Yes / Crude oil is an unrefined petroleum composed of wide range of hydrocarbon up to n‐C40+. However, there are also a percentage of light hydrocarbon components present in the mixture. Therefore, to avoid their flashing for safe storage and transportation, the live crude needs to be stabilized beforehand. This paper aims to find the suitable operating conditions to stabilize an incoming live crude feed to maximum true vapor pressure (TVPs) of 12 psia (82.7 kPa) at Terengganu Crude Oil Terminal, Malaysia. The simulation of the process has been conducted by using Aspen HYSYS. The obtained results illustrate that the simulation data are in good agreement with the plant data and in particular for the heavier hydrocarbons. For the lighter components, the simulation results overpredict the plant data, whereas for the heavier components, this trend is reversed. It was found that at the outlet temperature (85–90°C) of hot oil to crude heat exchanger (HX‐220X), the high‐pressure separator (V‐220 A/B) and the low‐pressure separator (V‐230 A/B) had operating pressures of (400–592 kPa) and (165–186 kPa), respectively, and the live crude was successfully stabilized to a TVP of less than 12 psia. The impact of main variables, that is, inlet feed properties, three‐phase separators operating pressure, and preheater train's performance on the product TVP, are also studied. Based on the scenarios analyzed, it can be concluded that the actual water volume (kbbl/day) has greater impact on the heat exchanger's duty; thus, incoming free water to Terengganu Crude Oil Terminal should be less than 19.5 kbbl/day (9.1 vol%) at the normal incoming crude oil flow rate of 195 (kbbl/day).

In this work, different optical techniques have been explored to study and characterize crude oil and its asphaltene. Crude oil is extremely complex fluid used to produce fuel for a wide range of applications. The characterization of this fluid is key for optimum operations in the oil and gas industry. First, we demonstrate the application of gold nanorods in characterizing a different set of crude oils. We utilize the high sensitivity of the Localized Surface Plasmon Resonance (LSPR) of the nanorods to the surrounding environment to measure the crude oil refractive index. We immobilized the nanorods on a glass substrate and took the measurement in a reflection configuration. The setup and the nanorods were calibrated using different fluids with known refractive index, and a sensitivity of 247 nm/RIU and a resolution of 0.013 RIU have been achieved. In addition to the simplicity of this approach, it has eliminated the absorption issue and made it possible to measure high optical density crude oils with typical Visible-NIR wavelengths. Surface-Enhanced Raman Spectra (SERS) can also be measured. SERS can provide additional useful information, especially to some applications such as downhole fluid analysis, where confirmation of the hydrocarbons presence is necessary. In the second part of this work, we used Terahertz Time-Domain Spectroscopy (THz-TDS) to study the asphaltene in three different crude oils. THz-TDS has a feature of measuring the amplitude and time delay and consequently the refractive index and absorption coefficient spectra simultaneously. Our approach is based on measuring the THz signal from neat crude oil samples and comparing it with the THz signal after removing the asphaltene from the samples (maltene). The results show that the difference in the time delay and the peak amplitude between the neat oil and the maltene have a linear relation with the asphaltene content. The refractive index spectra of different asphaltenes show variation in the low THz frequencies and comparable spectra in the higher frequencies. The absorption of asphaltene was mild and no distinctive absorption feature was observed except for some narrow absorption peaks that we attributed to water molecules adsorbed on the asphaltene. / Graduate

This thesis is focused on crude oil pipeline transport for the Czech Republic. It is concentrated on the company MERO ČR, a.s., which owns and operates czech part of the Družba crude oil pipeline and whole IKL crude oil pipeline. Futher it is concentrated on operation of both pipilines and the Central Crude Oil Tank Farm in Nelahozeves. At the end of my thesis there are concidered some alternative ways of crude oil transport for czech needs.

This thesis presents an in-depth study of the gas freeing of marine crude oil tanks using numerical simulation, beginning with a general summary of the problem, followed by an outline of the objectives of this work and the main difficulties involved. To outline essential background, a review of numerical methods, fluid flow, and related physical mechanisms has been undertaken, in addition to related ventilation fields, jet and jet impingement, and tanker-borne ventilation, in order to determine the state of the art and draw useful parallels between different ventilative fields, as well as identifying potential areas for model validation. A room-ventilation test case was studied in order to demonstrate the numerical method. It was found that assuming adiabatic walls and ignoring radiation resulted in highly idealised temperature predictions, and that radiation played a large part in enhancing vertical temperature prediction by redistributing thermal energy. For the gas-freeing analysis, the geometric models and solution procedures are introduced before simulation results presented and validated with analytical jet models and impingement penetration parameters. Analysis showed that the internal temperature of the tank was approximately homogeneous, allowing the tank to be considered isothermal. 2D simulations showed that after an initial period of time, the relative concentration distribution reaches steady state with decreasing average concentration as gas-freeing continues. Discussion of the results followed, examining aspects surrounding heat transfer and the choice of turbulence model, analysing the differences in the results between the first and secondmoment closure schemes and justification of assuming isothermal conditions. The variation in concentration was examined, and an analytical expression was derived which approximates the reduction in average gas concentration decay due to gas-freeing. It has been shown that double-hulled construction renders the internal temperature variation to around 10% of the temperature difference between the sea and deck. During the gasfreeing process proper, it was shown that after any stratified layer has been eroded and a stable flow field established, the relative concentration distribution remains constant. Gas freeing times were shown to be heavily dependent on the volume flux (and thus air change rate), and mathematical relations derived in order to provide approximately predict the time to gas free a crude oil tank (COT) given particular initial conditions.

The Canadian Council of Ministers of the Environment (CCME) endorsed the Reference Method for the Canada-Wide Standard (CWS) for Petroleum Hydrocarbons (PHC) in Soil – Tier 1 Method in 2001. The purpose of the CWS is to provide laboratories with analytical methods for producing accurate and reproducible PHC soil chemistry analysis results. CWS PHC concentrations are reported according to the following carbon ranges/fractions: F1 (C6-C10), F2 (C10-C16), F3 (C16-C34) and F4 (>C34). The Canada-wide Standards for Petroleum Hydrocarbons (PHC) in Soil provide generic soil quality guidelines for the each of the four PHC fractions. The CWS PHC extraction solvents inadvertently co-extract natural biogenic organic compounds (BOC) from organic soils. BOCs, such as waxes and fatty acids, are produced by living organisms such as plants, animals and microbes. PHC analysis of highly organic clean soils and manure compost can cause false exceedences of the F3 soil quality guidelines. This thesis presents a new mathematical Tier 2 approach to resolving biogenic interferences through the use of biogenic versus petrogenic Gas Chromatography - Flame Ionization Detector (GC-FID) chromatogram patterns produced by the CWS PHC Tier 1 method. This approach is based on the results of four studies: i) 300-day crude oil contaminated peat and sand microcosm experiment; ii) 300-day diesel drilling waste contaminated manure compost and sand microcosm experiment; iii) PHC analysis of 14 light to heavy crude oils and iv) Canadian background PHC soil field survey. These studies determined that the clean soils and compost had F3 ranges that were dominated by the F3b sub-fraction range (C22-C34). In contrast, the F3a (C16-C22) and F3b sub-fraction ranges were evenly distributed in the 14 fresh light to heavy crude oils. The diesel drilling waste was strongly dominated by the F3a sub-fraction range. The second important trend was that F2 concentrations were either non-detectable or slightly detectable in all of the clean soils and compost samples. In contrast, F2 concentrations were strongly prevalent in all of the crude oils and in the diesel drilling waste. F2 and F3b concentrations were applied to the F2:F3b ratio, which identified PHC absence in the clean materials (<0.10 ratio) and PHC presence (>0.10 ratio) in the contaminated materials. The %F3a:%F3b distributions were applied to the BOC-adjusted PHC F3 calculation, which estimated true PHC F3 concentrations in the clean and contaminated soils and manure compost. The combination of these two approaches provided an accurate and efficient solution to resolving false detections of crude oil and diesel PHCs and false exceedences of F3 soil toxicity guidelines by in clean soils and compost.

The recovery of ethylene glycol from its crude solutions in the production of polyethylene terephthalate (PET) has become important recently because of the rising cost of feedstocks for the manufacture of synthetic fibers and other polymeric materials. This work dealt with procedures for separation of ethylene glycol from its crude solutions and also with the identification of impurities, primarily phenols. The separation was carried out by fractional distillation techniques using three different additives: kerosene, hexachloronaphthalene, and naphthalene. The best additive was found by comparing the amounts of· recovered glycol. The identification of impurities was done by infrared spectroscopy and nuclear magnetic resonance spectroscopy.

In situ burning (ISB) is a practical method of oil spill cleanup in icy conditions. This study investigates one example of a likely oil spill scenario; burning oil in an ice cavity. In this situation, unique and unexplored physical processes come into play compared with the classical problem of confined pool fires in vessels. The icy walls of the cavity create a significant heat sink causing notable lateral heat losses especially for small cavity sizes (5-10 cm). Melting of ice because of the heat from the flame causes the geometry of cavity to change. Specifically, the diameter of the pool fire increases as the burning advances. This widening causes the fuel to stretch laterally thereby reducing its thickness at a faster rate. The melted ice water causes the oil layer to rise which causes the ullage height to decrease. The decrease in ullage and increase in diameter counteract the reduction in thickness because of widening or stretching of the fuel layer. There thus exists a strong coupling between the burning rate and the geometry change of the pool and cavity. To explore the problem, experiments were performed in circular ice cavities of varying diameters (5 - 25 cm). The change in shape of the ice cavity and the oil layer thickness are recorded using a combination of visual images, mass loss, and temperature data along the centerline and edge of the cavity. The average burning rate of crude oil in a cavity is greater than the corresponding burning rate in a vessel of equal diameter, yet the burning efficiency (% of fuel consumed during combustion) is lower. For example, the average mass loss rate in a 10 cm ice cavity is 50% higher than a steel vessel of similar size. However, the burning efficiency is lower by 50%. Widening of cavity (170%) contributes to the increase in the average mass burning rate. At the same time heat losses through fuel layer increase because of decrease in fuel thickness by widening of the fuel layer. This coupling is analyzed using a mathematical model which can predict burning rate and efficiency of crude oil in an ice cavity for the range of cavity diameters examined. Extension of the model to larger sizes comparable to realistic situations in the Arctic is discussed.

O processo de destilação do petróleo bruto é geralmente sujeito à atividade corrosiva dos equipamentos pelos ácidos, naturalmente presentes no petróleo. Este problema da corrosão pode ser atenuado pela adição de misturas de aminas neutralizantes que são inibidores da corrosão. Porém, esta adição significa um custo adicional ao processamento de petróleo. Para reduzir este custo direto da injeção de aminas o presente trabalho tem como objetivo aplicar a minimização do custo de misturas de aminas, utilizando dois diferentes métodos numéricos de otimização. Para isto foi utilizado um software desenvolvido no Laboratório Virtual de Predição de Propriedades (LVPP), onde os seguintes parâmetros operacionais são levados em consideração: temperatura de formação de sal, temperatura de orvalho do vapor d’água e pH do condensado da mistura. Esses parâmetros operacionais foram calculados e utilizados como restrições de desigualdade em otimizações com os métodos de Nelder-Mead (NM) e enxame de partículas (PSO). A escolha desses dois métodos numéricos foi devido a apresentarem características diferentes de busca do ótimo da função objetivo. O método NM apresenta caráter de busca local e o método PSO caráter de busca global. Assim, as duas restrições de desigualdade de otimização aplicadas foram: 1) o pH do condensado da mistura deve ser maior ou igual ao valor ótimo de 6,5; 2) a temperatura de formação de sal deve ser menor que temperatura do ponto de orvalho do vapor d’água. Quatro diferentes casos foram estudados, com estimativas iniciais das misturas escolhidas para satisfazer os itens 1) e 2). Os parâmetros operacionais calculados para as misturas de aminas apresentaram valores de pH abaixo dos valores considerados aceitáveis. Isso exigiu a implementação de uma condição de pH que aumentasse seu valor até a condição satisfatória, conforme restrição 1). A outra condição referente a restrição 2) foi satisfeita no cálculo das misturas para todos os casos estudados, exceto para o caso 2, de modo que a água na fase líquida arraste os sais potencialmente formados. Caso essa condição não fosse cumprida ocorreria a precipitação desses sais incrustando à superfície interna das tubulações e equipamentos, ocasionando um ataque corrosivo. As otimizações dos custos das misturas foram calculadas utilizando-se os próprios dados das misturas, com as condições dos itens 1) e 2) satisfeitas, como estimativa inicial. Para todos casos estudados, o método PSO foi capaz de obter resultados com custos menores que a metade do valor obtido com o método NM. / Crude distillation equipment is usually subject to the corrosive activity of acids. This problem can be mitigated by the addition of amines. With the addition of amines to this process a cost is generated, therefore to reduce this cost of neutralizing the amines the present work applies two different optimization methods, Nelder-Mead (NM) and Particle Swarm Optimization (PSO). This was accomplished using an in house software, developed in the Virtual Laboratory of Property Prediction (LVPP), where the following operating conditions are taken into account: salt formation temperature, condensation temperature of the water and pH of the condensate of the mixture. The operational parameters were calculated and used as inequality constraints in optimizations with both Nelder-Mead (NM) and a particle swarm optimization (PSO) methods. Two inequality constraints were considered: 1) The condensate pH of the mixture should be higher or equal than 6.5; 2) The salt temperature should be less than the dew temperature of water vapor. Four different cases were studied, throught estimates initials of the mixtures to satisfy items 1) and 2). It has been found that the operating parameters calculated for several amine mixtures produced pH values below the one considered optimal. This required the implementation of a pH condition that would increase its value up to the condition satisfactory, in accordance with restriction 1). The other condition concerning restriction 2) was satisfied in the calculation of the mixtures for all studied cases, except to case 2, through which the water in the liquid phase entrains the salts formed. If this condition were not met, the precipitation of salts would occur on the internal surface of pipes and equipments, causing a corrosive attack. The cost optimizations of the amine mixtures were calculated using their own data, with the constraints of items 1) and 2) satisfied by an initial estimate. Of all the cases studied, the PSO method obtained results with costs lower than half values obtained with the NM method.

With world crude oil reserves decreasing and energy prices continually increasing, interest in developing renewable alternatives to petroleum-based liquid fuels has increased. An alternative that has received consideration is the growth and harvest of microalgae for the production of biodiesel via extraction of the microalgal oil or lipids. However, costs related to the growth, harvesting and dewatering, and processing of algal biomass have limited commercial scale production of algal biodiesel. Coupling wastewater remediation to microalgal growth can lower costs associated with large scale growth of microalgae. Microalgae are capable of assimilating inorganic nitrogen and phosphorous from wastewater into the biomass. By harvesting the microalgal biomass these nutrients can be removed, thus remediating the wastewater. Standard methods of oil extraction require drying the harvested biomass, adding significant energetic cost to processing the algal biomass. Extracting algal lipids from wet microalgal biomass using traditional methods leads to drastic reductions in extraction efficiency, driving up processing costs. A wet lipid extraction procedure was developed that was capable of extracting 79% of the transesterifiable lipids from wet algal biomass (16% solids) without the use of organic solvents while using relatively mild conditions (90 °C and ambient pressures). Ultimately 77% of the extracted lipids were collected for biodiesel production. Furthermore, the procedure was capable of precipitating chlorophyll, allowing for the collection of algal lipids independently of chlorophyll. The capability of this procedure to extract lipids from wet algal biomass, to reduce chlorophyll contamination of the algal oil, and to generate feedstock material for the production of additional bio-products provides the basis for reducing scale-up costs associated with the production of algal biofuels and bioproducts.

This thesis describes a study in petroleum geochemistry and specifically of the application of Land-plant derived hydrocarbons to elucidating source matter type, depositional environment and thermal maturity of crude oils. Large volumes of petroleum have been generated from land-plant organic matter in many parts of the world, but especially in the Tertiary deltaic provinces of the USA, Canada, Africa, Southeast Asia, Australia and New Zealand. Compared to oils from other regions, these oils have a relatively complex pattern of biomarkers or molecular fossils, a feature reflecting the diversity of deltaic depositional environments and the advanced state of plant evolution during late Mesozoic and Tertiary time. The molecular and carbon isotopic composition of these oils is useful in identifying the character of their source beds and also in understanding the conditions that give rise to oil-prone sediments generally.Despite their widespread occurrence in oils and sediments, land-plant biomarkers have been used less frequently than compounds of algal origin as markers for source, depositional environment and thermal maturity. The present work sets out to extend the range of land-plant biomarker and isotope tools available to the petroleum geochemist and to provide a firmer foundation for some of the existing tools. A systematic study of the biomarker and n-alkane carbon-isotope composition of a set of late Mesozoic/Tertiary-age oils was carried out as a preamble to more focussed investigations. A comparison of the biomarker and n-alkane isotope data showed that parameters such as the oleanane/hopane ratio overestimate the higher plant contribution to marine deltaic oils. The abundance of bicadinane isomers was found to be much more variable than that of the oleananes, probably because of their close association with the highly resinous, dipterocarp hardwoods of ++ / Southeast Asia. However, small amounts of bicadinanes were found in an oil from outside the paleogeographic range of the dipterocarp family, indicating a more general source. Retention indices based on the regular hopane series were calculated for the main bicadinane and methyl bicadinane isomers and for a group of oleanoid triterpanes.Source rock depositional setting proved to be the primary control on the shape of the n-alkane isotope profile, with negatively sloping curves being characteristic of fluvio-deltaic and marginal lacustrine oils and flat or positively sloping curves typical of marine oils. The difference is probably related to the bacterial reworking of higher plant matter in the fluvio-deltaic environment. A slight isotopic anomaly at n-C(subscript)17 correlates with the abundance of algal-derived steranes and may indicate a minor marine contribution to the source of an fluvio-deltaic oil. A study of sediments from the South Sumatra Basin and New Zealand showed that the n-alkane isotope profile is determined mainly by source matter type and is little influenced by thermal maturity or depositional environment.Based on the results of the work described above, three aspects were chosen for further examination. These were: a) the factors controlling the carbon isotopic composition of n-alkanes and of resin-derived compounds in terrigenous oils; b) the influence of source, maturity and biodegradation on the abundance of bicadinanes, especially the effect of maturity on the isomer distribution, and c) the factors controlling the abundance of oleananes and rearranged oleananes in oils and Ancient sediments, especially the role of depositional environment.A preliminary study using sediments, from the Visayan Basin (Philippines) showed the bicadinane isomeric distribution to be sensitive to maturity. This suggested new maturity parameters which would be ++ / resistant to even severe biodegradation and largely immune to interference from diagenetic effects. A more detailed study of a marine-fluvio-deltaic depositional sequence from the South Sumatra Basin confirmed that the maturity indices based on bicadinanes and aromatic analogs were less subject to non-maturity influences than those based on the steranes and aromatic hydrocarbons. The values obtained for the bicadinane indices were compared with the maturity required for oil generation as estimated by kinetic modelling and with conventional maturity indicators such as sterane epimerisation and the methyl phenanthrene index. Values for several of the indices were also measured for 17 Tertiary-age oils from Southeast Asia, Papua New Guinea, New Zealand and Australia. The main bicadinane maturity indicator (BMI-1) continues to change into the oil window and hence is useful in ranking the relative maturity of oils as well as sediments. Values of BMI-1 for two oils having unusually low sterane maturities were found to be normal and, in the light of this observation, the conventional explanation for low sterane epimerisation of many Tertiary-age oils was critically evaluated.The oleananes, as markers for the angiosperms, provide valuable source and age information when present in an oil. Nevertheless, their abundance is not quantitatively related to the land plant input and indeed their presence results from a small "leak" in diagenetic processes leading primarily to aromatic oleanoids. Evidence is presented that contact of plant matter with seawater during early diagenesis enhances the expression of oleananes in a mature sediment or oil. Oleananes are absent or present at very low concentrations in samples from the base of an Eocene coal seam affected by post-depositional seawater intrusion. However, their abundance increases toward the top of the seam in correlation with ++ / % organic sulphur, dibenzothiophene/phenanthrene and the homohopane index. Similarly, in deltaic sediments from the South Sumatra Basin, oleanane/hopane is strongly correlated with indicators of marine influence such as C[subscript 27]/C[subscript 29] steranes and of oxic/anoxic conditions such as the homohopane index. In each case, increasing oleanane abundance is accompanied by a reduction in the extent of aromatisation and, for the South Sumatra Basin, the proportion of A-ring contracted oleananes. An angiosperm-derived Miocene coal from the Philippines, deposited under freshwater conditions, shows abundant aromatic oleanoids but no oleananes. These results show that oleananes need to be used with caution as age and source markers in fluvio- deltaic and lacustrine petroleum systems. On the other hand, their sensitivity to early diagenetic conditions may make them useful in locating effective source rocks in such systems.Compounds derived from plant resins are major components of some terrigenous oils. Although recent studies have elucidated the molecular structure of resinites, very little information was available on the carbon isotope composition of resinites prior to the present study. No carbon isotope studies of resin-derived compounds in oils had been performed. Hence, carbon stable isotope analyses were carried out on a set of modern and fossil resins of diverse origins and compound specific isotope analysis was used to characterise individual hydrocarbons in resin pyrolysates and oils derived from resinitic source matter. The results showed that "Class V' resinites derived from gymnosperms are enriched in the heavy carbon isotope compared with the angiosperm-derived "Class W' resinites. Furthermore, both the fossil resinites themselves and individual hydrocarbons derived from them are isotopically heavy compared with modern plant resins. The reasons for ++ / these differences and their implications for petroleum geochemical studies are discussed.