Thesis (MScIng)--University of Stellenbosch, 2003. / ENGLISH ABSTRACT: Both porous and dense hydrogen selective membranes have recently been an active area of research. The combination of a reactor and a separator in the form of a membrane reactor is seen as a feasible application in which to perform dehydrogenation reactions. These reactions are equilibrium limited so that the removal of the product H2 by a selective membrane can improve the process effectiveness. Early Pd-based membranes were made of thin-walled tubes. In an attempt to increase permeation rates, thin supported Pd membranes have been developed. This study investigated the development and performance of a catalytic membrane reactor. The membrane reactor consists of a tubular alumina membrane support coated on the inside with a film of palladium or a palladium-copper alloy. This reactor was used for the dehydrogenation of isopropanol. The thin film was coated on the alumina support using an electroless plating process. This process occurs in a liquid medium where palladium and copper are deposited by electrolysis or electroless means. With these methods alloys can also be deposited on the support. By plating a thin film of palladium on the alumina membranes, will attract hydrogen molecules from the reaction product, which will increase the reaction rate. The electroless plating process consists of four major components: (i) (ii) (iii) (iv) reducing agent ( 0.04 M hydrazine), temperature bath, stabilised source of metal ions, and support membrane (α-alumina). Heat treatment was carried out on the coated membranes for 5 hours in a hydrogen atmosphere at 450°C. The plated membranes supplied by Atech were characterised using X-ray diffraction (XRD), scanning electron microscopy (SEM) and particle induced Xray emission (PIXE) before and after heat treatment. SEM photographs showed that the pore size of the membranes was doubtful and due to that the films were not of a dense nature. XRD results revealed that heat treatment led to the formation of smaller Pd and Cu crystallites. The concentration profiles constructed from the PIXE results indicated that Cu and Pd penetrated deep into the pores of the membrane during film preparation. Different catalysts (Al2O3, MgO and SiO2) were tested and the best one was chosen as catalyst in the membrane reactor. These catalytic runs were done in a plug flow (fixedbed) reactor. Different particle sizes of catalysts were also tested. A 9.2 Cu wt % on silica achieved the highest acetone yields for the temperatures tested. Two different types of alumina membrane reactors were used. These were supplied from SCT. One membrane only coated with palladium and the other coated with palladium and copper. Selectivity and permeability tests were also carried out on these membranes. Selectivities of up to 90.6 could be reached with the palladium coated membrane. The palladium-copper plated membrane only achieved selectivities of up to 13. With heat treatment this value decreased even more. The palladium coated membrane also achieved much better conversion to acetone in the dehydrogenation of 2-propanol. The reason for that is its better selectivity. The palladium-copper membrane reactor did not show much better results than the fixed-bed reactor. / AFRIKAANSE OPSOMMING: Hierdie studie ondersoek die ontwikkeling en werk verrigting van ‘n katalitiese membraan reaktor. Die membraan reaktor bestaan uit ‘n dun film palladium of palladium-koper allooi wat aan die binnekant van ‘n silindriese alumina membraan geplateer word. Die alumina dien as membraanbasis. Hierdie reaktor sal gebruik word vir die dehidrogenering van isopropanol. Die dun films van metaal word neergeslaan op die alumina basis deur ‘n elektrodelose platerings proses. Hierdie proses vind plaas in ‘n vloeistof medium waar palladium en koper neerslag plaasvind op ‘n elektrodelose wyse. Met hierdie metode kan metaal allooie geplateer word op basis membrane. Deur ‘n dun palladium lagie aan die binnekant van die alumina membrane te plateer sal veroorsaak dat waterstof molekules uit die reaksie volume sal weg beweeg. Dit sal ‘n verhoging in reaksie tempo meebring. Die platerings proses bestaan uit vier komponente: (i) reduseermiddel (0.04M Hidrasien), (ii) temperatuur water bad, (iii) stabiliseerde bron van metaal ione (Pd/Cu kompleks oplossing), en (iv) basis membraan (α-alumina). Hittebehandeling vir 5 uur is uitgevoer op hierdie geplateerde membrane by 450°C in ‘n waterstofatmosfeer. Die geplateerde membrane is daarna gekarakteriseer- voor en na hittebehandeling. Dit is gekarakteriseer deur X-straal diffraksie (XRD), skanderings elektron mikroskopie (SEM) en partikel geïnduseerde X-straal emissie (PIXE). XRD eksperimente het gewys dat die koper en die palladium ‘n allooi gevorm het. Veranderinge in kristaltekstuur het voorgekom na hittebehandeling. Tydens hittebehandeling was kleiner palladium en koper kristalle gevorm. SEM resultate het getoon dat die film nie baie dig was nie en die porie grootte van die membrane was ook nie korrek nie. PIXE resultate het die konsentrasieprofiele van beide koper en palladium oor die dikte van die membraan bepaal. Dit het gewys dat die Cu en Pd diep binne die membraan penetreer het tydens voorbereiding van die membraan. Verskillende soorte kataliste (Al2O3, MgO and SiO2) is ondersoek vir die dehidrogenering van isopropanol. Hierdie katalitiese ondersoek is gedoen in ‘n propvloei reaktor. Die beste katalis is gekies om in die membraan reaktor te gebruik. Verskillende partikel groottes is ook ondersoek. ‘n 9.2 Cu massa % koper op silika katalis het die beste omsetting na asetoon verkry vir die temperature waarvoor toetse gedoen is. Twee tipes membraan reaktors is gebruik. Een met net ‘n palladium film, terwyl ‘n palladium-koper allooi op die ander membraan reaktor gedeponeer was. Selektiwiteits- en deurlaatbaarheids toetse is op altwee membrane gedoen. Selektiwiteite van 90.6% kon verkry word met die palladium membraan. Die palladium-koper membraan kon slegs ‘n selektiwiteit van 13% bereik. Met hittebehandeling daarvan het die selektiwiteit selfs meer afgeneem. Die palladium membraan het ook hoër omsettings na asetoon getoon. Die rede hiervoor is die membraan se hoë selektiwiteit. Die palladium-koper membraan het nie veel beter resultate as die propvloei reaktor gelewer nie.

ENGLISH ABSTRACT: The first successful captive spawning of the South African abalone Haliotis midae occurred in the 1980’s and subsequently the commercial abalone industry in South Africa has developed, with an estimated investment of US$ 12 million and annual output of 500 to 800 tons by 2001, making South Africa the biggest abalone producer outside of Asia. Natural kelp is currently the major feed and the development of a suitable substitute, and improved disease management in abalone culture are seen as the primary factors limiting expansion of the industry in South Africa. Further, abalone growth rates are very slow and improvements in growth rate will lead to shortened production times with benefits to producers. Diseases in aquaculture have traditionally been combated using antibiotics as treatment (therapeutic usage) and preventative measure (prophylactic usage). In terrestrial livestock management, antibiotics are also used as growth promoters. The use of antibiotics in aquaculture has recently sparked concerns about the development of antibiotic resistance in pathogens of humans and aquaculture organisms, and alternative strategies to using antibiotics mainly focus on manipulating the microbial composition in the host organism, in order to establish a beneficial microbial population to prevent disease. The role that organic acids and their salts can play as growth promoters in the South African abalone Haliotis midae, and as manipulators of the gut microflora of this species of abalone was investigated and compared to the effects of antibiotics. Three different treatments were tested against a negative control and a positive control containing 30ppm avilamycin, a commercial antibiotic growth promoter (AGP) used in the pig and poultry industry. The 3 treatments consisted of 1% acetic and 1% formic acid (treatment AF), 1% sodium benzoate and 1% potassium sorbate (treatment SBPS), and 1% benzoic and 1% sorbic acid (treatment BS). Three different experiments were conducted to test the effects of the different acids and salts. The first experiment was under controlled optimum water temperature conditions (16.5ºC), another at elevated water temperature (20.5ºC) in order to test response during temperature stress conditions, and the final trial was conducted under uncontrolled practical production conditions. In an attempt to establish the mechanism by which the treatments have their effects (if any), the composition of the gut microflora of the abalone was monitored. It was found that the organic acids and salts investigated can enhance the growth rate of Haliotis midae in the size class 23 mm to 33 mm mean length significantly when compared to both control treatments. It was further found that the tested AGP had no effect on growth rate. None of the treatments had a significant effect on feed conversion ratio (FCR), Incidence cost (IC) or feed intake. It could also not be shown that the treatments affected the intestinal microflora of the abalone, although this might be due to inadequate microbiological methods. The mechanism by which the acids and salts have their effects could not be established. It was found that the animals in the controlled system underwent an initial adaptation period, which led to improvement in specific growth rate (SGR), FCR and IC as the experiment progressed during the controlled optimal conditions experiment. Large differences in FCR and IC was seen for controlled optimal conditions and production conditions which means that there is still a large scope for developing methods to improve practical on-farm feed utilisation by abalone. SGR, FCR and IC were negatively influenced by raising water temperature from 16.5ºC to 20.5ºC. The composition of the gut microflora of the abalone also changed significantly after the water temperature was raised. It appears that animal weight gain and shell growth respond differently to changing water temperatures, which is reflected in a change in Fulton condition factor. A relationship between the length and weight of abalone between 15 mm and 47 mm was established and it was found that Haliotis midae does not follow an isometric growth relationship. This relation can be used as a tool to improve farm management and therefore also profitability. Various micro-organisms were isolated from Haliotis midae during the trial, but their relationship and interaction with abalone is not clear. Clear dominance by specific species of bacteria was observed during certain periods. The current research has clearly showed the potential of organic acids and their salts to act as growth promoters in the South African abalone Haliotis midae, with application in both the local aquaculture and feed manufacturing industries. The possibility further exists that some aspects of the current research can be adapted to be applicable in other abalone species and even in other aquaculture species. / AFRIKAANSE OPSOMMING: Die eerste suksesvolle aanteel van die Suid-Afrikaanse perlemoen Haliotis midae in gevangeskap is in die 1980’s gerapporteer, waarna ‘n suksesvolle akwakultuur industrie ontwikkel het met ‘n geskatte produksievermoë van 500 tot 800 ton en kapitaalbelegging van US$ 12 miljoen in 2001. Suid-Afrika is tans die grootste perlemoen-produserende land wat buite Asië geleë is. Die ontwikkeling van ‘n geskikte alternatiewe voedselbron vir natuurlike kelp (tans die algemeenste voedselbron wat gebruik word in die kweek van perlemoen), sowel as verbeterde siektebestryding word tans gesien as die hooffaktore wat verdere uitbreiding in die Suid-Afrikaanse industrie beperk. Perlemoen het verder baie stadige groeitempo’s en enige verbetering in hierdie verband sal produksietye verkort en dus produsente bevoordeel. Siektes in akwakultuur word tradisioneel bestry deur gebruik te maak van antibiotiese behandeling (terapeutiese bestryding) of van voorkomende behandeling (profilaktiese bestryding). In gewone diereproduksie-sisteme (bv. varke en hoenders) word antibiotika ook gebruik as groeistimulante. Die gebruik van antibiotika in akwakultuur het onlangs die bekommernis laat ontstaan dat sekere menslike en dierepatogene weerstand kan ontwikkel teen sommige middels, wat die behoefte laat ontstaan het om siektebestryding sonder die gebruik van antibiotika te ontwikkel. Alternatiewe strategieë fokus grootliks daarop om die samestelling van die mikrobiese bevolking van die gasheer te manipuleer en sodoende ‘n voordelige bevolking in die gasheer te vestig, wat dan siektes voorkom. Daar is ondersoek ingestel na die rol van organiese sure en hul soute as groeistimulante en manipuleerders van die mikrobiese bevolking in die Suid-Afrikaanse perlemoen Haliotis midae. Drie verskillende behandelings is getoets en vergelyk met beide ‘n negatiewe- en positiewe kontrole (wat 30 dele per miljoen van ‘n kommersiële antibiotiese groeistimulant bevat het). Die drie formulasies het onderskeidelik bestaan uit ‘n mengsel van 1% etanoëen 1% metanoësuur (behandeling AF), 1% bensoë- en 1% sorbiensuur (behandeling BS) en 1% natriumbensoaat en 1% kaliumsorbaat (behandeling SBPS). Om die effekte van hierdie formulasies te toets, is daar 3 proewe gedoen. Een proef is gedoen onder temperatuurbeheerde toestande teen ‘n optimum watertemperatuur van 16.5ºC terwyl ‘n ander gedoen is onder onbeheerde, praktiese produksie-omstandighede. ‘n Verdere beheerde proef is gedoen teen ‘n watertemperatuur van 20.5ºC om die effek van die verskillende formulasies te toets wanneer die diere aan temperatuur-spanning blootgestel word. Die samestelling van die mikrobiese bevolking in die dunderm van die perlemoen is deurentyd gemonitor in ‘n poging om die meganisme vas te stel waarvolgens die sure en soute hul effek het, indien daar enige effek waargeneem word. Daar is gevind dat die onderskeie sure en suursoute die groeitempo van Haliotis midae met ‘n gemiddelde lengte van 23 mm tot 33 mm beduidend kan verhoog in vergelyking met die groeitempo’s van beide kontroles. Daar is gevind dat die antibiotiese groeistimulant geen effek het op die groei van die diere nie en dat geen behandelings ‘n beduidende effek op voeromsetting, voerkoste of voerinname gehad het nie. Daar kon nie bewys word dat enige van die formulasies of die antibiotika ‘n effek gehad het op die mikrobes in die spysverteringskanaal van die perlemoene in die sisteem nie, alhoewel die gebrek aan ‘n effek moontlik toegeskryf kan word aan die onakkurate en onvoldoende mikrobiologiese metodes wat gebruik is tydens die studie. Die meganisme waarvolgens die sure werk kon nie vasgestel word nie. Daar is verder gevind dat die diere in die temperatuur-beheerde eksperiment aanvaklik deur ‘n aanpassingsperiode gegaan het, wat tot gevolg gehad het dat die spesifieke groeitempo, voeromsetting en voerkoste verbeter het met die verloop van die eksperiment. Daar is groot verskille gevind in die voeromsetting van beheerde optimale toestande en onbeheerde produksietoestande, wat impliseer dat daar nog baie ruimte en geleenthede is om metodes te ontwikkel wat beter voeromsetting bewerkstellig tydens perlemoenproduksie. Spesifieke groeitempo, voeromsetting en voerkoste is nadelig beïnvloed toe die watertemperatuur verhoog is vanaf 16.5ºC na 20.5ºC. Die samestelling van die mikrobiese bevolking in die spysverteringskanaal van die perlemoen het ook beduidende veranderinge ondergaan tydens hierdie temperatuur verhoging. Dit wil voorkom asof die lengtegroei van die dop en die toename in massa verskillend reageer op ‘n verandering in watertemperatuur en hierdie effek word weerspieël in die verandering in Fulton-kondisiefaktor. ‘n Verwantskap tussen totale doplengte en totale gewig van Haliotis midae kon vasgestel word vir diere tussen 15 mm en 47 mm en daar is gewys dat H. midae nie ‘n isometriese groeipatroon volg nie. Hierdie verwantskap kan aangewend word tydens produksiebestuur om produksie te verbeter en daardeur ook winsgewendheid te verhoog. Verskeie mikrobes is tydens die verloop van die proef geïsoleer, maar die rol van en interaksie tussen hierdie mikrobes en die Suid-Afrikaanse perlemoen is nie duidelik nie. Sekere bakterieë het die mikrobiese bevolking in die spysverteringskanaal van die perlemoen in hierdie proef oorheers tydens sekere groeiperiodes. Die huidige navorsing het duidelik aangetoon dat organiese sure en hul soute as groeistimulante kan optree in die Suid-Afrikaanse perlemoen Haliotis midae, met toepassings in die plaaslike akwakultuur- en voervervaardigins-industrieë. Dit beskik verder oor die potensiaal om aangepas te word sodat dit toepaslik is in ander perlemoenspesies en selfs ander akwakultuur organismes.

Thesis (MScIng)--University of Stellenbosch, 2003. / ENGLISH ABSTRACT: Vesiculated beads consist of aerated microvoids encapsulated in a solid spherical continuous polymeric shell. The difference in refractive index between the voids and polymer granules causes effective scattering of incident light on the particles, presenting it with a white appearance. The size of these beads generally range in the region of 0.5 – 40 μm, making it suitable for use as pigment extender in the surface coatings or paint industry. Currently, titanium dioxide pigment is predominantly used as opacifying agent in paint formulations, but due to the high cost associated in purchasing this pigment, as well as fluctuation in import prices, paint manufacturers are looking for alternative products to replace or at least partially replace this pigment. As an alternative, opaque vesiculated polymer particles can be produced locally at a cheaper price and in existing vessels available in the paint industry. Approximately five years ago a paint company in Mexico and member of the Nova Club, started research in developing vesiculated beads for production in their factories. However, it was found extremely difficult to scale-up the production to industrial size, since the system was very sensitive to process variables. A local paint company and member of the Nova Club acquired this technology and continued further research in developing vesiculated beads on large scale in existing Cowles disperser systems found in the paint industry. The beads consist mainly of an organic phase comprising of unsaturated carboxylated polyester and styrene. A polyamine is also added to assist the formation of vesicles in the organic phase. This phase is slowly added under agitation to an aqueous phase consisting of deionised water, a thickener and colloid stabilisers to form an oil-inwater emulsion. Agitation is continued for a specified period of time, also known as the emulsification period, to allow sufficient time for the organic globules to break-up to smaller particle sizes. These globules are subsequently catalysed with a freeradical initiator and redox activator and left static overnight to allow formation of the solid beads. To determine the most important process parameters during production of vesiculated beads, a fully integrated laboratory scale Cowles reactor system was designed and constructed, geometrically analogous to the vessels found in the paint industry. The system measures and controls production temperature, mixing speed and component addition rates. Production runs were performed where various process parameters were varied to investigate the effect on properties, which include average particle size and particle size distribution, pH, viscosity and opacity. The most important process parameters that were found to play a significant role include production temperature, organic phase addition rate, emulsification time, the Cowles impeller diameter and mixing speed. Production runs were performed in geometrically similar 5l and 20l vessels on the laboratory-scale system to investigate the effect of scale-up. A model presented by Klein et al. (1996) was used as basis for describing the average particle size as a function of mixing speed, impeller diameter, vessel diameter and emulsification time. The applicability of this model was tested on average particle size data obtained from industrial scale runs performed on the plants and proved to be reasonably accurate. / AFRIKAANSE OPSOMMING: Sferiese polimeerpartikels met klein lugholtes vasgevang in ‘n harde omhulsel word al jare in die verf industrie aangewend as pigment. Weens die verskil in brekingsindeks tussen die soliede polimeerpartikel en die vasgevange lugholtes, word invallende lig versprei op so ‘n manier dat die partikels ondeursigtig (of wit) voorkom. Hierdie partikels kan geproduseer word met deursneë wat strek van 0.5 – 40 μm, wat dit geskik maak vir gebruik in verf formulasies. Tans word titaandioksied poeier hoofsaaklik gebruik in verf as pigment, maar weens die hoë koste van die invoer en aankoop van hierdie produk, het verfmaatskappye begin soek na goedkoper alternatiewe. Aangesien hierdie ondeursigtige polimeerpartikels plaaslik goedkoper vervaardig kan word in bestaande mengvate beskikbaar in verf aanlegte, dien dit as moontlike plaasvervanger. Ongeveer vyf jaar gelede het ‘n Mexikaanse verfmaatskappy, wat lid is van die Nova Klub, navorsing begin doen om hierdie polimeerpartikels in hul fabrieke te produseer. Dit was egter vir hulle onmoontlik om die produksie op te skaal na industriële vervaardiging aangesien die proses baie sensitief was vir produksieveranderlikes. Sekere eienskappe soos die gemiddelde partikelgrootte, partikelverspreiding, pH, viskositeit en deursigtigheid van die partikels kon nie van lot tot lot herhaal word nie en verdere navorsing is gestaak. ‘n Plaaslike verfmaatskappy (ook lid van die Nova Klub) het die tegnologie oorgeneem en die proses verder ontwikkel. Die proses is aangepas sodat “Cowles” mengers, wat wydverspreid in die verf industrie beskikbaar is, gebruik kan word om dit te vervaardig. Die partikels bestaan hoofsaaklik uit ‘n organiese fase wat ‘n onversadigde gekarboksileerde poliëster en stireen insluit. ‘n Poli-amien word ook bygevoeg en is verantwoordelik vir die vorming van die lugholtes in die partikels. Hierdie fase word stadig onder menging by ‘n tweede water fase, bestaande uit gedeïoniseerde water, ‘n verdikker en kolloïdale stabiliseerders gevoeg om ‘n olie-in-water emulsie te vorm. Menging word voortgesit vir ‘n bepaalde emulsifiseringsperiode om die oliedruppels verder op te breek. Gevolglik word hierdie druppels gekataliseer met ‘n vry-radikaal inisieerder en redoksaktiveerder en oornag staties gelos om vorming van die soliede partikels toe te laat. Aangesien eienskappe van die polimeerpartikels so sensitief is vir prosesveranderlikes, is besluit om aanvanklik ‘n ten volle geïntegreerde laboratorium skaal “Cowles” reaktorsisteem te ontwerp en bou. Hierdie sisteem is geometries gelykvormig aan die mengvate wat in verffabrieke gevind word. Die produksietemperatuur, stuwergrootte, mengspoed en materiaal toevoertempo kan effektief gemeet, verstel en beheer word. Eksperimentele lopies is gedoen en die effek van verskeie produksieveranderlikes op eienskappe is ondersoek. Die belangrikste veranderlikes wat die proses beïnvloed, is die emulsifiseringstemperatuur, die toevoertempo van die organiese fase, emulsifiseringsperiode, stuwerdeursnit en mengspoed. Eksperimentele lopies is gedoen op twee geometriese gelykvormige mengvate (5l en 20l kapasiteit) om die effek van opskaling op eienskappe te ondersoek. ‘n Model wat deur Klein et al. (1996) voorgestel is, is as basis gebruik om die gemiddelde partikelgrootte te bepaal as ‘n funksie van mengspoed, stuwerdeursnit, mengvat deursnit en emulsifiseringstyd. Hierdie model is getoets op partikelgrootte data wat verkry is van groot industriële skaal lopies uitgevoer in die fabrieke onder bekende produksie kondisies en daar is gevind dat hierdie model bevredigend gebruik kan word om die gemiddelde partikelgrootte te voorspel.

Thesis (MScIng)--University of Stellenbosch, 2004. / ENGLISH ABSTRACT: The fine ash produced at the Sasol Secunda Petrochemical Plant is disposed of through a wet ash disposal system. Other process waste streams with high salt concentrations are co-disposed of in the Sasol Secunda ash disposal system. This has led to a steady rise in the salt concentrations of the recycled clear ash effluent (CAE) over the past 17 years. To combat this increase in salt concentrations, the capability of the Sasol Secunda ash disposal system to act as a salt sink, needs to be enhanced. This investigation focussed on ways to enhance the salt removal/retention capabilities of the Sasol Secunda ash disposal system and consisted of the following: • A literature survey of relevant information. • The mixing of different combinations of fine ash, brine and CAE. • Adding CO2 to the fine ash and CAE mixtures. • Investigation to enhance salt precipitation in the CAE and Evaporation dams. • Salt balances and a residence time calculation over the CAE and Evaporation dams. From these investigations it were concluded that the Sasol Secunda ash disposal system could be used as a salt sink for SO4 ions. Up to 43% of the SO4 is removed from the brines after the initial ash/water contact. It was also found that the tubular reverse osmosis (TRO) brine could be used as a carrier medium for the ash. The large amounts of Ca that is leached into the ash water during the mixing of the CAE and fine ash can be prevented by the addition of CO2 to the mixing point. There is usually an increase of 240% in the Ca concentration and this is reduced to only an 8% increase with the CO2 addition. The most feasible precipitation enhancement for the CAE and Evaporation dams is an increase in evaporation. This enhances CaCO3 precipitation, which is the main mechanism for salt removal in the CAE and Evaporation dams. Ca, Na and Cl are retained in the evaporation and CAE dams. SO4 is leached from solid phases in the dams. There is however an overall decrease in the total dissolved solids (TDS) of the ash water. The salt removal of the CAE and Evaporation dams is approximately 57 tons per day. The capability of the Sasol Secunda ash disposal system to act as a salt sink can be enhanced by the addition of CO2 at the mixing point and by increasing the evaporation rate in the CAE and Evaporation dams. Using the TRO brine as carrier medium may also increase the SO4 precipitation capabilities of the Sasol Secunda ash disposal system. / AFRIKAANSE OPSOMMING: Die fynas wat by die Sasol Secunda Petrochemiese Aanleg geproduseer word, word verwyder deur ‘n geslote nat asstelsel. Ander afvalstrome wat hoë konsentrasies soute bevat word ook in die Sasol Secunda asstelsel gestort. Dit het tot gevolg dat daar oor die afgelope 17 jaar ‘n volgehoue styging in die sout konsentrasies van die hergebruikte aswater (genoem CAE – “clear ash effluent”) was. ‘n Manier om hierdie styging in die sout konsentrasies teen te werk, is om die sout verwyderingsvermoë van die Sasol Secunda asstelsel te verbeter. Hierdie ondersoek het gefokus op maniere om die sout verwyderings- /terughoudingsvermoë van die Sasol Secunda asstelsel te verbeter en het die volgende ingesluit: • ‘n Literatuur oorsig van toepaslike inligting. • Die meng van verskillende kombinasies van fynas, soutstrome en CAE. • Toediening van CO2 by die fynas en CAE mengsels. • ‘n Ondersoek na metodes om die soutverwydering in die CAE en Verdampingsdamme te verbeter. • Soutbalanse en ‘n residensie tyd berekening vir die CAE en Verdampingsdamme. Na hierdie ondersoeke kon die gevolgtrekking gemaak word dat die Sasol Secunda asstelsel ‘n sout sink vir SO4 ione is. Tot 43% van die SO4 word verwyder na die aanvanklike as/water kontak. Daar is ook gevind dat die TRO (“tubular reverse osmosis”) soutstroom gebruik kan word as ‘n draer vir die fynas. Die groot hoeveelhede Ca wat in die aswater in loog, kan voorkom word deur die toediening van CO2 by die mengpunt van die fynas en aswater. Daar is normaalweg ‘n verhoging van 240% in die Ca konsentrasie van die aswater en dit word verminder na ‘n skrale 8% met die toediening van CO2. Die mees praktiese metode om die soutverwydering in die CAE en Verdampingsdamme te verbeter, is met die verhoging van die verdamping. Dit sal die neerslag van CaCO3, wat die meeste soutverwydering tot gevolg het, verhoog. Ca, Na en Cl word teruggehou in die Verdampings en CAE damme. SO4 loog uit soliede fases in die damme. Daar is wel ‘n afname in die algehele opgeloste spesies (“TDS”) van die aswater. Die soutverwydering van die Verdampings en CAE damme is ongeveer 57 ton per dag. Die vermoë van die Sasol Secunda asstelsel om as ‘n sout sink gebruik te word, kan verbeter word deur CO2 by die mengpunt by te voeg en die verdampingstempo in die Verdampings en CAE damme te verhoog. Die gebruik van die TRO pekelstroom as draer van die as kan die SO4 neerslag in die Sasol Secunda asstelsel ook verhoog.

Thesis (MScIngwet)--University of Stellenbosch, 2005. / ENGLISH ABSTRACT: Paint manufacturing through the dispersion process is an important part of the chemical industry that relies on limited and expensive supplies of titanium dioxide pigment. The aims of the project were to: (i) identify and evaluate the factors that affect the opacity and flocculation gradient, (ii) establish and evaluate the mechanism of the process, and (iii) evaluate and apply the rheology of the dispersion process. The mechanism of the dispersion process can be broken down into the following steps: (i) wetting, (ii) particle break down, and (iii) stabilisation against agglomeration. Wetting can be further broken down into adhesional, immersional and spreading wetting, which can be evaluated in terms of the contact angle. Titanium dioxide pigment particles are held together in the agglomerate state through attractive Van der Waals forces. These forces must be broken down through shear stresses applied through the Cowles mill or the homogeniser. The sensitivity analysis that was carried out confirms that Van der Waals forces are effective only for sub-micron-sized particles. Acoustic cavitation also increases the rate of particle break down in a homogeniser and it depends on turbulence intensity. The mechanism of dispersion can be evaluated in terms of the Reynolds number. The opacity and flocculation gradient of paint were found to depend on: (i) the mean pigment particle size of titanium dioxide and extender, (ii) the particle size distribution of titanium dioxide, (iii) the pigment volume concentration of titanium dioxide and extender, and (iv) the wavelength of the incident radiation. Correlations of opacity (contrast ratio) or flocculation gradient could be set up on the basis of the above explanatory variables in terms of a multiple linear regression. However, it was found out that the methods used for measuring the contrast ratio and flocculation gradient were unreliable. In the case of the contrast ratio, there was no standard procedure for preparing pigment dispersion samples, thus resulting in values that were very high and insensitive to process changes. Samples whose contrast ratio has to be determined must be diluted with resin. Measurements of the flocculation gradient were found to be erratic with very low linear association. Samples of pigment dispersions processed through the dispersion process were found to be shear thinning. Flow curves obtained showed that the high shear rate and low shear rate behaviour of dispersions were significantly different. Of the processing variables investigated, dispersant had the greatest impact on the dispersion process. It significantly affects wetting and the particle break down rate. Samples of dispersions from the dispersion process are thixotropic and recover their structure in a reasonable time after the application of shear stress. Overall, the agitator speed and diameter did not impart a significant effect on the dispersion process. / AFRIKAANSE OPSOMMING: Die vervaardiging van verf met die dispersie proses vorm ‘n belangrike deel van die chemiese industrie wat staatmaak op die verskaffing van ‘n beperkte voorraad, duur titaniumdioksied pigment. Die doel van hierdie projek was om (i) die faktore te identifiseer en te evalueer wat die ondeurskynendheid en flokkulasie gradiënt beïnvloed, (ii) die meganisme van die proses vas te stel en te evalueer, en (iii) die reologie van die dispersie proses te evalueer. Die meganisme van die dispersie proses kan verdeel word in die volgende stappe: (i) benatting, (ii) afbreking van partikels, (iii) stabilisering teen agglomerasie. Benatting kan verder verdeel word in adhesiebenatting, onderdompelingsbenatting en spreibenatting, wat dan in terme van die hoek van kontak ge-evalueer kan word. Titaniumdioksied pigment partikels word deur Van der Waals kragte bymekaar gehou in die agglomeraattoestand en hierdie kragte moet gebreek word met behulp van skuifspanning wat deur die Cowles Meul en Homogeniseerder aangewend kan word. ‘n Sensitiwiteits analise het bevestig dat die Van der Waals kragte slegs effektief is vir sub-mikron grootte partikels. Akoestiese kavitasie verhoog die tempo waarteen partikels breek in die (homogeniser) en dit hang af van die intensiteit van die turbulensie. Die meganisme van dispersie kan in terme van die Reynolds getal ge-evalueer word. Daar is gevind dat die ondeurskynendheid en flokkulasie gradiënt van die volgende afhanklik is: (i) die gemiddelde pigment partikel grootte van die titanium dioksied en aanvuller, (ii) die partikelgrootteverspreiding , (iii) die pigment volume konsentrasie van die titanium dioksied en die aanvuller, en (iv) die golflengte van die invallende bestraling. Korrelasies van die ondeurskynendheid of flokkulasie gradiënt kan opgestel word op grond van die bogenoemde verduidelikende veranderlikes in terme van ‘n veelvuldige linêere regressie. Daar is egter gevind dat die metodes vir die meet van die ondeurskynendheid en flokkulasie gradiënt nie betroubaar is nie. In die geval van die ondeurskynendheid was daar geen standaard prosedure vir die voorbereiding van die pigment dispersie monsters nie en die gevolg was waardes wat baie hoog was en onsensitief was vir proses veranderinge. Monsters waarvan die ondeurskynendheid bepaal moet word behoort met ‘n hars verdun te word of by relatiewe lae vastestof inhoude te wees. Flokkulasie gradiënt metings was baie wisselvallig. Pigment monsters wat deur die dispersie proses geprosesseer is , is pseudoplasties. Die vloeikurwes dui daarop dat die hoë skuif tempo en die lae skuif tempo gedrag van die dispersies grootliks verskil. Van die proses veranderlikes wat ondersoek is het die dispersant die grootste invloed op die dispersie proses gehad het. Dit het die benatting en partikel afbreking grootliks beïnvloed. Dispersie monsters van die dispersie proses is thixotropies en herwin hul struktuur redelik gou na die aanwending van skuifspanning. Die roerspoed het geen betekenisvolle invloed op die dispersie proses gehad nie binne die beperkte grense in roerspoed wat ondersoek is.

Thesis (MScEng (Process Engineering))--University of Stellenbosch, 2005. / Biomass is a significant renewable energy source and much research is currently being done to enable the production of biofuels and chemicals from biomass. This study looks at vacuum pyrolysis, a technology which has the potential to turn biomass, amongst other waste materials, into commercially valuable commodities. Vacuum pyrolysis is the thermal degradation of a feedstock in the absence of oxygen and under low pressure, to produce a bio-oil and char as main products, together with water and non-condensable gases. Both the oil and char have a high energy content and may be used as fuels. An incredible number of chemical compounds are also found in the oil and these compounds can be extracted and sold as high value chemicals.

Thesis (MScEng (Process Engineering))--University of Stellenbosch, 2006. / Genetic programming (GP) is a methodology that imitates genetic algorithms, which uses mutation and replication to produce algorithms or model structures based on Darwinian survival-of-the-fittest principles. Despite its obvious po-tential in process systems engineering, GP does not appear to have gained large-scale acceptance in process engineering applications. In this thesis, therefore, the following hypothesis was considered: Genetic programming offers a competitive approach towards the automatic generation of process models from data. This was done by comparing three different GP algorithms to classification and regression trees (CART) as benchmark. Although these models could be assessed on the basis of several different criteria, the assessment was limited to the predictive power and interpretability of the models. The reason for using CART as a benchmark, was that it is well-established as a nonlinear approach to modelling, and more importantly, it can generate interpretable models in the form of IF-THEN rules. Six case studies were considered. Two of these were based on simulated data (a regression and a classification problem), while the other four were based on real-world data obtained from the process industries (three classification problems and one regression problem). In the two simulated case studies, the CART models outperformed the GP models both in terms of predictive power and interpretability. In the four real word case studies, two of the GP algorithms and CART performed equally in terms of predictive power. Mixed results were obtained as far as the interpretability of the models was concerned. The CART models always produced sets of IF-THEN rules that were in principle easy to interpret. However, when many of these rules are needed to represent the system (large trees), the tree models lose their interpretability – as was indeed the case in the majority of the case studies considered. Nonetheless, the CART models produced more interpretable structures in almost all the case studies. The exception was a case study related to the classification of hot rolled steel plates (which could have surface defects or not). In this case, the one of the GP models produced a singularly simple model, with the same predictive power as that of the classification tree. Although GP models and their construction were generally more complex than classification/regression models and did not appear to afford any particular advantages in predictive power over the classification/regression trees, they could therefore provide more concise, interpretable models than CART. For this reason, the hypothesis of the thesis should arguably be accepted, especially if a high premium is placed on the development of interpretable models.

Thesis (MScEng (Process Engineering))--University of Stellenbosch, 2005. / The development of non-replicating vaccines is an emerging option for safe, effective vaccines, several of which contain virus-like particles (VLPs). Many recombinant expression systems have been evaluated as hosts for VLP production for the prevention of infectious diseases. The filamentous fungi Aspergillus niger has emerged as a potential alternative expression system for cost effective VLP vaccine production. Hepatitis B surface antigen (HBsAg) was used as a model VLP product to benchmark A. niger’s production capacity with those of Saccharomyces cerevisiae, Pichia pastoris and Hansenula polymorpha. Bioprocessing strategies were used to optimise VLP production by recombinant A. niger in batch culture. In particular, the effect of the parameters culture temperature, inoculum concentration, agitation intensity, dissolved oxygen (dO2) concentration and culture pH on biomass formation, morphology and VLP (HBsAg) production concentration was quantified. At an optimum agitation of 100 rpm and optimum dO2 concentration of 50 %, HBsAg production levels were increased 9-fold compared to yields obtained in shakeflask cultivation. Highest HBsAg production levels of 3.6 mg.ℓculture -1 and 350 μg.gDW -1 were recorded, at a biomass concentration of 10.5 gDW.ℓculture -1. These production levels compare favourable with those obtained by other production systems under similar conditions. HBsAg VLPs mostly accumulated intracellularly, although under optimum bioreactor conditions significant HBsAg accumulation in the cytoplasm and culture supernatant was also observed. The impact of these process parameters on VLP production and cell morphology was attributed to environmental stress conditions. Volumetric biomass and HBsAg production levels were maximised under conditions of lowest environmental stress, resulting in the most optimal small-pelleted morphology. These results indicate a substantial potential for further engineering of the A. niger production system for the high level of intracellular and extracellular VLP production.

Thesis (MScEng (Process Engineering))--Stellenbosch University, 2008. / A full scale, three dimensional, transient, mathematical model was developed to simulate fluid flow and mixing in gas stirred ladles. The volume of fluid (VOF) and discrete phase (DPM) models were used in combination to account for multiphase aspects, and a slightly modified version of the standard - model was employed for turbulence modelling. The model was validated to compare well against published physical modelling results. Model results were interpreted from the fundamental grounds of kinetic energy transport within the ladle. This approach led to the specification of three key measures of mixing efficiency: The rate and efficiency of kinetic energy transfer from the buoyant gas to the bulk steel as well as the total kinetic energy holding capacity of the ladle. These measures describe the quantity of mixing in any specific ladle setup, whereas the traditional measure of mixing time reflects mixing quality, i.e. the degree of kinetic energy distribution through the entire ladle. The model was implemented in designed experiments to assess various operating and design variables pertaining to mixing quantity and quality. Considerable time was invested in finding the correct balance between numerical accuracy and computational time so that the model could be used to generate the required data within the given time frame. Experiments on the operating variables drew an important distinction between factors influencing the shape and the strength of gas induced flow patterns. Flow pattern strengthening variables, such as gas purge rate, significantly affected the quantity of mixing, but had a limited effect on mixing quality. Variables such as mass loading that influence the shape of the flow patterns had much larger potential to influence both the quantity and quality of mixing. Minimization of turbulence losses in the region of the plume eye was identified as the primary outcome of ladle design. It was shown that a taller vessel allowed more distance over which the plume could disperse, thereby reducing velocity gradients and subsequent turbulence generation at the free surface. Multiple tuyere systems yielded similar improvements by dividing the gas flow into several weakened plumes. Surface wave formation was investigated as an added mixing mechanism and demonstrated to be impractical for application in full scale gas stirred ladles. The conditions for resonance between the surface wave and the bubble plume were met only in vessels with a very low aspect ratio. Performance improvements offered by swirl in these ladles could easily be replicated in more practical ways. This study demonstrated the potential of mathematical modelling as a tool for in-depth investigation into fluid flow and mixing in the hostile environment of a full scale gas stirred ladle. Scaled-down cold models are the only alternative and can offer no more than a reasonably reliable predictive framework. The ease of flow data extraction from the numerical model also proved invaluable in facilitating a fundamental understanding of the effects of various important independent variables on ladle hydrodynamics. At this stage of development, however, the model is recommended for use on a comparative basis only. Two important developments are required for complete quantitative agreement: The inclusion of turbulence modulation by the bubbles and the increased turbulence kinetic energy dissipation rate in the vicinity of the free surface. A general strategy was developed to account for these effects and it compared favourably with published cold model results. Further research is required to generalize this approach for application in full scale gas stirred ladles.

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.