product separation. The research was conducted in three parts namely the characterisation of the free amidase, the development of the experimental bioreactor system and the quantification of the membrane immobilised amidase process.

Thesis (MScEng (Process Engineering))--University of Stellenbosch, 2009. / ENGLISH ABSTRACT: The aim of this study was to modify the surface of polyethersulfone (PES) ultrafiltration (UF) membranes to produce a more hydrophilic membrane by cross-linking poly(vinyl alcohol) (PVA) with sodium tetraborate (Na2B4O7.10H2O) (SB) on the surface. Key preparation factors were identified as PVA molecular weight, concentrations of the PVA and SB, cross-linking reaction time, number of coatings and the mode of coating. The effect of these factors on the membrane performance (salt retention and permeate flux) is discussed. These PVA-SB membranes typically had 11.46% retention and 413.30 L/m2.h flux for a feed containing 2000 ppm NaCl (0.45 MPa, 20°C, 45 – 50 L/h). The coating was shown to be uniform and stable by Fourier transform infrared spectroscopy (FT-IR) analyses. Coating significantly increased hydrophilicity and a maximum flux increase of 500 L/m2.h was reached. Measurements showed a reduced water contact angle and this confirmed the obvious enhancement of surface hydrophilicity. As a control, the role of the PVA base layer without cross-linking and the effects of its drying and heating on the water permeability of the PES-UF membrane were also studied, in order to ascertain maximum treatment conditions. Retention and permeate flux were determined (feed solution: 2000 ppm NaCl, applied pressure 0.45 MPa, 25°C, 45 – 50 L/h). It was found that the heating had the largest effect on the reduction of water permeability and therefore 50°C was the limit for treatment of this specific PES-UF membrane. Thin-film composite (TFC) membranes were prepared by an interfacial polymerization (IP) reaction between a polyfunctional amine and tri- or di-functional carboxylic chloride and then evaluated for their reverse osmosis (RO) performance. The salt retention of the PVA-SB membranes was improved when covering the cross-linked PVA gel sub-layer with a polyamide (PA) layer. However, the permeate flux decreased to below 30 L/m2.h (2000 ppm NaCl, 1 – 2 MPa, 20°C, 45 – 50 L/h). Two TFC membranes made from trimesoyl chloride (TMC) with m-phenylenediamine (MPD) or 2,6-diaminopyridine (DAP) exhibited retentions of 96.71% to 89.65% and fluxes of 10.93 to 27.91 L/m2.h, depending on the type of diamine used, when tested with a 2000 ppm NaCl solution (2 MPa, 25°C, 45 – 50 L/h). Two TFC membranes made from a n ew 2,5-furanoyl chloride (FC) with MPD or DAP exhibited retentions of 34.22% to 58.54% and fluxes of 49.21 to 25.80 L/m2.h, depending on the type of diamine used, when tested with a 2000 ppm NaCl solution (1 MPa, 25°C, 45 – 50 L/h). Novel PVA-SB-DAP-FC membranes made from the DAP with FC had the highest hydrophilicity value and exhibited >58.54% NaCl retention and 25.80 L/m2.h flux, and 75.08% MgSO4 retention and 34.75 L/m2.h flux, when tested with (2000 ppm feed, 1 MPa, 25°C, 45 – 50 L/h). The effect of the chemical structures of the different amines and carboxylic chlorides used on the RO performances of the TFC membranes prepared by two amines reacting with TMC or FC, on the surfaces of the modified asymmetric PES-UF membranes, was investigated. FT-IR and water contact angle determination were used to characterize the chemical structure, morphology and hydrophilicity of the PA layers of the composite membranes. The response surface methodology (RSM) was used to optimize the preparation conditions that had the largest effects on the RO performance of the PVA-SB-DAP-FC membranes. Good membrane performance could be realized particularly by manipulating three variables: DAP concentration, FC concentration and polymerization time (PT). The regression equation between the preparation variables and the performance of the composite membranes was established. Main effects, quadratic effects and interactions of these variables on the composite membrane performance were investigated. The membranes were characterized in terms of pure water permeation (PWP) rate, molecular weight cut off (MWCO), solute separation and flux. Mean pore size (μp) and standard deviation (σp) of the membranes were determined using solute transport data. The results revealed that PVA-SB membranes have almost the same pure water permeation that PES-UF membranes have. The MWCO of the PES-UF membranes decreased from 19,000 to 13,000 Daltons when the membrane was coated with PVA. / AFRIKAANSE OPSOMMING: Die doel van hierdie studie is die modifikasie van die oppervlakte van poliëtersulfoon ultrafiltrasie (PES-UF) membrane om meer hidrofiliese membrane te berei deur die kruisbinding van polivinielalkohol (PVA) met natriumtetraboraat ((Na2B4O7.10H2O) (NaB) op die membraanoppervlakte. Sleutelfaktore in die bereidingsproses is geïdentifiseer, naamlik: PVA molekulêre massa, PVA en NaB konsentrasies, kruisbindingsreaksietyd, die aantal bestrykingslae, en die manier waarop die bestrykingslae aangewend is. Die invloed van hierdie faktore op die membraanontsouting en vloed is ondersoek, en word hier bespreek. Hierdie PVA-NaB membrane het die volgende tipiese resultate getoon: 11.46% ontsouting en 413.30 L/m2.h vloed (Kondisies: 2000 dpm NaCl oplossing, 0.45 MPa toegepaste druk, 20 °C, vloeitempo 45–50 L/h). Die deklaag was uniform en stabiel, soos bepaal d.m.v. FTIR. Die aanwesigheid van die deklaag het die hidrofilisiteit verhoog en 'n maksimum vloed van 500 L/m2.h is behaal. Die waterkontakhoek is ook gemeet; 'n laer waarde het 'n verbetering in die hidrofilisiteit van die oppervlakte bevestig. Die rol van die PVA basislaag, sonder kruisbinding (kontrole), en die effek van uitdroging en verhitting hiervan, is ook bestudeer, om sodoende optimale behandelingskondisies te bepaal. Membraanontsouting en vloed is bepaal (Kondisies: 2000 dpm NaCl oplossing, 0.45 MPa toegepaste druk, 25 °C, vloeitempo 45–50 L/h). Verhitting het die grootste effek gehad op die afname in vloed. Daar is bevind dat 'n maksimum temperatuur van 50°C geskik is vir die behandeling van hierdie spesifieke PES-UF membraan. Dunfilmsaamgestelde (DFS) membrane is berei d.m.v. 'n tussenvlakpolimerisasiereaksie tussen 'n polifunksionele amien en 'n di- of tri-funksionele karbonielchloried, en daarna is die tru-osmose (TO) gedrag bepaal. Die ontsouting van die PVA-NaB membrane was hoër nadat die kruisgebinde PVA jel sub-laag met 'n poliamied (PA) laag bedek is. Die vloed het egter afgeneem, tot onder 30 L/m2.h (Kondisies: 2000 dpm NaCl oplossing, 1–2 MPa toegepaste druk, 20 °C, vloeitempo 45–50 L/h). Twee DFS membrane is berei met trimesoïelchloried (TMC), naamlik met m-fenieldiamien (MFD) of 2,6-diaminopiridien (DAP). Afhangend van die diamien wat gebruik is, is die volgende ontsoutingsresultate en vloede verkry: 96.71% tot 89.65% en 10.93 to 27.91 L/m2.h (Kondisies: 2 000 dpm NaCl oplossing, 2 MPa toegepaste druk, 25 °C, v loeitempo 45–50 L/h). Twee DFS membrane is ook berei met 'n nuwe verbinding, 2,5-furanoïelchloride (FC), en MFD of DAP. Afhangend van die diamien wat gebruik is is die volgende ontsoutingsresultate en vloede behaal: 34.22% tot 58.54% en 49.21 tot 25.80 L/m2.h (Kondisies: 2000 dpm NaCl oplossing, 1 MPa toegepaste druk, 25 °C, vloeitempo 45–50 L/h). Die PVA-NaB-DAP-FC membrane het die hoogste hidrofilisiteit getoon: 58.54% NaCl ontsouting en 25.80 L/m2.h vloed, en 75.08% MgSO4 ontsouting en 34.75 L/m2.h vloed (2000 ppm NaCl oplossing, 1 MPa toegepaste druk, 25 °C, vloeitempo 5–50 L/h). Die invloed van die chemiese struktuur van die verskillende diamiene en karboksielsuurchloriedes wat gebruik is in die bereiding van die DFC membrane op die oppervlakte van die gewysigde PES-UF membrane is in terme van TO ondersoek. FTIR en kontakhoekbepalings is gebruik om die chemiese struktuur, morfologie en hidrofilisiteit van die PA lae van die saamgestelde membrane te bepaal. Die eksperimentele oppervlakte ontwerp metode is gebruik om die bereidingskondisies vir die TO aanwending van die PVA-NaB-DAP-FC membrane te optimiseer. Goeie resultate is verkry deur die volgende veranderlikes te manipuleer: DAP en FC konsentrasies en die tydsduur van die polimerisasie. 'n Regressie-vergelyking tussen die bereidingsverandelikes en die funksionering van die saamgestelde membrane is bepaal. Die volgende is ook ondersoek vir hul effek op die funksionering van die saamgestelde membrane: hoof-effekte, vierkantseffekte, en interaksie tussen veranderlikes. Die eienskappe van die membrane wat bepaal is, is: deurlatingstempo van suiwer water (DSW), molekulêre massa-afsnypunt (MMAP), skeiding van opgeloste sout en vloed. Deurlating van opgeloste sout data is gebruik om gemiddelde poriegrootte (μp) en standaard afwyking (σp) van die membrane te bepaal. Resultate het getoon dat die PVA-NaB membrane amper dieselfde DSW gehad het as die PES-UF membrane. Die MMAP van die PES-UF membrane het afgeneem van 19,000 tot 13,000 Daltons na behandeling met PVA.

Thesis (MScEng (Process Engineering))--University of Stellenbosch, 2009. / ENGLISH ABSTRACT: Membrane fouling is universally considered to be one of the most critical problems in the wider application of membranes in filtration separation. Fouling is caused by the deposition of particles not only on the surface of the membrane, but also inside the membrane pores, which reduces permeate flux and leads to a reduction of the efficiency and the longevity of the membrane. The backpulsing cleaning method can be used to remove deposited foulants from the surface of the membrane, without having to shut down the plant. Ultrasonic time-domain reflectometry (UTDR) is a nondestructive technique, used to detect and measure the growth of fouling layer on the membrane surface during microfiltration and ultrafiltration processes. In this study flat-sheet microfiltration (MF) and ultrafiltration (UF) membranes were fouled during a cross-flow filtration processes using dextrin, yeast or alumina (feed pressure 100 kPa and feed flow rate 0.45 liter/minute), in a flat cell. Infrasound frequency backpulsing, in the permeate space, was used to clean the membranes. Backpulsing was carried out using the permeate water or soap solutions. The peak pressure amplitude of the pulses used to clean the membranes was 140 kPa, the pulsing was applied at a frequency of 6.7 Hz. The main objectives of this research were: (1) to obtain a fundamental understandimg of how foulants deposit on membrane surfaces and how the foulant deposits can be removed using the backpulsing cleaning technique during MF and UF, (2) to use the ultrasonic measurement technique for monitoring the growth and removal of the fouling layer on the membrane surface and (3) Use scanning electron microscopy (SEM) as a direct measurement technique to analyze the structure the foulant deposits on membrane surfaces before and after cleaning. Results showed that a flux value of between 55% and 98% of the clean water flux value can be achieved by backpulsing cleaning. UTDR was successfully applied to monitor membrane cleaning and provide information about the growth and removal of fouling layers on the membrane surface. / AFRIKAANSE OPSOMMING: Membraanaanvuiling is wêreldwyd bekend as een van die mees kritieke probleme wat die wyer aanwending van membrane vir skeidingsprosesse benadeel. Aanvuiling word veroorsaak deur die deponering van partikels, nie net op die oppervlak van die membraan nie, maar ook binne-in die membraanporieë, wat die volgende tot gevolg het: 'n afname in vloed deur die membraan, 'n afname in die effektiwiteit van die membraan, en 'n korter membraanleeftyd. Die teenpulsskoonmaakmetode kan gebruik word om die aanvuilingslaag vanaf die membranoppervlakte te verwyder sonder dat dit nodig is om die membraantoetsapparaat af te skakel. Ultrasoniese-tydsgebied-weerkaatsing (UTW) is 'n nie-vernietigende tegniek wat gebruik kan word om die groei van 'n aanvuilingslaag op 'n membraanoppervlakte tydens mikrofiltrasie (MF) of ultrafiltrasie (UF) te identifiseer en te meet. In hierdie studie is plat-vel MF en UF membrane bevuil gedurende 'n kruisvloeifiltrasieproses deur gebruik to maak van dekstraan, gis of alumina, in 'n plat sel. Infraklank-frekwensieteenpols, in die permeaatgebied, is gebruik om die membrane skoon te maak. Hiervoor is die proseswater of 'n seepoplossing gebruik. Die maksimum drukamplitude van die pulse wat gebruik is was 140 kPa, en die puls was aangewend teen 'n frekwensie van 6.7 Hz. Die hoofdoelwite van hierdie studie was die volgende: (1) om inligting in te win oor hoe aanvuilingsmateriale op membraanoppervlaktes gedeponeer word tydens MF en UF en hoe hulle verwyder kan word deur gebruik te maak van die teenpulsskoonmaaktegniek; (2) om van die teenpulsskoonmaaktegniek gebruik te maak om die groei van die bevuilingslaag asook die verwydering daarvan op die membraanoppervlakte te monitor; en (3) om van skandeerelektronmikroskopie (SEM) as 'n direkte analitiesetegniekgebruik te maak om die struktuur van die aanvuilingsmateriaal voor en na die die skoonmaakproses te analiseer. Deur gebruik te maak van teenpulsskoonmaak kon die membraanvloed tot tussen 55–98% van die oorspronklike suiwerwatervloed verbeter word. Sodoende is ultrasoniese-tydsgebiedweerkaatsing suksesvol gebruik om die skoonmaak van membrane te monitor asook om inligting in te win i.v.m. die groei en verwydering van die aanvuilingslae op die membraanoppervlaktes.