The synthesis of a number of alkyl esters such as methyl lactate, methyl decanoate, and ethyl benzoate via esterification in a reactive distillation is quite challenging. It is due to the complexity in the thermodynamic behaviour of the chemical species in the reaction mixture in addition to the difficulty of keeping the reactants together in the reaction section. One of the reactants (in these esterification reactions) having the lowest boiling point can separate from the other reactant as the distillation continues. This can result in a significant drop in the reaction conversion in a conventional reactive distillation whether it is a batch or a continuous column. To overcome this challenge, new different types of batch reactive distillation column configurations: (1) integrated conventional (2) semi-batch (3) integrated semi-batch (4) integrated dividing-wall batch distillation columns have been proposed here. Four esterification reaction schemes such as (a) esterification of lactic acid (b) esterification of decanoic acid (c) esterification of benzoic acid (d) esterification of acetic acid are investigated here. A detailed dynamic model based on mass, energy balances, chemical reaction, and rigorous thermodynamic (chemical and physical) properties is considered and incorporated in the optimisation framework within gPROMS (general PROcess Modelling System) software. It is found that for the methyl lactate system, the i-SBD operation outperforms the classical batch operations (CBD or SBD columns) to satisfy the product constraints. While, for the methyl decanoate system, the i-DWCBD operation outperforms all CBD, DWBD and sr-DWBD configurations by achieving the higher reaction conversion and the maximum product purity. For the ethyl benzoate system, the performance of i-CBD column is superior to the CBD process in terms of product quality, and conversion rate of acid. The CBD process is found to be a more attractive in terms of operating time saving, and annual profit improvement compared to the IBD, and MVD processes for the benzyl acetate system. / The Higher Committee for Education Development in Iraq (HCED)

L'estérification de Fisher est une étape importante pour développer un procédé produisant de l'éthanol à partir de biomasse gazéifiée. Cette réaction réversible permet de transformer l'acide acétique et l'alcool, produits à partir de gaz de synthèse, en acétate de méthyle ou d'éthyle. L'ester peut, par la suite, subir une hydrogénolyse pour produire de l'éthanol. Le but de ce projet est de briser l'équilibre de réaction pour obtenir une plus grande conversion dans un procédé continu. Un montage de distillation réactive a permis d'obtenir une conversion élevée pour la formation d'acétate de méthyle, c'est-à-dire de plus de 96 % avec un ratio molaire de méthanol sur acide acétique de 2. Il y avait 3 % d'acide sulfurique comme catalyseur dans l'acide acétique et le ratio de reflux était de 1,4. Lorsque ce ratio molaire était de 1, la conversion était de 89 %, mais la pureté du distillat était plus élevée, 93 % d'acétate de méthyle sur une base massique. En effet, lorsque le méthanol est utilisé en excès, il se retrouve en tête de colonne. Un bullage de gaz inerte au rebouilleur a été évalué dans le but d'emporter plus aisément l'acétate de méthyle au fur et à mesure de sa formation et ainsi obtenir un produit plus pur. Cette stratégie s'est vue inefficace, car le méthanol était emporté et ce dernier traversait plus rapidement la zone réactive, résultant en une conversion moindre. De plus, les meilleurs résultats pour la formation d'acétate d'éthyle avec la distillation réactive étaient de 77 % de conversion avec 3 % d'acide sulfurique dans l'acide acétique et un ratio de reflux de 1,45. Il y avait alors une fraction massique d'acétate d'éthyle de 0,71 dans le distillat. Un réacteur en phase vapeur a été testé avec différents catalyseurs. La résine échangeuse d'ion cationique avait tendance à se désactiver en perdant son groupement sulfonique. De plus, certaines zéolithes présentaient une activité plus élevée comme la H-Mordenite avec un ratio Si/Al de 20 et la H-Y zéolithe avec un ratio Si/Al de 31. La H-Mordenite a présenté une activité constante sur un test de 72 heures avec une conversion d'environ 83 % et une fraction massique d'acétate d'éthyle de 0,67 au condensat. La température de réaction était alors de 140 ÀC, le GHSV était de 500 et le ratio molaire éthanol sur acide acétique de un. De plus, pour favoriser la réaction vers les produits selon le principe de Le Châtelier, la zéolithe LTA 3A a été utilisée avec succès pour absorber l'eau produite. Deux lits catalytiques superposés par deux lits de dessiccant ont servi à l'expérience. Une conversion de 97 % a été atteinte avec cette zéolithe et le pourcentage d'eau dans le condensat était de 0,13%. Pour la même configuration du réacteur avec du carbure de silicium au lieu du dessiccant, la conversion était de 91 % avec 9 % d'eau dans les produits. Ces résultats ont été obtenus avec un GHSV de 250, une température de 140 ÀC et un ratio molaire éthanol sur acide acétique de 0,5.

Thesis (PhD)--University of Stellenbosch, 2002. / ENGLISH ABSTRACT: This study describes the design, construction, complete industrialisation and operation of a dual bed vacuum swing adsorption (VSA) demonstration plant, which operates at atmospheric and sub-atmospheric conditions. All design objectives as set out initially were met. The plant removes contaminants such as methanol and water from neutral wine spirit. Neutral wine spirit is a key component of various local and international spirituous products which include liqueurs, gin, vodka, fortified wines and brandy. Neutral wine spirit can chemically be described as the azeotropic mixture of ethanol and water, which occurs at an ethanol content of 96.4 vol. %. Methanol is naturally present in all products from the vine. Fermentation and distillation concentrate methanol even more, and due to physical and chemical characteristics, its separation consumes as much as 45 % of total production costs. Neutral wine spirit is produced by the proven technology of continuous atmospheric distillation. Continuous improvement of the distillation process is limited due to the physical constraints of an old facility, but also due to previous design philosophies and approaches. The VSA plant consists of two adsorbers, packed to a total height of 1.71 m and a diameter of 0.4 m. Adsorption took place at 100 °C and regeneration at the same bed temperature with purified nitrogen gas at 170 °C and a vacuum of 17 kPa (abs). Experiments were divided into Group I and Group II experiments. Group I investigated the ability to separate methanol and water from the azeotrope and to which efficiency it occurred. It consisted of 120 adsorption cycles of 5 minutes each and 60 samples were drawn for analyses. Breakthrough was not allowed to occur. The azeotropic feed was consistently dehydrated to a water content < 0.05 wt %, while methanol was reduced to < 4 mg/100mLAA. The type of 3A molecular sieve (MS 564 CS) was specifically selected to ensure analytic as well as organoleptic compliance with the product specification. Molecular sieve 4A was removed due to organoleptic problems with the product. Group" experiments were performed in the format of a sensitivity analysis. The effects of various process parameters on the methanol breakthrough curves were individually assessed. Eighteen experiments were performed over a period of 8 days, with 86 samples drawn. The duration of an adsorption cycle was 30 minutes, allowing methanol breakthrough to occur. Water was preferentially adsorbed. Negative methanol bed loadings during high water loadings confirmed that water was able to displace methanol molecules. In the presence of water, molecular sieve 3A was capable of adsorbing 0.6 mg methanol/100mLAA, while in the absence of water with synthetically dosed methanol, molecular sieve 3A achieved a maximum loading of 12.3 mg methanol/100mLAA. The latter corresponded with a maximum methanol feed content of 1118 mg/100mLAA. In general, quicker breakthrough occurred at higher flow rates and feed concentrations. Continuous breakthrough caused bed contamination and a 24-hour thermal regeneration was performed following experiment 12. The feed flow rate was increased from the theoretical 50 f/hr to 70 f/hr without any additional capital layout. Selected process conditions were found to be effective in continuously separating methanol from ethanol. Depending on the strategy of integration, profitability studies shows a Return on Investment of between 110.1% - 220.8% for the adsorption project. Adsorption is superior to distillation in the separation of methanol. Due to the level of innovation involved, it is recommended that the contents of this study remain confidential and patent protection is to be extended. This dissertation speaks to both the wine making as well as the chemical engineering fraternity. It seeks to provide credibility to both parties, by clarifying the unknown issues fundamental to the respective disciplines. / AFRIKAANSE OPSOMMING: Hierdie studie definieer die ontwerp, vervaardiging en volledige industrialisasie van 'n dubbelbed vakuum adsorpsie demonstrasie aanleg (VSA) wat by atmosferiese en sub-atmosferiese kondisies bedryf word. Alle ontwerpsdoelwitte is bereik. Die aanleg verwyder selektief metanol en water vanuit neutrale wynspiritus. Neutrale wynspiritus is 'n sleutelkomponent van verskeie spiritualieë in die plaaslike en internasionale wyn en spiritus bedryf. Hierdie produkte sluit in likeurs, jenewer, vodka, gefortifiseerde wyne en brandewyn. Chemies, kan neutrale wynspiritus beskryf word as die azeotropiese mengsel van etanol en water teen 96.4 vol. %. Metanol het 'n natuurlike teenwoordigheid in alle produkte vanaf die wynstok. Gisting en distillasie konsentreer metanol tot 'n hoër mate en weens fisiese en chemiese eienskappe word metanol teen hoë koste vanaf die etanol stroom geskei. Die metanol verwyderingskomponent beloop soveel as 45 % van die produksiekoste van die totale proses. Neutrale wynspiritus word deur die gevestigde tegnologie van kontinue atmosferiese distillasie geproduseer. Kontinue verbetering van die proses word beperk deur die fisiese ouderdom en toestand van die fasiliteite, maar is ongelukkig ook die resultaat van vorige ontwerpsfilosofieë en benaderings. Die adsorbeerders is gepak tot 'n hoogte van 1.71 m met 'n deursnit van 0.4 m. Adsorpsie het by 100°C plaasgevind en regenerasie by dieselfde bedtemperatuur met stikstofgas by 170°C en 'n vakuum van 17 kPa (abs). Eksperimentele werk is in Groep I en Groep II eksperimente verdeel. Groep I het die effektiewe prosesvermoë om metanol en water vanuit die azeotroop te verwyder ondersoek. Dit het bestaan uit 120 adsorpsie siklusse van 5 minute elk. Sestig monsters is getrek vir analise. Deurbreek van metanol was nie toe gelaat om plaas te vind nie. Die azeotropiese toevoer is konsekwent tot 'n water inhoud < 0.05 massa % gedehidrateer is. 'n Metanol inhoud < 4 mg/100 mLAA is bereik. Die tipe 3A molekulêre sif (MS 564 CS) was spesifiek vir die toepassing geselekteer om sodoende 'n analities sowel as organolepties aanvaarbare produk te lewer. Molekulêre sif 4A was verwyder weens die vorming van produk wangeure. Groep II eksperimente is in die vorm van 'n sensitiwiteits analise uitgevoer. Die effek van verskeie veranderlikes is individueel op die metanol deurbreekkurwe getoets. Agtien eksperimente is oor 'n tydperk van 8 dae gedoen, met 'n totaal van 86 monsters wat getrek is. 'n Adsorpsie siklus het 30 minute geduur en het deurbreek van metanol toegelaat. Water is by voorkeur geadsorbeer. Negatiewe metanol bed ladings tydens hoë waterteenwoordigheid toon dat water wel metanolmolekule op 'n adsorpsie-posisie kan verplaas. In die teenwoordigheid van water is 'n bedlading van 0.6 mg metanol/100mLAA verkry, met 'n maksimum van 12.3 mg metanol/100mLAA in die afwesigheid van water. Laasgenoemde verteenwoordig 'n toevoer met 'n metanol inhoud van 1118 mg/100mLAA. In die algemeen is gevind dat 'n toename in toevoer vloeitempo en konsentrasie die tyd vir deurbreek verkort. Kontinue deurbreek het kontaminasie van die bed teweeg gebring en 'n termiese regenerasie is vir 24 ure na eksperiment 12 gedoen. Die teoretiese ontwerps vloeitempo was 50 .elhr, maar resultate het getoon dat die aanleg tot 70 .t'/hr kan verwerk sonder addisionele koste. Die geselekteerde proseskondisies was effektief in die versekering van die kontinue skeiding van metanol en etanol. Die lewensvatbaarheidstudie toon, afhangende van die strategie van integrasie, 'n Opbrengs op Belegging van tussen 110.1% - 220.8%. Adsorpsie het 'n beter skeidingsvermoë as konvensionele distillasie vir die verwydering van metanol vanuit etanol. Weens die vlak van innovasie betrokke, word dit voorgestel dat die inhoud van hierdie studie vertroulik gehou word en dat patent beskerming verleng sal word. Hierdie verhandeling spreek tot beide die wynmaak sowel as chemiese ingenieurs dissiplines. Daar is gepoog om geloofwaardigheid vir beide partye te skep deur die onbekende aspekte van albei dissiplines aan te spreek.

Depuis que l’industrie chimique vise à rejeter de moins en moins de gaz à effet de serre, cette dernière cherche à revaloriser les différents gaz à effet de serre tel que le dioxyde de carbone. Une des techniques est de combiner le dioxyde de carbone avec de l’ammoniac pour synthétiser l’urée qui pourrait par la suite être utilisé soit directement ou soit comme intermédiaire, pour la synthèse catalytique du diméthyle carbonate (DMC). Le DMC est à la base de plusieurs applications industrielles telles que la synthèse des polymères (les polycarbonates), les réactions de trans-estérification menant à d’autres carbonates comme le diphénylcarbonate et comme agent de méthylation ou d’alkylation. Plusieurs articles provenant de la littérature scientifique rapportent que le DMC peut être utilisé comme additif oxygéné dans les carburants tels l’essence [1]. Le but de ce projet est de déterminer la viabilité industrielle de la production de DMC par la méthylation de l’urée en premier lieu en méthyle carbamate puis en DMC. La première étape de ce projet reposera donc dans un premier temps sur la confirmation des résultats rapportés au sein de la littérature ouverte pour par la suite faire une étude de l’impact des différents types de catalyseurs et des conditions expérimentales sur le rendement de la réaction. Une fois que le montage batch sera optimisé, ce dernier sera modifié pour opérer en continu. Cette modification a pour but d’augmenter le rendement et la sélectivité pour éventuellement de l’adapter industriellement. Selon la littérature, les rendements anticipés pour la réaction batch sont d’environ 30 % [2] et pour un système en continu de plus de 50 %.

Thesis (MScEng)--Stellenbosch University, 2011. / ENGLISH ABSTRACT: The difficulties of chemical process control using plain Proportional-Integral- Derivative (PID) methods include interaction of process manipulated- and control variables as well as difficulty in tuning. One way of eliminating these problems is to use a centralized non-linear control solution such as a feed-forward neural network. While many ways exist to train such neurocontrollers, one of the promising active research areas is reinforcement learning. The biggest drawing card of the neurocontrol using reinforcement learning paradigm is that no expert knowledge of the system is neccesary - all control knowledge is gained by interaction with the plant model. This work uses episodic reinforcement learning to train controllers using two types of process model - non-linear dynamic models and non-linear autoregressive models. The first was termed model-based training and the second data-based learning. By testing the controllers obtained during data-based learning on the original model, the effect of plant model mismatch and therefore real-world applicability could be seen. In addition, two reinforcement learning algorithms, Policy Gradients with Parameter-based Exploration (PGPE) and the Covariance Matrix Adaptation Evolution Strategy (CMA-ES) were compared to one-another. Set point tracking was facilitated by the use of integral error feedback. Two control case studies were conducted to test the effectiveness of each type of controller and algorithm, and allowed comparison to multi-loop feedback control. The first is a ball mill grinding circuit pilot plant model with 5 degrees of freedom, and the second a 41-stage binary distillation column with 7 degrees of freedom. The ball mill case study showed that centralized non-linear feedback control using neural networks can improve on even highly optimized PI control methods, with the proposed integral error-feedback neural network architecture working very well at tracking the set point. CMA-ES produced better results than PGPE, being able to find up to 20% better solutions. When compared to PI control, the ball mill neurocontrol solution had a 6% higher productivity and showed more than 10% improvement of the product size set point tracking. In the case of some plant-model mismatch (88% fit), the data-based ball mill neurocontroller still achieved better set point tracking and disturbance handling than PI control, but productivity did not improve. The distillation case study showed less positive results. While reinforcement learning was able to learn successful controllers in the case of no plant-model mismatch and outperform LV - and (L/D)(V/B)-based PI control, the best-performing neurocontroller still performed up to 20% worse than DB-based PI control. Once again, CMA-ES showed better performance than PGPE, with latter even failing to find feasible control solutions. While on-line learning in the ball mill study was made impossible due to stability issues, on-line adaptation in the distillation case study succeeded with the use of a partial neurocontroller. The learner was able to achieve, with a success rate of just over 50%, greater than 95% purity in both distillate and bottoms within 2,000 minutes of interacting with the plant. Overall, reinforcement learning showed that, when there is sufficient room for improvement over existing control implementations, it can make for a very good replacement control solution even when no model is available. Future work should focus on evaluating these techniques in lab-scale control studies. / AFRIKAANSE OPSOMMING: Die probleme van prosesbeheer met behulp van gewone Proporsioneel-Integraal- Afgeleide (PID) metodes sluit interaksie van proses gemanipuleerde- en beheerveranderlikes, sowel as probleme met in-stemming in. Een manier om hierdie probleme te elimineer, is deur ’n gesentraliseerde nie-lineêre oplossing te gebruik, soos ’n vorentoe-gevoerde neurale netwerk. Daar is baie maniere is om sulke neurobeheerders op te lei, waarvan die meer innoverende maniere versterkingsleer is. Die grootste trekpleister van versterkingsleer is dat geen deskundige kennis van die stelsel nodig is nie - alle beheerkennis word opgedoen deur interaksie met die aanleg model. Hierdie werk gebruik episodiese versterkingsleer om beheerders met behulp van twee tipes van prosesmodel op te lei - nie-lineêre dinamiese modelle en nie-lineêre outoregressiewe modelle. Die eerste was model-gebaseerde opleiding en die tweede data-gebaseerde opleiding genoem. Deur die beheerders wat verkry is tydens datagebaseerde opleiding op die oorspronklike model te toets, kon die effek van die verskil tussen aanleg en model gesien word, en ’n aanduiding van werklike wêreld toepaslikheid gee. Twee versterkingsleer algoritmes was met mekaar vergelyk - Policy Gradients with Parameter-based Exploration (PGPE), en die Covariance Matrix Adaptation Evolution Strategy. Stelpunt volging was deur integraalfout-terugvoer gefasiliteer. Twee gevallestudies is uitgevoer om die doeltreffendheid van elke tipe beheerder en algoritme te toets, deur vergelyking met PI terugvoerbeheer. Die eerste is ’n balmeul toetsaanleg met ’n vryheidsgraad van 5 en die tweede ’n binêre distillasie kolom met ’n vryheidsgraad van 7. Die balmeul gevallestudie het getoon dat gesentraliseerde nie-lineêre terugvoerbeheer met behulp van neurale netwerke selfs op hoogs-geoptimeerde PI beheer metodes kan verbeter. In vergelyking met PI beheer, kon die balmeul neurobeheer oplossing ’n 6% hoër produktiwiteit handhaaf en het meer as 10% verbetering in die handhawing van die produkgrootte stel punt getoon. In die geval van ’n 12% aanleg-model verskil, het die data-gebaseerde balmeul neurobeheerder steeds beter stel punt handhawing en versteuring hantering as PI beheer gewys, alhoewel produktiwiteit nie verbeter het nie. In beide gevalle het die integraalfout oplossing sukses getoon, en CMA-ES het tot 20% beter as PGPE gevaar. Die distillasie gevallestudie het getoon dat die sukses van die balmeul gevallestudie nie noodwendig na ander aanlegte uitbrei nie. Alhoewel versterkingsleer in staat was om suksesvolle beheerders in die geval van geen aanleg-model verskil te leer, het die beste presterende neurobeheerder steeds tot 20% swakker as DB-gebaseerde PI beheer gevaar. Weereens het CMA-ES beter as PGPE gevaar, met die laasgenoemde wat selfs nie daarin kon slaag om werkende oplossings te vind nie. Alhoewel onstabiliteit aan-lyn aanpassing in die balmeul gevallestudie onmoontlik gemaak het, is an-lyn aanpassing in die distillasie gevallestudie moontlik gemaak deur die gebruik van ’n gedeeltelike neurobeheerder. Die leerder was in staat om, met ’n slaagsyfer van net meer as 50 %, meer as 95 % suiwerheid in beide uitlaatstrome te bereik in 2,000 minute van die interaksie met die aanleg. Op die ou end het versterkingsleer getoon dat, wanneer daar voldoende ruimte is vir verbetering oor bestaande beheer implementasies, kan dit ’n baie goeie vervanging wees selfs wanneer daar geen model beskikbaar is nie. Toekomstige werk moet fokus op laboratoriumskaal toepassings van hierdie tegnieke.

Thesis (MScEng)--Stellenbosch University, 2012. / ENGLISH ABSTRACT: Distillation is the most widely used separation technique in the chemical process industry and typically accounts for approximately one-third of the total capital cost and more than half of the total energy consumption of a typical petrochemical-chemical plant. Therefore, the design and optimization of the distillation sequence are of critical importance to the economics of the entire process. Azeotropic mixtures cannot be separated into their pure components via normal distillation. Enhanced distillation techniques such as heterogeneous azeotropic distillation should be considered for these mixtures. Isobaric vapour-liquid-liquid equilibrium (VLLE) data are highly important for the design and analysis of heterogeneous distillation columns. However, limited VLLE data are available in literature due to the difficulties involved with measuring such data. The objective of this work was to systematically evaluate and compare the performance of selected entrainers (including benzene, DIPE and cyclohexane) for the dehydration of C2 and C3 alcohols. To meet this objective, phase equilibrium data had to be measured. Isobaric VLLE at standard atmospheric conditions were measured with a dynamic Guillespie unit equipped with an ultrasonic homogenizer, which prevented liquid-liquid separation. Vapour-liquid equilibrium (VLE) and VLLE data were measured for ethanol/water/di-isopropyl ether (DIPE), n-propanol/water/DIPE and n-propanol/water/isooctane. The VLE data were found to be thermodynamically consistent according to the L-W (Wisniak 1993) and McDermott-Ellis consistency tests. No thermodynamic consistency test, specifically for VLLE data, could be found in literature, but the LLE part of the data followed a regular profile according to the Othmer-Tobias correlation. The binary DIPE/water and isooctane/water azeotropes, as well as ternary ethanol/DIPE/water and n-propanol/isooctane/water azeotropes, as measured in this work, agree well with those found in literature. Regressed parameters for the NRTL, UNIQUAC, and UNIFAC models, generally improved the model predictions compared with built-in Aspen parameters. This confirmed the importance of having actual measured VLLE data available for evaluation and improvement of estimations by thermodynamic models. NRTL predicted the ethanol/DIPE/water and n-propanol/DIPE/water VLLE most accurately. Despite the improved regressed parameters for n-propanol/isooctane/water predictions, the models are still considered unsuitable for accurate prediction of the VLLE behaviour of this system. Separation sequences were simulated in Aspen with built-in and regressed parameters, respectively, to illustrate the significant effect such inaccurate parameters have on these simulations. Phase diagram (VLLE data) evaluation of ethanol and isopropanol (IPA) with various entrainers, as found in literature, indicated that DIPE might be a good entrainer for the dehydration of these alcohols. Benzene and cyclohexane are generally used as entrainers in industry for these processes. Benzene is however carcinogenic and therefore an alternative has to be found (United States Department of Labour - Occupational Safety & Health Administration 2011). Separation sequences were simulated for ethanol dehydration with benzene and DIPE as entrainers, respectively. Taking cost and safety into account, DIPE can be considered an acceptable replacement for benzene as entrainer for ethanol dehydration. A separation sequence was also simulated for the dehydration of IPA with DIPE as entrainer and compared to a simulation with cyclohexane (Arifin, Chien 2007) as entrainer. DIPE was found to be a reasonable alternative to cyclohexane as entrainer for IPA dehydration. Two other separation sequences were simulated as practical examples where DIPE could be used as entrainer for the recovery of ethanol or n-propanol from aqueous Fischer Tropsch waste streams. DIPE is therefore found to be a feasible alternative entrainer to benzene and cyclohexane for the dehydration of ethanol and IPA via heterogeneous azeotropic distillation, based on pre-liminary cost considerations, separation ability and safety. Better entrainers than DIPE may exist, but from the data available in literature and the measurements made in this work DIPE appears to be superior to benzene, cyclohexane and isooctane. / AFRIKAANSE OPSOMMING: Distillasie is die mees algemeen-gebruikte skeidingstegniek in die chemiese proses-industrie. Dit is tipies verantwoordelik vir ʼn derde van die totale kapitaalkoste en meer as die helfte van die totale energie verbruik op ʼn tipiese petrochemiese chemiese aanleg. Daarom is die ontwerp en optimering van ʼn distillasie trein van kardinale belang vir die winsgewendheid van die proses. Azeotropiese mengsels kan nie slegs deur normale distillasie in suiwer komponente geskei word nie. Gevorderde distillasie tegnieke soos heterogene azeotropiese distillasie moet dus oorweeg word vir sulke mengsels. Isobariese damp-vloeistof-vloeistof ewewigsdata is een van die belangrikste fisiese eienskappe vir die ontwerp van heterogene distillasie kolomme. Die hoeveelheid damp-vloeistof-vloeistof ewewigsdata wat beskikbaar is in die literatuur is egter baie beperk omdat dit moeilik is om die data te meet. In hierdie werk is isobariese damp-vloeistof-vloeistof ewewigsdata met ʼn dinamiese Guillespie eenheid, by standaard atmosferiese druk gemeet. Die eenheid is toegerus met ʼn ultrasoniese homogeniseerder om vloeistof-vloeistof skeiding te voorkom. Temperatuur is gemeet met ʼn akkuraatheid van 0.03oC by 0oC. Die sisteem se druk is konstant gehou op 101.3 kPa met ʼn akkuraatheid van 0.35 % VSU (Vol Skaal Uitset). Die ewewigsamestellings is met ʼn relatiewe akkuraatheid van 2 % gemeet. Daar is damp-vloeistof en damp-vloeistof-vloeistof ewewigsdata van etanol/water/di-isopropiel eter (DIPE), npropanol/ water/ DIPE en n-propanol/water/iso-oktaan gemeet. Die damp-vloeistof ewewigsdata is deur die LW (Wisniak 1993) en McDermott-Ellis termodinamiese konsistensie toetse getoets en konsistent bevind. Geen termodinamiese konsistensie toets spesifiek vir damp-vloeistof-vloeistof ewewigsdata kon gevind word nie. Die Othmer-Tobias korrelasie dui egter aan dat die vloeistof-vloeistof ewewig gedeelte van die data ʼn reëlmatige gang volg. Die binêre DIPE/water en iso-oktaan/water azeotrope en ternêre etanol/DIPE/water en n-propanol/iso-oktaan/water fase-ewewigte wat in hierdie werk gemeet is, stem ooreen met die wat in die literatuur te vind is. Die parameters vir die modelle (NRTL, UNIQUAC en UNIFAC) wat in hierdie werk bestudeer is, is in die algemeen verbeter deur regressie van die eksperimentele data. Dit dui daarop dat dit belangrik is om eksperimentele damp-vloeistof-vloeistof ewewigsdata te hê om die voorspellings van termodinamiese modelle mee te evalueer en te verbeter. Die etanol/water/ DIPE en n-propanol/water/DIPE damp-vloeistof-vloeistof ewewigsdata is die akkuraatste deur NRTL voorspel. Ten spyte van die verbeteringe wat deur regressie behaal is met die NRTL en UNIQUAC parameters vir n-propanol/water/isooktaan, word hierdie modelle steeds nie as gepas vir die voorspelling van hierdie datastel beskou nie. Skeidingsreekse is gesimuleer met die ingeboude Aspen parameters en regressie parameters, onderskeidelik, om te illustreer dat onakkurate parameters ʼn beduidende effek op sulke simulasies het. Die evaluasie van fase diagramme van etanol en IPA met verskeie skeidingsagente, wat in die literatuur te vind is, dui aan dat DIPE ʼn goeie skeidingsagent kan wees vir die dehidrasie van hierdie alkohole. Skeidingsreekse vir die dehidrasie van etanol met benseen en DIPE, onderskeidelik, is gesimuleer. Met koste en veiligheid in ag geneem, is daar gevind dat DIPE ʼn aanvaarbare plaasvervanger vir benseen as skeidingsagent vir etanol dehidrasie kan wees. Daar is ook ʼn skeidingsreeks vir die dehidrasie van IPA met DIPE as skeidingsagent gesimuleer en met ʼn simulasie (Arifin, Chien 2007) wat sikloheksaan as skeidingsagent gebruik, vergelyk. Daar is bevind dat DIPE ʼn redelike alternatief vir sikloheksaan kan wees as skeidingsagent vir IPA dehidrasie. Nog twee skeidingsreekse is gesimuleer om as praktiese voorbeelde te dien van die gebruik van DIPE as skeidingsagent om etanol of n-propanol vanaf waterige Fischer-Tropsch afvalstrome te herwin. Daarom is daar bevind dat DIPE ʼn geldige alternatiewe skeidingsagent vir benseen en sikloheksaan is, gebaseer op koste, skeidingsvermoë en veiligheid. Daar kan beter skeidingsagente as DIPE bestaan, maar vanuit die data beskikbaar in literatuur en die metings geneem in hierdie werk, is DIPE die beste.

Thesis (MSc)--Stellenbosch University, 1958. / ENGLISH ABSTRACT: no abstract available / AFRIKAANSE OPSOMMING: geen opsomming

Horizontal drilling and hydraulic fracture stimulation have enabled the economic development of unconventional resource plays. An average horizontal well in the Barnett Shale requires 3 to 4 million gallons of fresh water, 90% of which is used for hydraulic fracture stimulation. While the water consumption of Barnett Shale operations is less than 1% of total Region C consumption, extended drought conditions and competing demands for water resources are placing pressure on operators to reduce terminal water consumption. Strategies which reduce water requirements associated hydraulic fracture stimulation without compromising the efficiency and cost of energy production are essential in developing a comprehensive policy on energy-water management. Recycling and reuse technologies were evaluated on the basis of performance, cost, and capacity to treat reclaimed flowback water and oilfield brine. Recycling flowback fluids for future hydraulic fracture applications is the most practical repurposing of oilfield waste. The low TDS content of flowback derived from water-based fracs permits multiple treatment options. Mobile thermal distillation technology has emerged as the prevailing technique for recycling flowback water, yielding maximum water savings and reduced operating costs. The estimated cost of recycling flowback water by thermal distillation is $3.35/bbl. Compared to the current cost of disposal, recycling provides an opportunity to minimize waste and reduce the fresh water requirements of hydraulic fracture stimulation at an incremental cost. The stewardship role of the Texas Legislature is to protect the water resources of the state and to facilitate the Regional Water Planning Process, ensuring future water needs are met. The support and participation of the Legislature and other planning entities is critical in advancing the energy-water nexus. As operators pursue innovative water management practices to reduce terminal water consumption in the oilfield, the Barnett Shale positions itself as a model for sustainable water use in the development of unconventional shale resources. The cost of recycling and reuse technology limits the participation of small and mid-size operators who possess the greatest market share of the Barnett Shale. Funding for research and implementation of water-conscious strategies such as shared recycling facilities, CO2 capture and storage, and pipeline infrastructure would create multi-user opportunities to promote conservation and reduce net consumption of fresh water supplies. Through the integration of technology and policy, terminal water consumption in the Barnett Shale can be greatly diminished. / text

Steam distillation is the most widely accepted process for the large scale production of volatile essential oils from herbaceous material and is also regarded as the standard practice throughout the flavour and fragrance industry. A mobile essential oil distillation unit for the extraction of oils from herbaceous materials would be extremely valuable to the essential oil industry in South Africa. Using a mobile platform, the extraction technology could be taken to rural areas where essential oil crops are grown in order to extract and then analyse the oils produced. Existing systems in South Africa are static distillation units which are usually owned by commercial growers that are generally positioned large distances away from the rural areas. The objective of this project was to design, construct and test a prototype mobile distillation unit for the extraction of essential oils from herbaceous materials. The unit was to have a charge vessel capacity of approximately 250 kg of plant material and should be able to perform in-field distillations in areas where electricity is not available. A literature review on all the essential oil extraction methods, the theory behind steam distillation and oil isolation and the effect that each of the distillation components have on the distillation process was performed. A small test distillation unit was set up in a laboratory in order to investigate the effects of varying steam flow . rates on the distillation time, oil yield and oil quality. A double charge vessel unit was designed, constructed and mounted onto a frame which in turn was fixed onto a trailer to be hauled by a light delivery vehicle (LDV). The steam generator with all its ancillary equipment was fixed onto a separate trailer. The unit could thus be easily transported and in-field distillations on various crops could be conducted. Field distillations were conducted with two crop types, namely rose geranium and lemon grass. Satisfactory results were obtained as the oil yields were within the expected oil yield range. / Thesis (M.Sc.)-University of KwaZulu-Natal, 2005.

South Africa is on a path of dramatically increasing its energy supplying capabilties. Eskom (the main utility supplying electricity to the national grid) recently announced that future power station technologies will focus on renewable energy and nuclear power. This is done in an effort to reduce South Africa’s dependance on burning fossil-fuels and thereby decreasing CO2 emissions and other harmful gases. This, together with the fact that there are a lot of fresh water scarce areas especially along the Eastern Cape coast of South Africa, is what inspired this study. This study investigates the use of a 200 MWth High Temperature Reactor (HTR) for cogeneration purposes. Heat from the reactor is utilised for electricity generation (Rankine cycle) and process heat (desalination). Two desalination concepts were evaluated thermodynamically and economically, namely Multi-Effect Distillation (MED) and Reverse Osmosis (RO). Computer software, Engineering Equation Solver (EES), was used to simulate different cycle configurations, where the heat available in the condenser was increased successively. The coupling of the two desalination technologies with a HTR was compared and it was found that a RO plant produces nearly twice as much water while sending the same amount of electricity to the grid (compared to coupling with MED). Coupling options were investigated and each simulation model was optimised to deliver maximum output (power and water). The best configuration was found to be the coupling of a HTR with a RO plant producing 86.56 MW generator power. This is equal to 2077 MWh/day. Using 332 MWh/day for desalination through RO, delivers 73 833 m3/day fresh water and results in 1745 MWh/day sent to the grid. This scenario is the best option from a thermodynamic and economic point of view. From an investment point of view, it will produce an Internal Rate of Return (IRR) of 10.9 percent and the Net Present Value (NPV) is calculated to be R 2,486,958,689. The results and analysis for the different cycle configurations are presented in such a way that an easy comparison can be made. / Thesis (M.Ing. (Nuclear Engineering))--North-West University, Potchefstroom Campus, 2011