The demand for the efficient utilisation of straw biomass requires detailed analyses of its fundamental chemical structures, morphological complexity, individual cell wall components and the correlation of physicochemical to mechanical properties. The study involved two main areas: understanding the details of microstructure and characterisation/differentiation of properties of various profiled wheat straw. Comprehensive and systematic experimental programmes were therefore designed in order to thoroughly investigate the node and internode of wheat straw with quantitative appraisals and qualitative interpretations. This could contribute towards its valorisation in bio-refinery pathways. The sophisticated morphology of node and internode, inner and outer surface was investigated. It was found that the morphology across node area has a great variety when the longitudinal profile is investigated in the upwards direction to grain head. A 3D image of nodes illustrated the dense core with elliptical shaped rings organised in order to provide the echanical strength to the overall stem. The variation of cell wall composition across wheat straw node and internode showed that node yielded slightly higher Klason lignin, extractives and ash content than internode, which could be related to their morphology, precisely the higher ash and extractives content in the node are explained by thicker epidermis tissue. The physicochemical and mechanical properties of node and internode were differentiated and the effects of a combination of mild physical pre-treatment were monitored. The results indicated: i) the reduction of waxes from the outer surface, ii) significantly lower (P < 0.05) extractives and iii) the dissolution of silicon (Si weight %) on the outer surface of node and internode. The tensile strength of nodes and internodes after pre-treatments also resulted in a significant increase (P < 0.05). The accumulated characteristic data enabled the investigation of interfacial properties and bonding mechanisms of the inner and outer surface of wheat straw with thermosetting resins. Different surface functionalities and anatomical sections, altered the bonding performance, i.e. waxes and silica concentrated on the outer surface inhibited the quality of the interface. Nevertheless, the treatment improved interface (P < 0.05) between resins and the micro-porous surface of wheat straw by causing the microcellular structure of straw to expand and hence inspire the mechanical entanglement on a micro level upon resin solidification.

Molecular management targets the right molecules to be at the right place, at the right time and at the right price. It consists of molecular characterisation of refining streams, molecular modelling and optimisation of refining processes, as well as overall refinery optimisation integrating material processing system and utility system on the molecular level. The need to increase modelling details to a molecular level is not just a result of political regulations, which force refiners to managing the molecule properly, but also seems to be a very promising to increase the refining margin. In this work, four aspects of molecular management are investigated respectively. Molecular Type Homologous Series (MTHS) matrix framework is enhanced on both representation construction and transformation methodology. To improve the accuracy and adequacy of the representation model, different strategies are formulated separately to consider isomers for light and middle distillates. By introducing statistical distribution, which takes the composition distribution of molecules into account, the transformation approach is revolutionised to increase the usability, and tackle the challenge of possibly achieving significantly different compositions from the same bulk properties by the existing approaches. The methodology is also enhanced by applying extensive bulk properties. Case studies demonstrate the effectiveness and accuracy of the methodology. Based on the proposed characterisation method, refining processes are modelled on a molecular level, and then process level optimisation is preformed to have an insight view of economic performance. Three different processes, including gasoline blending, catalytic reforming, and diesel hydrotreating, are investigated respectively. Regarding gasoline blending, the property prediction of blending components, and the blending nonlinearity are discussed. To tightly control on the property giveaway, a molecular model of gasoline blending is developed, and then integrated into the recipe optimisation. As for the conversion processes, catalytic reforming and diesel hydrotreating, reactions and reactors are modelled separately, and then followed by the consideration of catalyst deactivation. A homogeneous rigorous molecular model of a semiregenerative catalytic reforming process, considering pressure drop, has been developed. In addition, a multi-period process optimisation model has been formulated. Regarding diesel hydrotreating, a molecular model of reactions with a three-phase trickle-bed reactor has been developed. The concept of reaction family is successfully applied. A structural contribution approach is used to obtain kinetics and adsorption parameters. A series of procedures are developed to solve the complex problem. Thereafter, a process optimisation model has been developed with the consideration of catalyst deactivation, with a new strategy on the division of catalyst life. Finally, a two-level decomposition optimisation method is extended to incorporate molecular modelling into the overall refinery optimisation, and then applied in two aspects. Firstly, with the integration of the process and the site-level models, a better perspective is obtained with regard to a material processing system. By molecular modelling of refining streams and processes, the integrated approach not only controls the molecules in products properly, but also increases the overall performance. In the second application, a framework integrating a hydrogen network with hydroprocesses is developed to target the maximum profit, rather than saving hydrogen. It allocates hydrogen on the hydrogen network level and utilise hydrogen efficiently on the process level by optimising operating conditions. Consequently, the extent of achieving the maximum profit could be fully exploited with optimal hydrogen utilisation.

The focus of this work is an industrial refinery model developed by TotalEnergies SE. The model is a sparse, large-scale, nonconvex, mixed-integer nonlinear program (MINLP). The nonconvexity of the problem arises from the many bilinear, trilinear, fractional, logarithmic, exponential, and sigmoidal terms. In order to account for various sources of uncertainty in refinery planning, the industrial refinery model is extended into a two-stage stochastic program, where binary scheduling decisions must be made prior to the realization of the uncertainty, and mixed-integer recourse decisions are made afterwards. Two case studies involving uncertainty are formulated and solved in order to demonstrate the economic and logistical benefits of robust solutions over their deterministic counterparts. A full-space solution strategy is proposed wherein the integrality constraints are relaxed and a multi-step initialization strategy is employed in order to gradually approach the feasible region of the multi-scenario problem. The full-space solution strategy was significantly hampered by difficulties with finding a feasible point and numerical problems. In order to facilitate the identification of a feasible point and to reduce the incidence of numerical difficulties, a hybrid surrogate refinery model was developed using the ALAMO modelling tool. An evaluation procedure was employed to assess the surrogate model, which was shown to be reasonably accurate for most output variables and to be more reliable than the high-fidelity model. Feasible solutions are obtained for the continuous relaxations of both case studies using the full-space solution strategy in conjunction with the surrogate model. In order to solve the original MINLP problems, a decomposition strategy based on the generalized Benders decomposition (GBD) algorithm is proposed. The binary decisions are designated as complicating variables that, when fixed, reduce the full-space problem to a series of independent scenario subproblems. Through the application of the GBD algorithm, feasible mixed-integer solutions are obtained for both case studies, however optimality could not be guaranteed. Solutions obtained via the stochastic programming framework are shown to be more robust than solutions obtained via a deterministic problem formulation. / Thesis / Master of Applied Science (MASc)

No description available.

The purpose of this work aims to develop and explore a nonlinear multiperiod petroleum refinery model based on a real-world model. Due to the inherent complexity and interconnected nature of petroleum refineries, various studies are implemented to describe the multiperiod model. The model is based around maximizing the profit of a petroleum refinery, starting from the crude inputs through the crude distillation unit, to the intermediate product processing through various unit operations, and finally to the blending of the final products. The model begins as a single period model, and is re-formulated as a multiperiod model by incorporating intermediate product tanks and dividing the model into partitions. In solving the multiperiod model, the termination criteria for convergence was varied in order to investigate the effect on the solution; it was found that it is acceptable to terminate at a relaxed tolerance due to minimal differences in solution. Several case studies, defined as deviations from normal operation, are implemented in order to draw comparisons between the real-world model and the model studied in this thesis. The thesis model, solved by CONOPT and IPOPT, resulted in significant gains over the real-world model. Next, a Lagrangean decomposition scheme was implemented in an attempt to decrease computation times. The decomposition was unable to find feasible solutions for the subproblems, as the nonlinear and nonconvex nature of the problem posed difficulty in finding feasibilities. However, in the case of a failed decomposition, the point where the decomposition ends may be used as an initial guess to solve the full space problem, regardless of feasibility of the subproblems. It was found that running the decomposition fewer times provided better initial guesses due to lower constraint violations from the infeasibilities, and then combined with the shorter decomposition time resulted in faster computation times. / Thesis / Master of Applied Science (MASc) / Petroleum refineries consist of complex units that serve a certain purpose, such as separating components of a mixed stream or blending intermediate products, in order to create final commercial products, e.g. gasoline and diesel. Due to the complexity and interconnectivity in a refinery, it is difficult to determine the optimal mode of operation. Thus, by formulating the refinery in mathematical form, optimization techniques may be used to find optimal operation. Furthermore, optimization problems can be formulated in a multiperiod fashion, where the problem is repeated over a set time horizon in partitions. The advantage is a higher detail in the operation of the refinery but this comes at a cost of higher computation time. In this work, a multiperiod refinery is formulated and studied by exploring model size, computation times, comparison of solvers, and solution strategies such as decomposition.

"This paper is the result of a study of the oil industry in Cooke County Texas. Consideration was given to the following factors: the physiography and geology of Cooke County, the first oil developments, opening of various fields, the Tydal Refinery, and the benefits of the oil industry to the county in terms of employment, busines establishments, schools, and social efforts. Both persona and documentary source were utilized for obtaining data on the present problem. Primary sources included statements made by land owners of Cooke County, oil operators, drillers, refinery personnel, business men, civic leaders, and the superintendents of schools, both in Gainesville, Texas, and in Cooke County. Secondary sources included newspapers, oil publications, and books on geology and the oil industry. "-- leaf vi.

La tendance sur le marché mondial du raffinage est à la fermeture ou aux réductions de capacités en Europe et en Amérique du Nord pendant que les nouveaux pays consommateurs, comme le sont certains pays producteurs, développent leur industrie. Depuis quelques années, les pays producteurs de pétrole ont annoncé la construction de "mega-projets" de raffinage et de pétrochimie de base. La question de la localisation des raffineries a été maintes fois posée depuis les années 1970 et plusieurs courants de la littérature proposent des éléments d'analyse selon les conditions économiques et politiques des pays. L'objectif de cette thèse est de comprendre les enjeux et les limites de l'intégration verticale des pays producteurs dans l'aval pétrolier, compte tenu des évolutions et perspectives sur l'offre de brut, la localisation de la demande et la mise en place accrue de politiques environnementales. Une analyse empirique des caractéristiques pétrolières et macroéconomiques des pays producteurs de pétrole permet d'identifier dans quel cadre théorique d'investissement les projets annoncés s'inscrivent. La revue de littérature permet de comprendre l'intégration dans l'aval, mais le développement de certains projets est plus difficile à expliquer. De ces analyses théoriques et empiriques, une typologie des pays producteurs est proposée selon leurs stratégies d'investissement. Par ailleurs, afin de mieux comprendre les marchés auxquels s'adressent ces nouveaux projets, une analyse économétrique des prix des produits pétroliers sur les marchés mondiaux majeurs est menée. Si la relation entre les prix des produits raffinés et le pétrole brut est significative, conformément à la littérature, la hiérarchie des prix entre les produits traduit une évolution de la demande. Une analyse de portefeuille est développée pour identifier les choix industriels efficaces qu'un pays producteur peut envisager pour assurer son développement économique en maîtrisant l'exposition aux risque de variation de ses revenus. Avec l'augmentation des enjeux industriels et financiers associés à ces nouvelles raffineries, la coopération des pays producteurs avec des Majors internationales permet de partager le risque et de répondre à leurs enjeux respectifs de développement économique. Chacune des parties maîtrise, en effet, certains facteurs de production essentiels à la réussite d'un projet qui, réunis, augmentent la valeur globale du projet. / On the whole, the refining industry in North America and Europe is reduced as new consuming countries, like producing countries, are developing their industry. In the past years 'mega-projects' in refining and basic petrochemicals have been announced by petroleum producing countries. Since the 1970s the question of location is repeatedly asked and authors have presented elements to analyze its implementation in different economical and political contexts. This thesis intends to review the incentives and limits to vertical integration by the producing countries, given the current evolutions and future prospects for supply, location of demand and increasing environmental regulation. An empirical analysis of the petroleum and macro economical conditions in producing countries enables the positioning of current projects in the theoretical context. The literature review helps understand current developments, but some projects cannot as easily be explained. Based these theoretical and empirical analyses, a typology of petroleum producers is built according to their refinery investment strategies. Moreover in order to understand the opportunities for refiners on the world markets an econometric analysis of world refined oil prices is undertaken. The strong correlation to crude oil price is confirmed, as in historical literature, but with different hierarchies between products explained by evolution of demand. Based on the observations of petroleum countries and their opportunities on world markets, a portfolio analysis is developed to identify the efficient industrial choices a producing country may proceed with in order to ensure the local development while containing risk on variations of revenue. Because the industrial and financial stakes of these refining projects are greater than before and they represent a lion's share of the future offer in refining, joint cooperation of producing countries with International Oil Companies enable a share of risk while also benefiting both players in their development objectives. Indeed each party detains different factors of production, essential for the success of a refining project that, brought together, increase the global value of the project

Scheduling refinery operation promises a big cut in logistics cost, maximizes efficiency, organizes allocation of material and resources, and ensures that production meets targets set by planning team. Obtaining accurate and reliable schedules for execution in refinery plants under different scenarios has been a serious challenge. This research was undertaken with the aim to develop robust methodologies and solution procedures to address refinery scheduling problems with uncertainties in process parameters. The research goal was achieved by first developing a methodology for short-term crude oil unloading and transfer, as an extension to a scheduling model reported by Lee et al. (1996). The extended model considers real life technical issues not captured in the original model and has shown to be more reliable through case studies. Uncertainties due to disruptive events and low inventory at the end of scheduling horizon were addressed. With the extended model, crude oil scheduling problem was formulated under receding horizon control framework to address demand uncertainty. This work proposed a strategy called fixed end horizon whose efficiency in terms of performance was investigated and found out to be better in comparison with an existing approach. In the main refinery production area, a novel scheduling model was developed. A large scale refinery problem was used as a case study to test the model with scheduling horizon discretized into a number of time periods of variable length. An equivalent formulation with equal interval lengths was also presented and compared with the variable length formulation. The results obtained clearly show the advantage of using variable timing. A methodology under self-optimizing control (SOC) framework was then developed to address uncertainty in problems involving mixed integer formulation. Through case study and scenarios, the approach has proven to be efficient in dealing with uncertainty in crude oil composition.

[pt] Este trabalho tem como objetivo realizar um estudo de modelagem dos processos e identificação das melhores práticas utilizadas nas refinarias da empresa Sigma sugerindo adaptações e melhorias nos processos da Transferência e Estocagem. A pesquisa apresenta a construção do Modelo de Referência de alto desempenho para a Transferência e Estocagem bem como sua implementação para a empresa em estudo, focando um modelo padronizado que contenha as boas práticas defendidas pela organização e aprovadas por todas as partes interessadas. / [en] This dissertation aims to develop a study of processes modelling and the identification of the best practices held by the oil refineries of Sigma Co. in order to analyze the performance of their activities and suggesting adaptations and improvements in Oil Transfer and Stockpiling processes. This work presents the high performance reference model construction for Oil Transfer and Stockpiling and its implementation for use in the case studied company, focusing a standard model which contains the whole practices supported by the organization and the sponsors departments.

O hidrogênio molecular (H2) é um gás muito útil nas indústrias químicas e petroquímicas por conta de sua facilidade de reação com outros elementos químicos. Nas refinarias é o principal insumo no processo de remoção do enxofre de diversos combustíveis como a gasolina e óleo diesel, tendo sua demanda aumentada por conta de novas legislações ambientalmente mais restritivas. O hidrogênio é normalmente encontrado na natureza associado a outros elementos químicos, como a água ou os hidrocarbonetos, sendo necessária a aplicação de processos específicos para sua obtenção. Considerada a rota mais econômica para a produção de hidrogênio, o processo de reforma a vapor do gás natural é avaliado pela aplicação da metodologia de análise exergética e termoeconômica, a fim de determinar a eficiência exergética do processo e o custo de produção do hidrogênio. Este custo de produção é muito sensível ao custo do gás natural, fato que pode prejudicar a competitividade desta rota de produção e, consequentemente, abrir a possibilidade de investir na produção de hidrogênio através de tecnologias alternativas. A unidade de geração de hidrogênio estudada está presente em uma das refinarias da Petrobras e sua produção destina-se à remoção do enxofre presente no óleo diesel. Uma planta síntese do processo foi elaborada e as eficiências exergéticas dos componentes foram determinadas. Em seguida, foi realizada uma análise econômica para determinar o custo de construção, operação e manutenção da planta. Com base nos resultados obtidos, aplicou-se a metodologia de análise termoeconômica para determinar o custo de produção de hidrogênio. Dois tipos de custo foram determinados, o custo atual (ou atualizado) de produção, que indica o custo corrente (2010) do produto, e o custo nivelado, que leva em consideração a produção total prevista ao longo vida útil da planta. Para um custo de gás natural igual a 9,11 US$/GJ, o custo de produção do hidrogênio em base exergética foi igual a 17,36 US$/GJ (2.093,13 US$/t) para o valor atual e 25,35 US$/GJ (3.056,97 US$/t) para o valor nivelado. Por fim, estes valores são comparados com outros custos de produção de hidrogênio presentes na literatura. / Pure hydrogen (H2) is an useful gas in chemical and petrochemical industries because it reacts easily with several other elements. On refineries, hydrogen is used to sequestrate sulphur from diesel and gasoline. Emission restrictions regard to fossil fuels are rising the world hydrogen demands. In spite of its abundance, hydrogen is normally found associated with other chemical species like water or hidrocarbons like methane or butane. Some especific processes are required to obtain pure hydrogen. Considered the most economic production route, the natural gas reforming process is analyzed by exergetic and thermoeconomic methods in order to determine the efficiencies and the hydrogen production cost. The hydrogen production cost is very sensitive to the cost of natural gas, which has suffered constant increases due to rising demand. This fact opens the possibility of using technologies that were previously considered economically unviable. The hydrogen unit studied was constructed in one of the Petrobras refineries, and the hydrogen produced is for the removal of sulfur in diesel oil. Based on project documents exergetic efficiencies of each component were determined. After that, an economic analysis was conducted in order to determine the construction, operation and maintenance costs of the whole plant. Two types of cost were determined, the actual cost production, which indicates the current cost product (2010), and the levelized cost, which takes into account the total production over life of the plant. Considering a natural gas cost equal to 9.11 US$/GJ, it was obtained an actual hydrogen production cost of 17.36 US$/GJ (2,093.13 US$/t) and a levelized cost of 25.35 US$/GJ (3,056.97 $/t). These values were compared with some hydrogen production costs presents on scientific papers and related references.