Twenty years ago, Chang et al. (1998) introduced the three-yield stresses concept (dynamic, static and elastic limits) to describe yielding of waxy crude oils cooled below the wax appearance temperature (WAT). At the time, the limits in rheological instruments were such that they never actually measured the elastic-limit, a key fundamental property. Using modern instruments, this research succeeds in recording for the first time the entire yielding process down to stresses of 10-7 Pa and shear rate of 10-6 min-1 as a function of temperature, cooling rate and stress loading rate using two waxy oils of different origins and wax content. A four-yield stress model is established using derivative data (dynamic fluidity and failure acceleration). In addition, calorimetry (DSC) and microscopy (CPM) helped extract WAT, the gel and pour points and link gel crystal structure and its yielding and breakage to rheological properties. The yielding stresses measured rheologically were tested in laboratory pipelines at two diameter scales, 6.5mm and 13.5mm to compare stresses in uniform and non-uniform cooling. It is demonstrated that rheological instruments can only predict gel breaking pressure when the cooling rate is low, i.e. yielding at the pipe wall. A complementary heat transfer study was performed on a section of pipe statically cooled, both experimentally and theoretically to predict the gel front-liquid oil interface that develops in industrial pipeline where gel breaking occurs. This key information together with rheological data provide the means to predict accurately restart pressures of shut gelled pipelines that have eluded previous research. / Ministry of Higher Education of the Libyan Government

Catalytic hydrotreating (HDT) is a mature process technology practiced in the petroleum refining industries to treat oil fractions for the removal of impurities (such as sulfur, nitrogen, metals, asphaltene). Hydrotreating of whole crude oil is a new technology and is regarded as one of the more difficult tasks that have not been reported widely in the literature. In order to obtain useful models for the HDT process that can be confidently applied to reactor design, operation and control, the accurate estimation of kinetic parameters of the relevant reaction scheme are required. This thesis aims to develop a crude oil hydrotreating process (based on hydrotreating of whole crude oil followed by distillation) with high efficiency, selectivity and minimum energy consumption via pilot plant experiments, mathematical modelling and optimization. To estimate the kinetic parameters and to validate the kinetic models under different operating conditions, a set of experiments were carried out in a continuous flow isothermal trickle bed reactor using crude oil as a feedstock and commercial cobaltmolybdenum on alumina (Co-Mo/¿-Al2O3) as a catalyst. The reactor temperature was varied from 335°C to 400°C, the hydrogen pressure from 4 to10 MPa and the liquid hourly space velocity (LHSV) from 0.5 to 1.5 hr-1, keeping constant hydrogen to oil ratio (H2/Oil) at 250 L/L. The main hydrotreating reactions were hydrodesulfurization (HDS), hydrodenitrogenation (HDN), hydrodeasphaltenization (HDAs) and hydrodemetallization (HDM) that includes hydrodevanadization (HDV) and hydrodenickelation (HDNi). An optimization technique is used to evaluate the best kinetic models of a trickle-bed reactor (TBR) process utilized for HDS, HDAs, HDN, HDV and HDNi of crude oil based on pilot plant experiments. The minimization of the sum of the squared errors (SSE) between the experimental and estimated concentrations of sulfur (S), nitrogen (N), asphaltene (Asph), vanadium (V) and nickel (Ni) compounds in the products, is used as an objective function in the optimization problem using two approaches (linear (LN) and non-linear (NLN) regression). The growing demand for high-quality middle distillates is increasing worldwide whereas the demand for low-value oil products, such as heavy oils and residues, is decreasing. Thus, maximizing the production of more liquid distillates of very high quality is of immediate interest to refiners. At the same time, environmental legislation has led to more strict specifications of petroleum derivatives. Crude oil hydrotreatment enhances the productivity of distillate fractions due to chemical reactions. The hydrotreated crude oil was distilled into the following fractions (using distillation pilot plant unit): light naphtha (L.N), heavy naphtha (H.N), heavy kerosene (H.K), light gas oil (L.G.O) and reduced crude residue (R.C.R) in order to compare the yield of these fractions produced by distillation after the HDT process with those produced by conventional methods (i.e. HDT of each fraction separately after the distillation). The yield of middle distillate showed greater yield compared to the middle distillate produced by conventional methods in addition to improve the properties of R.C.R. Kinetic models that enhance oil distillates productivity are also proposed based on the experimental data obtained in a pilot plant at different operation conditions using the discrete kinetic lumping approach. The kinetic models of crude oil hydrotreating are assumed to include five lumps: gases (G), naphtha (N), heavy kerosene (H.K), light gas oil (L.G.O) and reduced crude residue (R.C.R). For all experiments, the sum of the squared errors (SSE) between the experimental product compositions and predicted values of compositions is minimized using optimization technique. The kinetic models developed are then used to describe and analyse the behaviour of an industrial trickle bed reactor (TBR) used for crude oil hydrotreating with the optimal quench system based on experiments in order to evaluate the viability of large-scale processing of crude oil hydrotreating. The optimal distribution of the catalyst bed (in terms of optimal reactor length to diameter) with the best quench position and quench rate are investigated, based upon the total annual cost. The energy consumption is very important for reducing environmental impact and maximizing the profitability of operation. Since high temperatures are employed in hydrotreating (HDT) processes, hot effluents can be used to heat other cold process streams. It is noticed that the energy consumption and recovery issues may be ignored for pilot plant experiments while these energies could not be ignored for large scale operations. Here, the heat integration of the HDT process during hydrotreating of crude oil in trickle bed reactor is addressed in order to recover most of the external energy. Experimental information obtained from a pilot scale, kinetics and reactor modelling tools, and commercial process data, are employed for the heat integration process model. The optimization problem is formulated to optimize some of the design and operating parameters of integrated process, and minimizing the overall annual cost is used as an objective function. The economic analysis of the continuous whole industrial refining process that involves the developed hydrotreating (integrated hydrotreating process) unit with the other complementary units (until the units that used to produce middle distillate fractions) is also presented. In all cases considered in this study, the gPROMS (general PROcess Modelling System) package has been used for modelling, simulation and parameter estimation via optimization process. / Tikrit University, Iraq

[ES] Durante la presente tesis doctoral se ha desarrollado un proceso de mejora parcial in-situ en superficie de un crudo extrapesado que ha permitido obtener un buen rendimiento a un crudo sintético que cumple con las especificaciones necesarias para ser transportado a través de un oleoducto, esto es, un crudo sintético con una gravedad API superior a 19, una viscosidad inferior a los 300 cSt y libre de asfaltenos. Además, se ha conseguido eliminar prácticamente el 99% en peso de los metales, níquel y vanadio, presentes en el crudo de partida, lo que facilita el posterior procesado de este crudo sintético en una refinería. Las reacciones necesarias para desarrollar este proceso se han llevado a cabo utilizado una unidad Micro-Downer (MDU). Dicha unidad consta de un reactor de lecho transportado descendente y permite obtener resultados a nivel de laboratorio similares a los que se obtendrían al procesar cualquier crudo en un reactor tipo FCC a escala industrial. Se han estudiado las condiciones de reacción (temperatura, tiempo de residencia y relación sólido a carga) más adecuadas para llevar a cabo el craqueo térmico de un crudo extrapesado en este tipo de reactores. Asimismo, se ha encontrado que entre varios materiales sólidos con diferentes propiedades ácidas y texturales, es con el caolín, una arcilla natural con un cierto grado de porosidad residual en su estructura cristalina, con el que se obtiene el mayor rendimiento a productos líquidos que cumplen los requisitos de densidad y viscosidad necesarios para poder ser transportados a través de un oleoducto. Estos resultados se han obtenido tras llevar a cabo la reacción en condiciones no severas (530ºC, 0,3 s de tiempo de residencia y una relación sólido a carga de 8 g g¿1), y que por tanto no requieren de un elevado gasto energético. En contrapartida, se ha detectado que con cada uno de los sólidos utilizados y en cualquiera de las condiciones de operación estudiadas, todos los crudos sintéticos recogidos son inestables con respecto a la floculación de los asfaltenos. Con el fin de subsanar esta limitación de la tesis doctoral, en el apartado siguiente se ha intentado eliminar la fracción de asfaltenos de los líquidos finales. Para ello se ha utilizado, ya sea como sustituto del caolín o como aditivo junto a él, un material sólido con actividad para el craqueo de fondo (BCA, del inglés Bottom Cracking Additive). De este modo se pretende eliminar esta fracción de asfaltenos mediante craqueo catalítico, dando lugar a la formación de otras fracciones más ligeras de crudo, y/o mediante reacciones de condensación dan- do lugar a la formación de coque. En este apartado ha quedado demostrado que la presencia de un cierto grado de acidez, aunque residual, en el sólido de intercambio de calor empleado para procesar un crudo extrapesado como el utilizado para realizar este estudio, conlleva un incremento en el rendimiento a coque cuya principal consecuencia es una importante bajada en el rendimiento a crudo sintético final sin que, en contrapartida, se consiga eliminar el problema de la presencia de asfaltenos en los líquidos finales. Tras comprobar que para obtener crudos sintéticos estables con respecto a la fioculación de los asfaltenos es necesario eliminar la fracción residuo, es decir, los hidrocarburos con puntos de ebullición superior a los 537ºC, el siguiente paso se ha centrado en encontrar una combinación de etapas con las que sea posible convertir, o reciclar hasta la extinción, esta fracción residuo. Con este fin se han ideado tres estrategias de procesos de mejora y se han llevado a cabo estimaciones teóricas que nos han permitido conocer la mejor estrategia de procesado para obtener el mayor rendimiento a crudo sintético estable. Finalmente, la validez de este nuevo procesos se ha estimado comparando estos resultados experimentales obtenidos a escala de laboratorio con los generados al procesar este mismo crudo extrapesado en una planta piloto de delayed coking. / [CA] Durant la present tesi doctoral s'ha desenvolupat un procés de millora parcial in-*situ en superfície d'un cru extrapesado que ha permès obtenir un bon rendiment a un cru sintètic que compleix amb les especificacions necessàries per a ser transportat a través d'un oleoducte, això és, un cru sintètic amb una gravetat API superior a 19, una viscositat inferior als 300 cSt i lliure de asfaltenos. A més, s'ha aconseguit eliminar pràcticament el 99% en pes dels metalls, níquel i vanadi, presents en el cru de partida, la qual cosa facilita el posterior processament d'aquest cru sintètic en una refineria. Les reaccions necessàries per a desenvolupar aquest procés s'han dut a terme utilitzat una unitat Micro-Downer (MDU). Aquesta unitat consta d'un reactor de llit transportat descendent i permet obtenir resultats a nivell de laboratori similars als que s'obtindrien en processar qualsevol cru en un reactor tipus FCC a escala industrial. S'han estudiat les condicions de reacció (temperatura, temps de residència i relació sòlid a càrrega) més adequades per a dur a terme el craqueig tèrmic d'un cru extrapesado en aquest tipus de reactors. Així mateix, s'ha trobat que entre diversos materials sòlids amb diferents propietats àcides i texturales, és amb el caolí, una argila natural amb un cert grau de porositat residual en la seua estructura cristal·lina, amb el qual s'obté el major rendiment a productes líquids que compleixen els requisits de densitat i viscositat necessaris per a poder ser transportats a través d'un oleoducte. Aquests resultats s'han obtingut després de dur a terme la reacció en condicions no severes (530 °C, 0,3 s de temps de residència i una relació sòlid a càrrega de 8 g g1), i que per tant no requereixen d'una elevada despesa energètica. En contrapartida, s'ha detectat que amb cadascun dels sòlids utilitzats i en qualsevol de les condicions d'operació estudiades, tots els crus sintètics arreplegats són inestables respecte a la floculació dels asfaltenos. Amb la finalitat d'esmenar aquesta limitació de la tesi doctoral, en l'apartat següent s'ha intentat eliminar la fracció de asfaltenos dels líquids finals. Per a això s'ha utilitzat, ja siga com a substitut del caolí o com a additiu al costat d'ell, un material sòlid amb activitat per al craqueig de fons (BCA, de l'anglès Bottom Cracking Additive). D'aquesta manera es pretén eliminar aquesta fracció de asfaltenos mitjançant craqueig catalític, donant lloc a la formació d'altres fraccions més lleugeres de cru, i/o mitjançant reaccions de condensació donen- do lloc a la formació de coc. En aquest apartat ha quedat demostrat que la presència d'un cert grau d'acidesa, encara que residual, en el sòlid d'intercanvi de calor emprada per a processar un cru extrapesado com l'utilitzat per a realitzar aquest estudi, comporta un increment en el rendiment a coc la principal conseqüència del qual és una important baixada en el rendiment a cru sintètic final sense que, en contrapartida, s'aconseguisca eliminar el problema de la presència de asfaltenos en els líquids finals. Després de comprovar que per a obtenir crus sintètics estables respecte a la fioculación dels asfaltenos és necessari eliminar la fracció residu, és a dir, els hidrocarburs amb punts d'ebullició superior als 537 °C, el següent pas s'ha centrat en trobar una combinació d'etapes amb les quals siga possible convertir, o reciclar fins a l'extinció, aquesta fracció residu. A aquest efecte s'han ideat tres estratègies de processos de millora i s'han dut a terme estimacions teòriques que ens han permès conèixer la millor estratègia de processament per a obtenir el major rendiment a cru sintètic estable. Finalment, la validesa d'aquest nou processos s'ha estimat comparant aquests resultats experimentals obtinguts a escala de laboratori amb els generats en processar aquest mateix cru extrapesado en una planta pilot de delayed coking. / [EN] During this doctoral thesis it has been developed an in-situ extra-heavy crude oil partial upgrading process that has allowed to obtain a good yield to a synthetic crude oil that meets the requirements of density and viscosity to be transported through a pipeline, that is, a synthetic crude with an API gravity grater than 19, a viscosity of less than 300 cSt and free of asphaltenes. Furthermore, practically all the metals, nickel and vanadium, have been removed from the starting extra-heavy crude oil, which greatly facilitates the further processing of this syncrude in a refinery. In order to develop this process a study has been conducted to determine the ideal reaction conditions (temperature, residence time and solid to oil ratio) to carry out the thermal cracking reaction of an extra-heavy crude oil in a downflow transported bed reactor. Moreover, it has been found that among several solid materials with different acidities and textural properties, it is the Kaolín, a natural clay with a small degree of porosity in its crystalline structure, which yields the largest amount of synthetic crude with the density and viscosity values required to be transported through an oil pipeline. These results have been obtained after performing the reaction under non-severe conditions (530ºC, 0.3 seconds and 8g g¿1) and therefore do not require a high energy expenditure. However, the liquids collected after each of the reactions carried out are unstable with respect to asphaltene flocculation, regardless of the solid heat exchanger or the reaction conditions used. To overcome this shortcoming, the next step has focused on eliminating asphaltenes from the synthetic crude. To do so, it has been employed, either alone or as an additive together with kaolin, a heat exchange solid with a certain grade of activity to performe the catalytic cracking of heavy molecules (BCA, Bottom Cracking Additive). This would allow asphaltenes removal by means of catalytic cracking reactions, giving rise to lighter hydrocarbons formation, and/or by means of condensation reactions, giving rise to coke formation. In this section it has been concluded that, due to the characteristics of the composition of the extraheavy crude oil used in the present study, the presence of any kind of acidity on the solid used as heat exchanger lead to a such increase in coke yield, with the concomitant reduction in the yield to syncrude, that made its used inadvisable. In addition, asphaltene flocculation continues to be observed within the reduced amount of liquids collected. So that, after assuming that in order to obtain stable liquids respect asphaltenes flocculation it is mandatory to get a syncrude free of residue fraction, hydrocarbon products with boiling points higher than 537ºC, in the next section has been analyzed the combination of different process steps to either thermally convert or recycle to extinction this heavy hydrocarbons fraction. Three different strategies of improvement processes have been schematized and the best one to produce the greatest amount of stable synthetic crude has been determined through theoretical calculations. Finally, this new partial upgrading process has been assessed by comparing these results obtained experimentally in the laboratory with the ones obtained after processing the same extraheavy crude oil in a Delayed Coking pilot plant. / Corresa Mateu, E. (2023). Aprovechamiento y mejora de crudos extrapesados [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/198857

We evaluated the effect of cyanobacterial crude extracts containing microcystin (CCEMC+) from a natural bloom on seed germination and initial development of three economically important legume species: green mung bean Vigna radiata, cowpea Vigna cylindrical and red mung bean Vigna angularis and compared it to crude extracts of cyanobacteria without the toxin (CCEMC–). Results showed that CCEMC+ and CCEMC– caused different effects on seed germination and initial development of the three species. There was a clear inhibition on germination and root growth of the green mung bean exposed to the CCEMC+ (20, 200 and 500 μg/L), indicating that the green mung bean being more sensitive to CCEMC+ when compared to the cowpea and red mung bean. CCEMC+ induced a greater occurrence of abnormal seedlings in the green mung bean, duce to inhibition the germination as well as reduction of fresh weight and root length. The CCEMC– extract caused no harmful effects to germination and seedlings growth of the green mung bean and red mung bean. However, it reduced shoot and root length in cowpea bean, suggesting that the cowpea being more sensitive to both extracts. Our results indicated that the sensitivity in germination and root growth of the green mung bean V. radiata could be used as an indicator to evaluate the toxic effect and monitor the toxin concentration of water contaminated with microcystins. / Nghiên cứu này khảo sát và so sánh các tác động bất lợi của ly trích vi khuẩn lam có chứa và không chứa độc tố lên sự nẩy mầm và sự phát triển ở giai đoạn đầu của ba loại cây họ đậu gồm đậu xanh Vigna radiata, đậu đỏ Vigna angularis và đậu đen Vigna cylindrical. Kết quả cho thấy hai loại ly trích gây ra các tác động khác nhau lên ba loại cây đậu thí nghiệm. Ly trích vi khuẩn lam có chứa độc tố ở nồng độ 20, 200 và 500 μg/L ngăn chặn đáng kể sự nẩy mầm và sự phát triển rể ở đậu xanh. Cả hai loại ly trích có chứa và không chứa độc tố đều ngăn chặn sự nẩy mầm và sự phát triển rể ở đậu đen. Ngược lại ly trích vi khuẩn lam có chứa độc tố ở nồng độ 500 μg/L lại kích thích chiều dài rể, thân mầm và trọng lượng tươi ở đậu đỏ. Kết quả cho thấy đậu đen khá nhạy cảm với cả hai loại ly trích có chứa và không chứa độc tố, trong khi đó đậu xanh nhạy cảm hơn với ly trích có chứa độc tố. Tính nhạy cảm của các loại cây họ đậu khi phơi nhiễm với ly trích vi khuẩn lam có thể được sử dụng để chỉ thị cho sự ô nhiễm và quan trắc độc tố vi khuẩn lam trong môi trường.

Some of anaerobic, mesophilic sulfate-reducing bacteria that produce H₂S and cause microbial metal corrosion can degrade crude oil in anaerobic conditions. In this study, a mesophilic sulfate-reducing bacterial strain D107G3 isolated from Bach Ho gas-oil field in Vung Tau, Vietnam that is able to utilize crude oil in the anaerobic condition is reported. The strain D107G3 was classified as a Gram-negative bacterium by using Gram staining method. Basing on scanning microscopy observation, the cell of a strain D107G3 had a curved rod shape. The 16S rRNA gene sequence analysis showed that the strain D107G3 was identified as Desulfovibrio vulgaris with 99.7% identity. The suitable conditions for its growth that was determined via estimating its H₂S production was the modified Postgate B medium containing 1% (v/v) crude oil, 1% NaCl (w/v), pH 7 and 300C incubation. In these conditions, the strain D107G3 can consume 11.4 % of crude oil total and oxidize heavy crude oil (≥ C45) for one month at anoxic condition. These obtained results not only contribute to the science but also continue to warn about the dangers of mesophilic sulfate reducing bacteria to the process of crude oil exploitation, use, and storage in Vung Tau, Vietnam. / Trong bài báo này, chủng vi khuẩn khử sunphat (KSF) ưa ấm D107G3 phân lập từ giếng khoan dầu khí mỏ Bạch Hổ, Vũng Tàu, Việt Nam có khả năng sử dụng dầu thô trong điều kiện kị khí được công bố. Chủng D107G3 được xác định là vi khuẩn Gram âm nhờ phương pháp nhuộm Gram. Quan sát trên kính hiển vi điện tử quét cho thấy tế bào chủng D107G3 có hình que cong. Kết quả phân tích trình tự gen 16S rRNA đã xác định được chủng D107G3 thuộc loài Desulfovibrio vulgaris với độ tương đồng 99.7%. Thông qua đánh giá lượng H₂S tạo thành đã khám phá được điều kiện thích hợp cho sinh trưởng của chủng D107G3: môi trường Postgate B cải tiến chứa 1% (v/v) dầu thô, 1 % NaCl (gL⁻¹), pH 7 và nuôi cấy ở 30°C. Trong điều kiện đó, chủng D107G3 đã sử dụng được 11.4 % hàm lượng dầu tổng số, thành phần dầu bị phân huỷ là các n-parafin có mạch C≥45 sau 1 tháng nuôi cấy kỵ khí. Các kết quả này đóng góp về mặt khoa học và tiếp tục cảnh báo mối nguy hại của KSF ưa ấm đến việc khai thác, sử dụng và bảo quản dầu mỏ ở Vũng Tàu, Việt Nam.

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Recently, based on the physics of viscosity, we developed a new technology, which utilizes electric or magnetic fields to change the rheology of complex fluids to reduce the viscosity, while keeping the temperature unchanged. The method is universal and applicable to all complex fluids with suspended particles of nano-meter, sub-micrometer, or micrometer size. Completely different from the traditional viscosity reduction method, raising the temperature, this technology is energy-efficient, as it only requires small amount of energy to aggregate the suspended particles. In this thesis, we will first discuss this new technology in detail, both in theory and practice. Then, we will report applications of our technology to energy science research. Presently, 80% of all energy sources are liquid fuels. The viscosity of liquid fuels plays an important role in energy production and energy conservation. With an electric field, we can reduce the viscosity of asphalt-based crude oil. This is important and useful for heavy crude oil and off-shore crude oil production and transportation. Especially, since there is no practical way to raise the temperature of crude oil inside the deepwater pipelines, our technology may play a key role in future off-shore crude oil production. Electrorehology can also be used to reduce the viscosity of refinery fuels, such as diesel fuel and gasoline. When we apply this technology to fuel injection, the fuel droplets in the fuel atomization become smaller, leading to faster combustion in the engine chambers. As the fuel efficiency of internal combustion engines depends on the combustion speed and timing, the fast combustion produces much higher fuel efficiency. Therefore, adding our technology on existing engines improves the engine efficiency significantly. A theoretical model for the engine combustion, which explains how fast combustion improves the engine efficiency, is also presented in the thesis. / Physics

Chemical EOR processes such as polymer flooding and surfactant polymer flooding must be designed and implemented in an economically attractive manner to be perceived as viable oil recovery options. The primary expenses associated with these processes are chemical costs which are predominantly controlled by the crude oil properties of a reservoir. Crude oil viscosity dictates polymer concentration requirements for mobility control and can also negatively affect the rheological properties of a microemulsion when surfactant polymer flooding. High microemulsion viscosity can be reduced with the introduction of an alcohol co-solvent into the surfactant formulation, but this increases the cost of the formulation. Experimental research done as part of this study combined the process of hot water injection with ASP flooding as a solution to reduce both crude oil viscosity and microemulsion viscosity. The results of this investigation revealed that when action was taken to reduce microemulsion viscosity, residual oil recoveries were greater than 90%. Hot water flooding lowered required polymer concentrations by reducing oil viscosity and lowered microemulsion viscosity without co-solvent. Laboratory testing of viscous microemulsions in core floods proved to compromise surfactant performance and oil recovery by causing high surfactant retention, high pressure gradients that would be unsustainable in the field, high required polymer concentrations to maintain favorable mobility during chemical flooding, reduced sweep efficiency and stagnation of microemulsions due to high viscosity from flowing at low shear rates. Rough scale-up chemical cost estimations were performed using core flood performance data. Without reducing microemulsion viscosity, field chemical costs were as high as 26.15 dollars per incremental barrel of oil. The introduction of co-solvent reduced chemical costs to as low as 22.01 dollars per incremental barrel of oil. This reduction in cost is the combined result of increasing residual oil recovery and the added cost of an alcohol co-solvent. Heating the reservoir by hot water flooding resulted in combined chemical and heating costs of 13.94 dollars per incremental barrel of oil. The significant drop in cost when using hot water is due to increased residual oil recovery, reduction in polymer concentrations from reduced oil viscosity and reduction of microemulsion viscosity at a fraction of the cost of co-solvent. / text