Thesis (M.Tech-Chemical Engineering)--Cape Technikon, Cape Town, 2001 / The white-rot fungus (WRF), Phanerochaete chrysosporium, is a well known microorganism which produces ligninolytic enzymes. These enzymes can play a major role in the bioremediation of a diverse range of environmental aromatic pollutants present in industrial effluents. Bioremediation of aromatic pollutants using ligninolytic enzymes has been extensively researched by academic, industrial and government institutions, and has been shown to have considerable potential for industrial applications. Previously the production of these enzymes was done using batch cultures. However, this resulted in low yields of enzyme production and therefore an alternative method had to be developed. Little success on scale-up and industrialisation of conventional bioreactor systems has been attained due to problems associated with the continuous production of the pollutant degrading enzymes. It was proposed to construct an effective capillary membrane bioreactor, which would provide an ideal growing environment to continuously culture an immobilised biofilm of P; chrysosporium (Strain BKMF-1767) for the continuous production of the ligninolytic enzymes, Lignin(LiP) and Manganese(MnP) Peroridase. A novel membrane gradostat reactor (MGR) was shown to be superior to more conventional systems of laboratory scale enzyme production (Leukes et.al., 1996 and Leukes, 1999). This concept was based on simulating the native state ofthe WRF, which has evolved on a wood-air interface and involved irnmobilisng the fungus onto an externally skinless ultrafiltration membrane. The MGR however, was not subjected to optimisation on a laboratory scale. The gradostat reactor and concept was used in this work and was operated in the deadend filtration mode. The viability of the polysulphone membrane for cultivation of the fungus was investigated. The suitability of the membrane bioreactor for enzyme production was evaluated. The effect of microbial growth on membrane pressure and permeability was monitored. A possible procedure for scaling up from a single fibre membrane bioreactor to a multi-capillary system was evaluated. Results indicated that the polysulphone membrane was ideal for the cultivation of P chrysosporium, as the micro-organism was successfully immobi1ised in the macrovoids of the membrane resulting in uniform biofilm growth along the outside of the membrane. The production of Lignin and Manganese Peroxidase was demonstrated. The enzyme was secreted and then transported into the permeate without a rapid decline in activity. Growth within the relatively confined macrovoids of the membrane contributed to the loss of membrane permeability. A modified Bruining Model was successfully applied in the prediction of pressure and permeability along the membrane The study also evaluated the effect of potential1y important parameters on the production of the enzymes within the membrane bioreactor. These parameters include air flow (Ch concentration), temperature, nutrient flow, relative redox potential and nutrient concentrations A sensitivity analyses was performed on temperature and Ch concentration. The bioreactor was exposed to normal room temperature and a controlled temperature at 37°C. The reactors were then exposed to different O2 concentration between 21% and 99"10. It was found that the optimum temperature fur enzymes production is 3TJC. When oxygen was used instead of air, there was an increase in enzyme activity. From the results obtained, it was clear that unique culture conditions are required for the production of LiP and MnP from Phanerochaete chrysosporium. These culture conditions are essential fur the optimisation and stability of the bioreactor.

Thesis (MTech (Chemical Engineering))--Cape Peninsula University of Technology, 2017. / Hydrogen is widely regarded as the clean energy carrier for future use in both transportation and electricity sectors. It has become an important new focus as an alternative fuel for cleaner energy technologies especially in the Polymer Exchange Membranes (PEM) fuel cells. However, specific technical and marketing demands must be met by a fuel processor for ultra-pure hydrogen production and at a very competitive cost. Liquid Petroleum gas (LPG) is seen as a potential source for low cost hydrogen production due to its relatively high energy density, easy storage and well-established infrastructure for fuel. There is a growing interest in the use of membrane in reaction engineering with the selective separation of the products from the reaction mixture provided opportunities to achieve higher conversion. Membrane separation technologies have potential to reduce operating costs, minimise unit operations and lower energy consumption. The overall goal of this project is to investigate the engineering feasibility associated performance of employing a palladium or palladium alloy membrane reactor for the production of ultra-pure hydrogen from the products of a liquefied petroleum gas (LPG) pre-reformer in determining the optimal process conditions for the production of high purity hydrogen from the LPG feedstock and evaluating of the performance of a Pd-based membrane in relation to maximizing the yield of hydrogen from the feedstock as well as minimizing the CO content of the reformate.

Thesis (PhD (Process Engineering))--University of Stellenbosch, 2010. / ENGLISH ABSTRACT: Future chemical production is faced with a challenge of limited material and energy resources. However, process intensification might play a significant role to alleviating this problem. Vision of process intensification through multifunctional reactors has stimulated research on membrane-based reactive separation processes, in which membrane separation and catalytic reaction occur simultaneously in one unit. These processes are rather attractive applications because they are potentially compact, less capital intensive, and have lower processing costs than traditional processes. Moreover, they often enhance the selectivity and yield of the target product. For about three decades, there has been a great evolution in p-Xylene production technology, with many equipment improvements being instituted in the industry. Typically, these improvements bring economic as well as processing advantages to the producers. Such developments are vital, as the capital costs for process equipment to produce and separate p-Xylene from xylene isomers, especially into high purity p-Xylene, still remain very high. However, with numerous advantages of membrane-based reactive separation processes compared to the conventional processes, the research focus has been channelled toward application of MFI-type zeolite membranes for in situ separation and isomerization of xylene in extractor-type catalytic membrane reactors. To contribute to this research line, this study has focused on characterization and optimization of an extractor-type catalytic membrane reactor (e-CMR) equipped with a nanocomposite MFI-alumina membrane as separation unit for m-Xylene isomerization over Pt-HZSM-5 catalyst. Nanocomposite MFI-alumina zeolite membranes (tubes and hollow fibres) used in this study were prepared via a so-called “hydrothermal pore-plugging synthesis technique” developed by Dalmon and his group more than a decade ago. In this concept, MFI material is grown by 'pore-plugging' direct hydrothermal synthesis in a porous matrix rather than forming thin films on top of the support. The advantages of this type of architecture over conventional film-like zeolite membranes include: (i) minimization of the effect of thermal expansion mismatch between the support and the zeolite, (ii) easy to scale-up, and (iii) easy module assembly, because the separative layer (zeolite crystals) are embedded within the pores of the ceramic support, reducing the effects of abrasion and thermal shocks. After membrane synthesis, the membrane quality and separation performance of these membranes were evaluated through single gas permeation (H2), binary gas separation (n-butane/H2) and ternary vapour mixture of xylene isomers using the vapour permeation (VP) method with p-Xylene as the target product. After evaluating the xylene isomer separation performance of the membranes, the membranes were used in extractor-type catalytic membrane reactors to carry out m-Xylene isomerization over Pt-HZSM-5 catalyst with p-Xylene as the target product. This dissertation has shown that nanocomposite MFI-alumina membrane tubes and hollow fibre membranes were selective to p-Xylene from xylene isomers. The dissertation also reports for the first time in open literature the excellent xylene separation performance of nanocomposite MFI-alumina membrane tubes at higher xylene loading (or vapour pressure). Unlike their film-like counterparts, the membranes still maintain increased selectivity to p- Xylene at higher xylene vapour pressures without showing a drastic decrease in selectivity. This outstanding property makes it a promising choice for pervaporation applications where concentration profile is usually a major problem at higher loading of xylene. With the use of nanocomposite MFI-alumina hollow fibre membranes, this research has demonstrated that membrane configuration and effective membrane wall thickness play a prominent role in enhancing cross membrane flux. Results presented in the study show, for the first time in open literature, that nanocomposite MFI-alumina hollow fibre membrane could enhance p-Xylene fluxes during the separation of ternary vapour mixture of xylene due to the smaller effective wall thickness of the membrane (membrane thickness <1 μm) when compared to conventional randomly oriented MFI zeolite films (membrane thickness >3 μm). During xylene isomers separation with nanocomposite hollow fibre membrane, about 30% increase in p-Xylene flux was obtained compared to the membrane tubes, operated under the same conditions. Additionally, hollow fibres offer the added advantage of membrane surfaceto- volume ratios as high as 3000 m2/m3 compared to conventional membrane tubes. Using this type of system could be instrumental in reducing both the size and cost of permeating modules for future xylene separation processes. However, obtaining high quality nanocomposite MFI-alumina membrane fibres is subject to the availability of high quality fibre supports. Regarding the application of nanocomposite MFI-alumina membrane tubes as extractor-type catalytic membrane reactors (referred to as extractor-type zeolite catalytic membrane reactor (e-ZCMR) in this study) for m-Xylene isomerization over Pt-HZSM-5, the results presented in this study further substantiate and confirm the potentials of e-ZCMRs over conventional fixed-bed reactors (FBRs). In the combined mode (products in the permeate plus products in the retentate), the e-ZCMR displayed 16-18% increase in p-Xylene yield compared to an equivalent fixed-bed reactor operated at the same operating conditions. On the basis of the high p-Xylene-to-o-Xylene (p/o) and p-Xylene-to-m-Xylene (p/m) separation factors offered by the membranes, p-Xylene compositions in the permeate-only mode (products in the permeate stream) in the range 95%-100% were obtained in the e-ZCMR. When a defect-free nanocomposite MFI-alumina membrane tube with p-Xylene-too- Xylene (p/o) separation factor >400 was used, ultra pure p-Xylene with p-Xylene purity approaching 100% in the permeate-only mode was obtained. Moreover, the e-ZCMR displayed 100% para-selectivity in the permeate-only mode throughout the temperatures tested. This is not possible with conventional film-like MFI-type zeolite membranes. Therefore, the application of nanocomposite MFI-alumina membranes in extractor-type catalytic membrane reactors could catalyse the development of energy-efficient membrane-based process for the production of high purity p-Xylene. Furthermore, in this dissertation, a report on modelling and sensitivity analysis of an e-ZCMR equipped with a nanocomposite MFI-alumina membrane tube as separation unit for m-Xylene isomerization over Pt-HZSM-5 catalyst is presented. The model output is in fair agreement with the experimental results with percentage errors (absolute) of 17%, 29%, 0.05% and 19.5% for p-Xylene yield in combined mode, p-Xylene selectivity in combined mode, p-Xylene selectivity in permeate-only mode and m-Xylene conversion, respectively. Therefore, the model is adequate to explain the behaviour of e-ZCMR during m-Xylene isomerization over Pt-HZSM-5 catalyst. The model is also adaptable to e-ZCMRs of different configurations such as hollow fibre MFI-alumina membrane-based e-ZCMRs. To gain more insight into the behaviour of the model to small changes in certain design parameters, sensitivity analysis was performed on the model. As expected, the sensitivity analysis revealed that intrinsic property of membrane (porosity, tortuosity), membrane effective thickness and reactor size (indicated with reactor internal diameter) play a significant role on the performance of e-ZCMR during p-Xylene production from the mixed xylenes. MFI-alumina zeolite membranes with optimized parameters such as membrane porosity, membrane tortuosity, and membrane effective wall thickness might enhance transport of p-Xylene through the membrane and thus resulting in higher p-Xylene flux through the membrane. This eventually would translate into an increase in p-Xylene yield in permeate-only mode. As far as it could be ascertained, this is the first report in open literature on modelling study with sensitivity analysis of e-ZCMR equipped with nanocomposite MFI-alumina membrane tubes as separation unit for m-Xylene isomerization over Pt-HZSM- 5 catalyst. In addition, the results of this study have confirmed previous research efforts reported on the application of extractor-type catalytic membrane reactors, having MFI-type membranes as separation units, for p-Xylene production via m-Xylene isomerization over a suitable catalyst. Also, new ideas were developed, tested and proposed that now provide a solid basis for further scale-up and techno-economical studies. Such studies are necessary to evaluate the competitiveness of the technology with the traditional processes for the production of high purity p-Xylene from mixed xylene. In summary, the encouraging results, as documented in this dissertation and also communicated to researchers in the area of membrane-based reactive separation (in the form of four peer-reviewed international scientific publications and four conference proceedings), could provide a platform for developing a scaled-up membrane-based energy-efficient industrial process for producing high purity p-Xylene through isomerization. / AFRIKAANSE OPSOMMING: Die produksie van chemiese stowwe word belemmer deur die uitdaging van beperkte materiaal- en energiebronne. Prosesuitbreiding kan egter ‘n noemenswaardige rol in die verligting van hierdie probleem speel. Die moontlike gebruik van multi-funksionele reaktore in prosesuitbreiding het navorsing in membraan-gebaseerde reaktiewe skeidingsprosesse (waar membraanskeiding en die katalitiese reaksie gelyktydig in ‘n enkele eenheid plaasvind) aangemoedig. Hierdie prosesse is aantreklik omdat hulle potensieel kompak en minder kapitaal-intensief is en ook teen laer koste as tradisionele prosesse bedryf kan word. Dit is ook dikwels die geval dat die multi-funksionele reaktor die selektiwiteit en opbrengs van die gewenste produk verhoog. In die afgelope drie dekades was daar ’n sterk verandering in die tegnologie wat gebruik word in die produksie van p-Xileen, met vele verbeterings aan nuwe toerusting wat in die nywerheid in bedryf gestel is. Hierdie verbeteringe hou gewoonlik ekonomiese-, sowel as bedryfsvoordele vir die produsente in. Ontwikkelings in hierdie veld is noodsaaklik aangesien die kapitale uitgawes vir die toerusting om p-Xileen, veral baie suiwer p-Xileen, van xileenpolimere te produseer en te skei, steeds baie hoog is. Met talle voordele gekoppel aan membraangebaseerde reaktiewe skeidingsprosesse in vergelyking met normale prosesse, is die navorsing egter gekanaliseer na die gebruik van MFI-tipe zeolietmembrane vir die in-situ skeiding en isomerisasie van xileen in ekstraksie-tipe katalitiese membraanreaktore. As bydrae tot hierdie navorsingsveld het hierdie studie op die karakterisering en optimering van ‘n ekstraksie-tipe katalitiese membraanreaktor (e-KMR), toegerus met ’n nanosaamgestelde MFI-alumina membraan as skeidingseenheid vir m-Xileen isomerisasie in die teenwoordigheid van ‘n Pt-HZSM-5 katalis, gefokus. Nanosaamgestelde MFI-alumina zeolietmembrane (buise en hol vesels) wat in hierdie studie gebruik is, is voorberei deur die sogenaamde “hidrotermiese porie-sperring sintese tegniek” wat meer as ‘n dekade gelede ontwikkel is deur Dalmon en sy groep. In hierdie tegniek word MFI-materiaal gekweek deur direkte hidrotermiese sintese in ‘n poreuse matriks, eerder as die vorming van dun films bo-op die ondersteuningsbasis. Die voordele van hierdie ontwerp bo dié van die konvensionele filmagtige zeolietmembrane sluit in: (i) minimering van die effek van termiese uitsetting op die gaping tussen die ondersteuningsbasis en die zeoliet, (ii) die gemak van opskalering, en (iii) die gemak waarmee die modules aanmekaar gesit kan word, omdat die skeidingslaag (zeolietkristalle) binne die porieë van die keramiek-ondersteuningsbasis geleë is, wat die effek van erodering en termiese skok verminder. Ná die membraansintese is die membraankwaliteit en skeidingsvermoë geevalueer deur enkel-gas-deurdringing (H2), binêre-gas-skeiding (n-butaan/H2), en ternêre dampmengsel van xileen-isomere deur die gebruik van die damp-deurdringingsmetode met p-Xileen as die teikenproduk. Hierdie tesis het gewys dat nanosaamgestelde MFI-alumina membraanbuise en hol vesel membrane selektief was ten opsigte van p-Xileen vanuit xileen-isomere. Die tesis doen ook, vir die eerste keer in die oop literatuur verslag, oor die uitstekende p-Xileen skeidingsvermoë van nanosaamgestelde MFI-alumina buise by hoër xileenladings (of dampdrukke). Anders as hulle filmagtige eweknieë het die membrane steeds hul verhoogde selektiwiteit vir p-Xileen by hoër dampdrukke behou, sonder ‘n merkbare verlaging in die selektiwiteit. Hierdie merkwaardige eienskap maak dit ‘n belowende keuse vir pervaporasie toepassings, waar die konsentrasieprofiel (as gevolg van hoër xileenladings) gewoonlik ’n noemenswaardige probleem is. Met die gebruik van nanosaamgestelde MFI-alumina membrane het hierdie navorsing gewys dat membraankonfigurasie en –wanddikte ‘n prominente rol speel in die verbetering van vloei oor die membraan. Resultate wat in die studie voorgelê word, wys, vir die eerste keer in oop literatuur, dat hol vesel nanosaamgestelde MFI-alumina membrane die deurvloei van p-Xileen kan verbeter gedurende die skeiding van ternêre dampmengsels van xileen, as gevolg van die kleiner effektiewe wanddikte van die membraan (<1 μm) wanneer dit vergelyk word met konvensionele kansgewys-geörienteerde MFI-zeoliet films met ‘n membraandikte van >3 μm. Tydens die skeiding van xileen-isomere met nanosaamgestelde hol vesel membrane is ‘n verbetering van ongeveer 30 % in die deurvloei van p-xileen verkry, vergeleke met membraanbuise, by identiese bedryfstoestande. Hol vesels bied ook die verdere voordeel van oppervlak-tot-volume verhoudings van so hoog as 3000 m2/m3 vergeleke met konvensionele membraanbuise. Die gebruik van hierdie tipe sisteem kan deurslaggewend wees in die vermindering van die grootte en koste van deurlatingseenhede in toekomstige xileen-skeidingsprosesse. Die vervaardiging van hoë-kwaliteit nanosaamgestelde MFIalumina membraanvesels is egter onderworpe aan die beskikbaarheid van hoë-kwaliteit vessel-ondersteuningsbasisse. Wat die gebruik van nanosaamgestelde MFI-alumina membraanbuise as ekstraksietipe katalitiese membraanreaktore betref (ekstraksie-tipe zeoliet katalitiese membraanreaktor, of e-ZKMR in hierdie studie) vir m-Xileen isomerisasie in die teenwoordigheid Pt-HZSM-5, bevestig die resultate die potensiaal van e-ZKM reaktore bo konvensionele vaste-bed reaktore (VBR). In die gekombineerde verstelling (met produkte in die permeaat sowel as die retentaat) toon die e-ZKMR ‘n 16 – 18% verbetering in die opbrengs van p-Xileen vergeleke met ‘n ekwivalente VBR by dieselfde bedryfskondisies. Gegrond op die hoë p-Xileen-tot-o- Xileen (p/o) en p-Xileen-tot-m-Xileen (p/m) skeidingsfaktore wat deur die membraan gebied word, is p-Xileen-samestellings in die slegs-permeaat verstelling (produkte in die permeaatstroom) van tussen 95 en 100% in die e-ZKMR verkry. Toe ‘n defek-vrye nanosaamgestelde MFI-alumina membraanbuis met ‘n (p/o) skeidingsfaktor van >400 gebruik is, is p-Xileen met ‘n suiwerheid na aan 100% in die slegs-permeaat verstelling verkry. Die e-ZKMR het ook 100% para-selektiwiteit in die slegs-permeaat verstelling getoon by alle toets-temperature, iets wat onmoontlik is met gewone filmagtige MFI-tipe zeolietmembrane. Om hierdie rede is dit moontlik dat die gebruik van MFI-alumina membrane in ekstraksie-tipe katalitiese membraanreaktore die ontwikkeling van energie-doeltreffende membraangebaseerde prosesse vir die produksie van suiwer p-Xileen kan bevorder. Verder word daar in hierdie tesis verslag gedoen oor die modelering en sensitiwiteitsanalise van ‘n e-ZKMR wat toegerus is met ‘n nanosaamgestelde MFI-alumina membraanbuis as skeidingseenheid vir m-Xileen isomerisasie in die teenwoordigheid van ‘n Pt-HZSM-5 katalis. Die model-uitsette is redelik in ooreenstemming met eksperimentele resultate met absolute fout-persentasies van 17, 27, 0.05 en 19.5 % vir die p-Xileen opbrengs in die gekombineerde verstelling, p-Xileen selektiwiteit in die gekombineerde verstelling, p-Xileen selektiwiteit in die slegs-permeaat verstelling en m-Xileen omsetting, onderskeidelik. Om hierdie rede kan die model die gedrag van ‘n e-ZKMR verduidelik tydens die m-Xileen isomerisasie in die teenwoordigheid van ‘n Pt-HZSM-5 katalis. Die model kan ook aangepas word na e-ZKM reaktore met verskillende konfigurasies, soos hol vesel MFIalumina membraan-gebaseerde e-ZKMRe. Om meer insig te kry in die gedrag van die model op klein veranderinge in sekere ontwerpparameters, is ‘n sensitiwiteitsanalise op die model uitgevoer. Soos verwag, het die sensitiwiteitsanalise gewys dat die intrinsieke eienskappe van die membraan (porositeit, tortuositeit), die effektiewe van membraandikte en die reaktorgrootte (gemeet as die interne deursnit van die reaktor) ‘n noemenswaardige rol speel in die gedrag van die e-ZKMR gedurende p-Xileen produksie vanuit gemengde xilene. MFI-alumina zeolietmembrane met geoptimeerde parameters soos membraanporositeit, -tortuositeit, en –wanddikte mag dalk die oordrag van p-Xileen deur die membraan bevorder en sodoende ‘n hoër vloei van p-Xileen oor die membraan bewerkstellig. Dit sal uiteindelik lei tot ‘n verhoging in die opbrengs van p-Xileen in die slegs-permeaat verstelling. So ver dit vasgestel kon word, is hierdie die eerste verslag in die oop literatuur wat die modelering en sensitiwiteitsanalise van ‘n e-ZKMR, toegerus met nanosaamgestelde MFIalumina membraanbuise as skeidingseenheid vir m-Xileen isomerisasie in die teenwoordigheid van ‘n Pt-HZSM katalis, aanspreek. Verder ondersteun die resultate van hierdie studie vorige navorsingspogings op die gebruik van e-KMRe, met MFI-tipe membrane as skeidingseenhede, vir die produksie van p-Xileen deur middel van m-Xileen isomerisasie in die teenwoordigheid van ‘n geskikte katalis. Verder is nuwe idees ontwikkel, getoets en voorgestel wat dien as ’n stewige basis vir verdere opskalering- en tegno-ekonomiese studies. Sodanige studies is nodig om die vatbaarheid van die tegnologie relatief tot die tradisionele prosesse te bepaal. Ter opsomming, die bemoedigende resultate, soos in die tesis gedokumenteer (en ook gepubliseer in vier ewe-knie beoordeelde internasionale wetenskaplike joernale en vier konferensiestukke), kan as ‘n platform dien vir die ontwikkeling van ’n opgeskaleerde membraan-gebaseerde energie-doeltreffende nywerheidsproses vir die produksie van suiwer p-Xileen deur middel van isomerisasie.

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.

A novel batch reactor concept is proposed for the catalytic production of hydrogen in distributed and portable applications. In the proposed CHAMP (CO2/H2 Active Membrane Piston) reactor, a batch of hydrocarbon or synthetic fuel is held in the reaction chamber where it reacts to produce hydrogen with simultaneous removal of the hydrogen by permeation through an integrated, selective membrane. These processes proceed to the desired level of completion at which point the reaction chamber is exhausted and a fresh batch of fuel mixture brought in. Unique to the CHAMP reactor is the ability to precisely control the residence time, as well as the ability to compress the reaction chamber dynamically, or mid-cycle, in order to increase the instantaneous hydrogen yield rate. An idealized reactor model demonstrates that the ideal limits of performance (in the absence of transport limitations) exceed those of comparable continuous flow designs. A comprehensive, coupled, transport-kinetics model is used to quantify the effects of mass transport limitations on reactor performance and search the design parameter space for optimal points. Two modes of operation are studied: fixed-volume mode wherein the piston is stationary and constant-pressure mode in which the rate of compression matches the permeation of hydrogen through the membrane. Finally, to validate these numerical models and confirm our understanding of the key operating principles, prototype reactors were built and experimentally characterized.

Tez (Doktora) - Süleyman Demirel Üniversitesi, Fen Bilimleri Enstitüsü, Çevre Mühendisliği Anabilim Dalı, 2007. / Bibliyografya var.

Thesis (Ph. D.)--Ohio State University, 2007. / Title from first page of PDF file. Includes bibliographical references (p. 185-195).

Thesis (Ph. D.)--Ohio State University, 2007. / Full text release at OhioLINK's ETD Center delayed at author's request

Thesis (MTech (Chemical Engineering))--Cape Peninsula University of Technology, 2005 / The white rot fungus, Phanerochaete chrysosporium, produces enzymes, which are capable of degrading chemical pollutants. It was detennined that this fungus has multiple growth phases. The study provided infonnation that can be used to classify growth kinetic parameters, substrate mass transfer and liquid medium momentum transfer effects in continuous secondary metabolite production studies. P. chrysosporium strain BKMF 1767 (ATCC 24725) was grown at 37 QC in single fibre capillary membrane bioreactors (SFCMBR) made of glass. The SFCMBR systems with working volumes of 20.4 ml and active membrane length of 160 mm were positioned vertically. Dry biofilm density was determined by using a helium pycnometer. Biofilm differentiation was detennined by taking samples for image analysis, using a Scanning Electron Microscope at various phases of the biofilm growth. Substrate consumption was detennined by using relevant test kits to quantify the amount, which was consumed at different times, using a varying amount of spore concentrations. Growth kinetic constants were detennined by using the substrate consumption and the dry biofilm density model. Oxygen mass transfer parameters were determined by using the Clark type oxygen microsensors. Pressure transducers were used to measure the pressure, which was needed to model the liquid medium momentum transfer in the lumen of the polysulphone membranes. An attempt was made to measure the glucose mass transfer across the biofilm, which was made by using a hydrogen peroxide microsensor, but without success.

Experiences in treating wine distillery wastewaters (WDWs) contribute to the field of oenology as many oenologists are concerned with the selection, efficiency and economy of their wastewaters. Wine distillery wastewaters are strongly acidic, have high chemical oxygen demand (COD), high polyphenol content and are highly variable. Primary attention was focussed on sustainable biological treatment of raw wine distillery wastewater (RWDW) and fungally pre-treated wine distillery wastewater (FTWDW) by energy-efficient high rate anaerobic digestion (AD). This study also explored the development of a novel dual-stage anaerobic digestion ultrafiltration (ADUF) process, using a ceramic submerged membrane bioreactor (SMBR) in the treatment of both RWDW and FTWDW. The first stage was for the selection of microorganisms that were able to treat the toxic pollutants from WDWs. It was operated at a high feed-to-microorganism ratio. The second stage, a secondary digester, was operated like a typical membrane bioreactor at a low feed-to-microorganism ratio to sustain a stable efficient population for a long period. The characteristics of RWDW were as follows: pH 3.83, 15 000 mg/l soluble COD (CODs) and 5229 mg/l of phenols. After pre-treatment of RWDW with Trametes pubescens, starting parameters for FTWDW were as follows: pH 6.7, 7000 mg/l soluble COD (CODS) and 1440 mg/l of phenols. During operation of a high rate anaerobic digester for RWDW treatment, K2HPO4 was required for buffering the digester. Volatile fatty acid concentrations were <300 mg/l throughout the study, indicating degradation of organic acids present. Mean CODS removal efficiency for the 130 day study was 87 %, while the mean polyphenol removal efficiency was 85 %. Addition of 50 mg/l Fe3+ increased the removal efficiencies of CODS to 97 % and of polyphenols to 99 %. High removal efficiencies of CODS and polyphenols were attributed to the addition of macronutrients and micronutrients that caused pH stability and stimulated microbial activity. The CODS removal efficiency of high rate anaerobic digestion of FTWDW reached 99.5%. During FTWDW digestion, pH buffering was achieved using K2HPO4. A combination of a SMBR and a secondary digester was tested for the treatment of RWDW and FTWDW during a 30 day study. Results for RWDW showed that pH buffering was achieved by dosing the feed stream with CaCO3 and K2HPO4. Buffering proved to be significant for optimum performance of the system in removal of soluble CODS, and volatile fatty acids (VFAs). Different batches of RWDW used for feeding the reactor had variable compositions with respect to concentrations of nitrates, ammonium and total phenolic compounds. Ammonium accumulated in the secondary digester after 14 days of system operation, indicated the time required for the establishment of anaerobic conditions in the system. Dosing of the SMBR treating FTWDW with CaCO3 and K2HPO4 buffered the pH; iii this proved significant for optimum performance of the system in removal of CODS. The system eliminated an average of 86 (± 4) % of CODS present in the FTWDW. The residual CODS levels in the effluent were approximately 400 mg/l, significantly lower than the concentrations observed when treating RWDW, indicating that fungal pre-treatment might have provided additional nutrients for removal of recalcitrant components of the wastewater. The resulting effluent was rich in nitrates and phosphates and might be used as a fertiliser. Alternatively, a membrane process, such as reverse osmosis (RO) or nanofiltration (NF) could be applied to raise the water quality to meet the levels required for reuse. Biomass samples were obtained from the four treatment systems and population shifts characterization using phospholipids fatty acids (PLFA) and 16S rRNA analysis to provide an indication of limitations within the microbial population. The values of the concentrations of the individual PLFAs detected in the samples indicated that ten bacterial species were present, with the GC content of the 16S rRNA increasing from 1 to 10. Analysis of denaturing gradient gel electrophoresis DGGE data indicated that the composition of the archeal community changed the consortia used for both RWDW and FTWDW treatment. Changes in band intensities indicated the presence of different components of the archeal communities. The results were not conclusive in terms of species identity as cloning, sequencing and phylogenetic analyses were not performed, but they did indicate microbial population shifts and species diversity for high rate anaerobic digestion. The results also confirmed prevalence of relatively few species during operation of SMBRs for treatment of RWDW and FTWDW, which suggested that the microorganisms that survived were either tolerant of toxic components of RWDW and FTWDW or they were able to remove polyphenols.