Thesis (M.S.)--Ohio University, March, 2004. / Title from PDF t.p. Includes bibliographical references (leaves 129-131).

Submitted in fulfillment of the requirements for the Master's of Technology: Chemistry, M L Sultan Technikon, 1999. / Saturated long chain hydrocarbons, such as paraffin waxes, have a large variety of applications. These applications may, however, be restricted by certain properties of the wax such as brittleness and in compounding. Cross-linking of the long chains in waxes may provide improved physical properties and hence a wider application of these waxes / M

Thesis (PhD)--University of Stellenbosch, 2001. / ENGLISH ABSTRACT: In this study the deoiling and fractionation of paraffin wax using supercritical fluid extraction (SCFE) has been investigated. SCFE was compared with state-of-the-art processes such as wax crystallisation, static crystallisation and short path distillation. Ethane and carbon dioxide were investigated as supercritical solvents for the supercritical fluid extraction of paraffin wax. Supercritical phase equilibrium data for ethane - n-alkane and CO2 - n-alkane systems close to the mixture critical region were obtained from the literature, and were correlated with several equations of state. Statistical mechanical equations of state failed to correlate the data close to the mixture critical region due to the neglect of density fluctuations which influences phase behaviour close to critical points, or due to inadequate mixing rules. It was found that simple cubic equations of state such as Soave-Redlich-Kwong, Peng-Robinson and Patel-Teja could correlate the data using two interaction parameters. This can be attributed more to their flexibility as correlating tools than to their fundamental accuracy. The Patel-Teja EOS was modified by fitting it to predict low vapour pressure data for long-chain n-alkanes. This modified Patel-Teja EOS was then fitted to the phase equilibria by adjusting two interaction parameters per binary system. The interaction parameters for each solvent (ethane or CO2) system were then fitted to generalised correlations to enable extrapolation to solvent - n-alkane systems for which no equilibrium data were available. The Simplified Perturbed Hardchain theory (SPHC) equation of state was used to correlate lower-pressure solubility data used to model the extract separator. A pilot plant SCFE unit was constructed and used to obtain experimental fractionation data of a low-molecular weight Fischer-Tropsch wax. The experimental results indicate that fractionation of the wax is possible and that the separation efficiency is enhanced by returning some of the extract to the column as reflux. An equilibrium stage model was constructed and used to simulate the extraction experiments. It was possible to obtain good agreement between the experimental results and model predictions. Deoiling of petroleum waxes with a low n-paraffin content (which are not currently deoiled commercially) was investigated. Experimental SCFE and SPD results indicated that selective deoiling is not possible, since the separation is based on differences in molecular weight (or vapour pressure). Simulations of wax crystallisation or solvent extraction and practical tests indicate that deoiling is possible, based on differences in structure and therefore melting point of the components in the wax. Practical problems associated with crystallisation or solvent extraction such as filtration, the use of chlorinated solvents and low yields currently prevent the commercial deoiling of these waxes. During crystallisation of these waxes a soft wax cake is formed which impedes the operation of static crystallisation. A detailed study of the economics of n-paraffin wax deoiling using SCFE was conducted. Flow sheets were proposed to minimise the energy consumption of the SCFE process. Comparison of SPD, static crystallisation and SCFE indicates that a SPD plant will be the cheapest option for deoiling the wax feed investigated. Fractionation of heavier waxes using SPD might not be economically feasible, since the distillation temperature increases dramatically with increasing molecular weight, which leads to higher energy cost. For medium to long chain n-paraffin waxes SCFE should be very competitive, since the capacity of the supercritical solvent can be manipulated to extract longer chain waxes without increasing the extraction temperature. Static crystallisation appears to be the more expensive deoiling option, due primarily to the large initial capital investment cost. / AFRIKAANSE OPSOMMING: Die olieverwydering en fraksionering van paraffienwasse met behulp van superkritiese ekstraksie is in hierdie studie ondersoek. Die modellering van moderne olieverwyderings- en fraksioneringsmetodes soos waskristallisasie, statiese kristallisasie en kortpad distillasie is ook ondersoek. Etaan en koolstofdioksied is ondersoek as superkritiese oplosmiddels vir die superkritiese ekstraksie van paraffienwasse. Literatuurdata van superkritiese fase-ewewigte vir etaan - n-alkaan en CO2 - n-alkaan stelsels naby die mengselkritiese punt is versamel en gekorreleer met verskeie toestandsvergelykings. Statisities-meganiese toestandsvergelykings kon nie data naby mengselkritiese punte korreleer nie, moontlik weens digtheidsvariasies wat afwykings van klassieke gedrag teweegbring, of onakkurate mengreëls. Eenvoudige kubiese toestandsvergelykings soos Soave-Redlich-Kwong, Peng-Robinson en Patel-Teja kon op die ewewigsdata gepas word deur gebruik van twee interaksieparameters. Dit kan eerder toegeskryf word aan hulle buigsaamheid eerder as hulle fundamentele akkuraatheid. Die Patel-Teja toestandsvergelyking is gemodifiseer deur dit te pas op lae dampdruk data van langketting n-alkane. Hierdie gemodifiseerde toestandsvergelyking is gepas op die fase-ewewig data deur twee interaksieparameters te gebruik per binêre sisteem. Die interaksieparameters vir die oplosmiddel stelsels (etaan of CO2) is gekorreleer met algemene vergelykings sodat dit vir ekstrapolasie na oplosmiddel - n-alkaan stelsels gebruik kan word waarvoor ewewigsdata nie beskikbaar is nie. Die "Simplified Perturbed Hardchain" teorie (SPHC) toestandsvergelyking is gebruik om laer druk oplosbaarheidsdata te korreleer vir gebruik in die modellering van die ekstrak skeier. In Superkritiese ekstraksie loodsaanleg is gebou en gebruik om eksperimentele fraksioneringsdata van 'n lae molekulêre massa Fischer- Tropsch was te genereer. Vanaf die eksperimentele resultate blyk fraksionering van was moontlik te wees. Die doeltreffendheid van die skeiding kan verhoog word deur terugvloei van ekstrak na die kolom. 'n Ewewigsmodel is opgestel en gebruik om die ekstraksie eksperimente te modelleer. Deur die ekstraksiedruk en aantal stadia te verander kon goeie ooreenstemming met eksperimentele resultate verkry word. Die verwydering van olie uit petroleumwasse met In lae n-paraffien inhoud (wat nie tans kommersiëel ontolie word nie) is ondersoek. Eksperimentele resultate vir superkritiese ekstraksie en kortpad distillasie dui daarop dat selektiewe olieverwydering nie moontlik is nie, omdat die skeiding gebaseer is op verskille in molekulêre massas en dus (of dampdrukke). Simulasies van waskristallisasie dui op die moontlikheid van olieverwydering gebaseer op verskille in strukture van die komponente in die was. Praktiese probleme geassosieer met kristallisasie of oplosmiddel ekstraksie soos filtrasie, lae opbrengste en gebruik van gechlorineerde koolwaterstowwe as oplosmiddel belemmer die kommersialisering van olieverwydering vir hierdie tipes wasse. 'n Gedetaileerde studie van die ekonomiese lewensvatbaarheid van superkritiese olieverwydering is uitgevoer. Vloeidiagramme is voorgestelom die energieverbruik van die superkritiese ekstraksieproses te minimeer. Vergelyking van kortpad distillasie, statiese kristallisasie en superkritiese ekstraksie dui daarop dat kortpad distillasie die goedkoper opsie vir die olieverwydering van die spesifieke was is. Fraksionering van swaarder wasse met kortpad distillasie sal moontlik nie haalbaar wees nie omdat die distillasietemperatuur drasties toeneem met molekulêre massa. Die skeiding van medium tot langketting wasse met superkritiese ekstraksie behoort meer mededingend te wees, want die kapasiteit van die superkritiese oplosmiddel kan maklik verstel word om langer kettinglengtes wasse te ekstraeer sonder om die temperatuur te verhoog. Statiese kristallisasie blyk die duurder olieverwyderingsopsie te wees hoofsaaklik weens die hoë kapitaalkoste van so 'n aanleg.

Driving with the cold engine increases fuel consumption and greenhouse gases emissions. A latent heat energy storage device has been proposed to recover waste heat and reduce engine warm-up time by using phase change materials (PCMs) as an energy storage medium. Two types of paraffin waxes and 50/50 mixture of the two have been examined to characterize their behaviors under repetitive heating/freezing. From the results, the heat transfer is more effective in the case of narrower spacing distances between the cooling plates and high circulating flow rate of the heat transfer fluid. A 50/50 mixture of two paraffin waxes also provides better heat transfer due to the possible existence of both conduction and natural convection. The results of the metal block simulation experiments demonstrated the potential of latent heat TES’s for use in engine warm-up.

Driving with the cold engine increases fuel consumption and greenhouse gases emissions. A latent heat energy storage device has been proposed to recover waste heat and reduce engine warm-up time by using phase change materials (PCMs) as an energy storage medium. Two types of paraffin waxes and 50/50 mixture of the two have been examined to characterize their behaviors under repetitive heating/freezing. From the results, the heat transfer is more effective in the case of narrower spacing distances between the cooling plates and high circulating flow rate of the heat transfer fluid. A 50/50 mixture of two paraffin waxes also provides better heat transfer due to the possible existence of both conduction and natural convection. The results of the metal block simulation experiments demonstrated the potential of latent heat TES’s for use in engine warm-up.

No description available.

Durante as atividades de produção de petróleo offshore são utilizadas tubulações que transportam o petróleo bruto do fundo do poço até à plataforma ou até à costa marítima. No fundo mar as tubulações são submetidas a temperaturas da ordem de 4 oC. Nessas condições, quando a atividade de produção é interrompida para manutenções ou por paradas de emergência, o óleo bruto, com alto teor de parafinas, tende a se gelificar. Para reiniciar o escoamento são necessárias pressões acima da pressão usual de trabalho para promover a quebra do gel. A literatura mostra que não só o histórico de térmico, mas também o histórico de cisalhamento afetam a gelificação de óleos parafínicos e, portanto, a pressão de reinício do escoamento. O objetivo deste trabalho é avaliar experimentalmente as variáveis que influenciam o reinício do escoamento de petróleo parafínico. Para isso, uma unidade experimental foi construída de modo a reproduzir experimentalmente o reinício do escoamento de petróleo parafínico gelificado. A unidade permite o controle da temperatura, da taxa de resfriamento, da taxa de cisalhamento e do tempo de repouso na formação do gel. A pressão máxima necessária para o início do escoamento foi observada, os valores coletado e analisado. A investigação realizada mostra que todos os parâmetros testados apresentam alguma influência na pressão durante o reinício do escoamento de óleo parafínicos gelificados. / In offshore production, pipelines are used to transport crude oil from the well bore to the platform and from the plataform to the seacoast. When production is interrupted for maintenance or emergency, waxy crude oils tend to form gel at seabed low temperatures. At flow start-up, an increase in pressure above the usual operating pressure is required to break the gel. The literature has reported that not only the temperature but also the cooling rate, the shear rate during cooling and the material aging time affect the gelation of waxy crude oils, and, therefore, the start-up pressure. The objective of the current work is to evaluate experimentally the start-up flow of waxy crude oils in pipelines. In order to accomplish that, an experimental lab loop was build to reproduce the flow start-up of gelled waxy crude oils. The loop allows the control of temperature, cooling rate, shear rate and aging time in the gel formation. The pressure peaks measured during the flow restart were presented and analized as a function of the controlled parameters. The research shows that all parameters tested have some influence on the picks of pressure during the start up flow of paraffinic oil gelled.

Agência Nacional de Petróleo; FINEP / A obstrução das paredes internas de tubulações de transporte e produção de petróleo devido à sedimentação de hidrocarbonetos é um problema grave que pode acarretar riscos operacionais, perdas de equipamentos e gerar prejuízos à indústria. Este trabalho tem por objetivo realizar experimentos utilizando ultrassom, na caracterização de depósitos de parafina em superfícies metálicas, com enfoque na estimativa da espessura desses acúmulos. Os testes foram realizados em uma bancada experimental onde corpos de prova com diferentes espessuras de aço e depósitos de parafina foram mensurados. Os resultados experimentais mostraram que devido à diferença entre as propriedades acústicas do aço e da parafina a utilização de ultrassom, para detectar a presença de depósitos de parafina, torna-se uma tarefa bastante complexa. A medição com exatidão será dependente do meio que fará interface com a parafina, o qual deverá ter certas características para um casamento de impedância acústica com o depósito, permitindo uma maior reflexão do sinal. A técnica de supressão de ecos utilizada para detecção dos depósitos mostrou-se bastante satisfatória, fornecendo uma resposta final com incerteza inferior a 0,32mm. / An obstruction in the oil pipelines’ inner walls of transport and production due to hydrocarbon deposition is a serious problem that can cause operational risks, equipment losses and lead to losses to the industry. This work aims to conduct experiments using ultrasonic waves, to detect paraffin deposits on steel surfaces, focusing in the estimation of the thickness of these accumulations. The tests were conducted in a test rig where specimens with different thicknesses of steel and paraffin deposits were measured. The experimental results showed that due to the difference between the acoustic properties of the steel and paraffin the use of ultrasound, for detecting paraffin deposits, becomes a very complex task. Measuring accurately is dependent on the medium that will interface with the wax, which must have certain characteristics for the acoustic impedance coupling with the deposit, allowing a greater reflection of the ultrasound signal. The echo suppression technique used to detect the deposits proved to be quite satisfactory, providing a response value with uncertainty of less than 0.32mm.

Agência Nacional de Petróleo; FINEP / A obstrução das paredes internas de tubulações de transporte e produção de petróleo devido à sedimentação de hidrocarbonetos é um problema grave que pode acarretar riscos operacionais, perdas de equipamentos e gerar prejuízos à indústria. Este trabalho tem por objetivo realizar experimentos utilizando ultrassom, na caracterização de depósitos de parafina em superfícies metálicas, com enfoque na estimativa da espessura desses acúmulos. Os testes foram realizados em uma bancada experimental onde corpos de prova com diferentes espessuras de aço e depósitos de parafina foram mensurados. Os resultados experimentais mostraram que devido à diferença entre as propriedades acústicas do aço e da parafina a utilização de ultrassom, para detectar a presença de depósitos de parafina, torna-se uma tarefa bastante complexa. A medição com exatidão será dependente do meio que fará interface com a parafina, o qual deverá ter certas características para um casamento de impedância acústica com o depósito, permitindo uma maior reflexão do sinal. A técnica de supressão de ecos utilizada para detecção dos depósitos mostrou-se bastante satisfatória, fornecendo uma resposta final com incerteza inferior a 0,32mm. / An obstruction in the oil pipelines’ inner walls of transport and production due to hydrocarbon deposition is a serious problem that can cause operational risks, equipment losses and lead to losses to the industry. This work aims to conduct experiments using ultrasonic waves, to detect paraffin deposits on steel surfaces, focusing in the estimation of the thickness of these accumulations. The tests were conducted in a test rig where specimens with different thicknesses of steel and paraffin deposits were measured. The experimental results showed that due to the difference between the acoustic properties of the steel and paraffin the use of ultrasound, for detecting paraffin deposits, becomes a very complex task. Measuring accurately is dependent on the medium that will interface with the wax, which must have certain characteristics for the acoustic impedance coupling with the deposit, allowing a greater reflection of the ultrasound signal. The echo suppression technique used to detect the deposits proved to be quite satisfactory, providing a response value with uncertainty of less than 0.32mm.

Incorporating insulation material with phase change materials (PCMs) could help enhance the insulation capability for further building energy savings by reducing the HVAC loadings. During the phase change process between the solid and liquid states, heat is being absorbed or released by PCMs depending on the surrounding temperature. This research explores the benefits of a polyurethane (PU)-PCM composite insulation material through infiltrating paraffin wax as PCM into PU open cell foam. The new PU-PCM composite provides extra shielding from the exterior hot temperatures for buildings. Through this study, it was demonstrated that PU-PCM composite insulation could potentially help building energy savings through reducing the loads on the HVAC systems based on the building energy modeling using EnergyPlus. The Zero Energy Lab (ZØE) at the University of North Texas was modeled and studied in the EnergyPlus. It is a detached building with all wall facades exposed to the ambient. It was determined that the new PU-PCM insulation material could provide 14% total energy saving per year and reduce the electricity use due to cooling only by around 30%.