Silicon-containing species in used lube oil re-refining

Nowadays, the re-refining of the used lube oils has gained worldwide a lot of attention due to the necessity for added environmental protection and increasingly stringent environmental legislation. One of the parameters determining the quality of the produced base oils is the composition of feedstock. Estimation of the chemical composition of the used oil collected from several European locations showed that the hydrocarbon structure of the motor oil is changed insignificantly during its operation and the major part of the changes is accounted for with depleted oil additives. In the lube oil re-refining industry silicon, coming mainly from antifoaming agents, is recognized to be a contaminant generating undesired solid deposits in various locations in the re-refining units. In this thesis, a particular attention was paid to the mechanism of solid product formation during the alkali treatment process of silicon-containing used lube oils. The transformations of a model siloxane, tetramethyldisiloxane (TMDS), were studied in a batch reactor at industrially relevant alkali treatment conditions (low temperature, short reaction time) using different alkali agents. The reaction mechanism involving solid alkali metal silanolates was proposed. The experimental data obtained demonstrated that the solids were dominant products at low temperature and short reaction time. The liquid products in the low temperature reactions were represented mainly by linear siloxanes. The prolongation of reaction time resulted in reduction of solids, whereas both temperature and time increase led to dominance of cyclic products in the reaction mixture. Experiments with the varied reaction time demonstrated that the concentration of cyclic trimer being the dominant in the beginning of the reaction diminished with time, whereas the cyclic tetramer tended to increase. Experiments with lower sodium hydroxide concentration showed the same effect. In addition, a decrease of alkali agent concentration in the initial reaction mixture accelerated TMDS transformation reactions resulting in solely liquid cyclic siloxanes yields. Comparison of sodium and potassium hydroxides applied as an alkali agent demonstrated that potassium hydroxide was more efficient, since the activation energy in KOH presence was almost 2-fold lower than that for sodium hydroxide containing reaction mixture. Application of potassium hydroxide for TMDS transformation at 100° C with 3 hours reaction time resulted in 20 % decrease of solid yields compared to NaOH-containing mixture. Moreover, TMDS transformations in the presence of sodium silanolate applied as an alkali agent led to formation of only liquid products without formation of the undesired solids. On the basis of experimental data and the proposed reaction mechanism, a kinetic model was developed, which provided a satisfactory description of the experimental results. Suitability of the selected siloxane as a relevant model of industrial silicon-containing compounds was verified by investigation of the commercially available antifoam agent in base-catalyzed conditions.

Käytetyn voiteluöljyn regenerointilaitoksen prosessivesien karakterisointi

Käytetyn voiteluöljyn regeneroinnissa muodostuu prosessivettä useista lähteistä. Tehokas päästöjenhallinta on yksi tärkeimmistä tavoitteista regenerointilaitoksen operoinnissa ja sen takia sitä tulee kehittää jatkuvasti entistä paremmaksi. Tavoitteisiin pääsemiseksi on oleellista tunnistaa vesienkäsittelyprosessin laadullinen massatase ja laadunvaihtelut ajotilanteiden mukaan. Työssä tutkitaan ja analysoidaan veden sisältämiä epäpuhtauksia sekä kirjallisuuslähteiden perusteella, että standardimenetelmillä ja modifioiduilla menetelmillä, joilla on akkreditointi. Analyysituloksista muodostetaan laadullinen massatase, josta nähdään epäpuhtauksien ja niitä kuvaavien parametrien kuormitukset kussakin prosessivesivirrassa. Tulosten perusteella arvioidaan nykyisen vesienkäsittelyn tehokkuutta, sen säätömahdollisuuksia ja kehitystarvetta. Tarkastelun ulkopuolelle kuitenkin jätetään vesienkäsittelystä ulosjohdettavan prosessiveden puhdistuslaitos. Tutkimusten perusteella regenerointilaitoksessa muodostuvien prosessivesien epäpuhtaudet koostuvat öljystä, BTEX-yhdisteistä, fenoliyhdisteistä, liuottimista, polttoaineiden ja voiteluöljyjen lisäaineista, typpi- ja rikkiyhdisteistä, metalliyhdisteistä sekä kiintoaineesta. Öljy jakautuu kevyisiin (C5-C10), keskiraskaisiin (C10-21) ja raskaisiin (C21-40) jakeisiin. Vesienkäsittelyssä suurin osa öljystä ja epäpuhtauksista saadaan erottumaan vedestä, jolloin puhdistuslaitokselle päätyy jäämäpitoisuudet öljyä, haihtuvia yhdisteitä sekä muita epäpuhtauksia. Puhdistuslaitosta kuormittavat eniten liuenneet orgaaniset yhdisteet sekä korkeaa kemiallista hapenkulutusta aiheuttavat epäorgaaniset yhdisteet (suolat), joiden erottamista prosessivesistä on syytä tulevaisuudessa kehittää.

Radio-frequency-based measurement methods for bearing current analysis in induction motors

The most common reason for a low-voltage induction motor breakdown is a bearing failure. Along with the increasing popularity of modern frequency converters, bearing failures have become the most important motor fault type. Conditions in which bearing currents are likely to occur are generated as a side effect of fast du/dt switching transients. Once present, different types of bearing currents can accelerate the mechanical wear of bearings by causing deformation of metal parts in the bearing and degradation of the lubricating oil properties.The bearing current phenomena are well known, and several bearing current measurement and mitigation methods have been proposed. Nevertheless, in order to develop more feasible methods to measure and mitigate bearing currents, better knowledge of the phenomena is required. When mechanical wear is caused by bearing currents, the resulting aging impact has to be monitored and dealt with. Moreover, because of the stepwise aging mechanism, periodically executed condition monitoring measurements have been found ineffective. Thus, there is a need for feasible bearing current measurement methods that can be applied in parallel with the normal operation of series production drive systems. In order to reach the objectives of feasibility and applicability, nonintrusive measurement methods are preferred. In this doctoral dissertation, the characteristics and conditions of bearings that are related to the occurrence of different kinds of bearing currents are studied. Further, the study introduces some nonintrusive radio-frequency-signal-based approaches to detect and measure parameters that are associated with the accelerated bearing wear caused by bearing currents.

Improvement of pyrolysis oil quality by scrubbing

Diplomityössä tutkittiin kuuman pyrolyysihöyryn puhdistamista haisevista ja kevyistä haihtuvista yhdisteistä. Työn kirjallisuusosassa selvitettiin pyrolyysiöljyn kannattavuutta uusiutuvana energialähteenä. Lisäksi eri pesurityyppejä tarkasteltiin ja ja vertailtiin. Työn kokeellisessa osassa käytettiin kahta erilaista koelaitteistoa. Tuotteen talteenotossa vertailtiin reaktorilämpötilan ja raaka-aineen kosteuden vaikutusta pyrolyysisaantoihin. Komponenttien talteenotossa tutkittiin epästabiilien ja pistävän hajuisten yhdisteiden poistamista kuumasta pyrolyysihöyrystä. Raaka-aineena käytettiin kuusen metsätäh-dehaketta, joka sisältää runsaasti neulasia ja kaarnaa. Kokeet toteutettiin lämpötila-alueella 460 - 520 °C. Koelaitteistot koostuivat kaasun (N2) syöttöjärjestelmään kytketystä kuumasta ja kyl-mästä puolesta. Tuotteen talteenotossa kuuma pyrolyysihöyry jäähdytettiin ja otettiin talteen. Komponenttien talteenotossa tuote kerättiin suodattimelle ja metyleeniklo-ridiloukkuun. Tuotteiden koostumukset analysoitiin kaasukromatokrafilla. Korkeimmat orgaaniset saannot saatiin 480 °C reaktorilämpötilalla ja 8-9 p-% raaka-ainekosteudella. Pyrolyysiveden määrä putosi raaka-aineen kosteutta nostettaessa. Eri reaktorilämpötiloilla ja raaka-ainekosteuksilla ei ollut vaikutusta hiiltosaantoihin. Kaasusaannot (pääosin CO2, CO ja hiilivedyt) olivat noin 10 p-%. Komponenttien talteenotossa suodatin tukkeutui matalissa (< 250 °C) lämpötiloissa. Suodattimelle jäänyt materiaali oli pääosin neulasista ja kaarnasta peräisin olevia uuteaineita (pääosin hartsi- rasvahappoja) ja sokereita. Korkeimmissa lämpötiloissa (> 250 °C) uuteaineet läpäisivät suodattimen paremmin. 250 ja 300 °C:n lämpötiloissa suuri määrä lyhytketjuisia helposti haihtuvia epästabiileja ja haisevia yhdisteitä (ketoneja, furaani- ja furfuraalijohdannaisia jne.) jäi metyleenikloridi- ja metanoliloukkuihin.

Advanced welding technologies used for arctic metal structures

Rapid depletion of easy-to-access fossil fuel, predominantly, oil and gas resources has now necessitated increase in need to develop new oil and gas sources in ever more remote and hostile environments. This is necessary in order to explore more oil and gas resources to meet rapidly rising long-term energy demand in the world, both at present and in the nearest future. Arctic is one of these harsh environments, where enormous oil and gas resources are available, containing about 20% of the world total oil and gas, but the environmental conditions are very harsh and hostile. However, virtually all the facilities required for the exploration and development of this new energy source are constructed with metals as well as their alloys and are predominantly joined together by welding processes and technologies. Meanwhile, due to entirely different environment from the usual moderate temperate region, conventional welding technologies, common metals and their alloys cannot be applied as this Arctic environment demand metals structures with very high toughness and strength properties under extremely low temperature. This is due to the fact that metals transit from ductility to brittleness as the temperature moves toward extreme negative values. Hence, this research work investigates and presents the advanced welding technologies applicable to Arctic metal structures which can give satisfactory weldments under active Arctic service conditions. .

IT Investment Portfolio Management Over Joint Ventures: Case Study in a Multinational Oil & Gas Company

With information technology (IT) playing an increasing important role in driving the business, the value of IT investment is often challenged because not all of those investment decisions are made in a reasonable way or aligned with business strategies. IT investment portfolio management (PfM) is an effective way to prioritize and select the right IT projects to invest in, by taking all the project proposals into consideration as a whole, based on their business value, risks, costs, and interrelationships. There are different decision models to prioritise projects, and the Analytic Hierarchy Process (AHP) is one of the most commonly-used methods and is discussed in this master thesis. At the same time, there are IT projects on different levels for a multinational company, from global to local. For instance, many of them are probably proposed by joint ventures on local level. In the oil & gas industry, joint ventures are often formed especially in the area of the upstream (exploration & production). How to involve those projects into the IT investment PfM approach of the parent company is a challenge, because the parent company cannot make the decisions on its own. It needs to prioritize all projects in an adequate way, communicate with JVs and influence them. Also, different control levels on JVs need to be considered. This paper hence attempts to introduce a tailored approach of IT investment PfM for a multinational oil & gas company to address the issues around JVs.

Feasibility studies of the weldability of structural steels used in the offshore environment

The rising demand for oil and gas has made it very necessary for the oil and gas industries to explore the offshore. There is a huge resources which is available in the offshore. The search for oil and gas is faced with greater challenges because of the nature of the marine environment as it poses difficult and harsh conditions for the construction of offshore structures. The major problem of the construction of offshore structure is the ability to produce a sound weld that gives the whole structure the structural integrity needed to withstand the harsh environmental conditions. This research work presents the performance of typical offshore steels with improved weldability. The ability of reducing the carbon content of thermo-mechanically rolled steels down to 0.08% makes it possible to achieve good weldability, toughness and strength for high strength steels used in offshore applications. Importantly, the ideal welding procedure should be strictly followed as recommended. The fabrication process is as important as the welding procedure in achieving a sound weld which is free of weld defects such as hydrogen induced cracking, lamellar tearing and solidification cracking. This research work also considers the corrosion as it affects offshore structure and necessary measures to mitigate the problem caused by corrosion.

Optimization of strength and toughness on the effect of the weldable high strength steels (hss) used in offshore structures

Optimization of high strength and toughness combination on the effect of weldability is very vital to be considered in offshore oil and gas industries. Having a balanced and improved high strength and toughness is very much recommended in offshore structures for an effective production and viable exploration of hydrocarbons. This thesis aims to investigate the possibilities to improve the toughness of high strength steel. High carbon contents induce hardness and needs to be reduced for increasing toughness. The rare combination of high strength with high toughness possibilities was examined by determining the following toughening mechanism of: Heat treatment and optimal microstructure, Thermomechanical processing, Effect of welding parameters on toughness and weldability of steel. The implementation of weldability of steels to attain high toughness for high strength in offshore structures is mostly in shipbuilding, offshore platforms, and pipelines for high operating pressures. As a result, the toughening mechanisms suggested have benefits to the aims of the effect of high strength to high toughness of steel for efficiency, production and cost reduction.

Managing innovation in oil and gas companies: A proposed framework for the management of innovation at Ecopetrol S.A.

Actually, the term innovation seems to be one of the most used in any kind of business practices. However, in order to get value from it, companies need to define a systematic and structured way to manage innovation. This process can be difficult and very risky since it is associated with the development of firm´s capabilities which involves human and technical challenges according to the context of a firm. Additionally, it seems not to exist a magic formula to manage innovation and what may work in a company may not work in another, even though in the same type of industry. In this sense, the purpose of this research is to identify how the oil and gas companies can manage innovation and what are the main elements, their interrelations and structure, required for managing innovation effectively in this critical sector for the world economy. The study follows a holistic single case study in a National Oil Company (NOC) of a developing country to explore how innovation performs in the industry, what are the main elements regarding innovation management and their interactions according to the nature of the industry. Contributory literature and qualitative data from the case study company (with the use of non-standardized interviews) is collected and analyzed. The research confirms the relevance and importance of the definition and implementation of an innovation framework in order to ensure the generation of value and organize as well as guide the efforts in innovation done by a firm. In this way based on the theoretical background, research´s findings, and in the company´s innovation environment and conditions, a framework for managing innovation at the case study company is suggested. This study is one of the few, if not only one, that has reviewed the way as oil and gas companies manage innovation and its practical implementation in a company from a developing country. Both researchers and practitioners will get a photograph of understanding innovation management in the oil and gas industry and its growing necessity in the business world. Some issues have been highlighted, so that future study can be focused in those directions. In fact, even though research on innovation management has significantly grown, there are still many issues that need to be addressed to get insight about managing innovation in various contexts and industries. Studies are mostly performed in the context of large firms and in developed countries, so then research in the context of developing countries is still almost an untouched area, especially in the oil and gas industry. Finally, from the research it seems crucial to explore the effect of some innovation-related variables such as: open innovation in third world economies and in state-own companies; the impact of mergers and acquisitions in innovation performance in oil and gas companies; value measurement in the first stages of the innovation process; and, development of innovation capabilities in companies from developing nations.

Blackcurrant seed oil for prevention of atopic dermatitis

One hypothesis for the increased incidence of atopic diseases has been that it is associated with changing dietary habits, especially the changed intake of essential fatty acids (EFAs). The metabolism of EFAs produces eiconasoids, prostaglandins and leukotrienes, which are essential to organs and play a major role in regulation of inflammation and immune response. In some studies persons with atopic dermatitis have been found to have reduced levels of EFAs. The first year of infancy as well as the foetal period are crucial for the development of atopic immune response. The composition of blackcurrant seed oil (BCSO) corresponds to the recommended ratio of EFAs n-3 and n-6 in the diet (1/3-1/4) and as a dietary supplement could, even in small doses, modify the unbalance of EFAs in an efficient way. The purpose of this study was to find out whether atopic allergies can be prevented by supplementing the diet of pregnant mothers with blackcurrant seed oil and whether it could affect the immunological balance of a child. We also sought to find out whether a blackcurrant seed oil supplementation can affect the composition of breast milk to suppress the T helper 2 lymphocyte (Th2) responses in infants. 313 pregnant mothers were randomly assigned to receive BCSO (n=151) or olive oil as placebo (n=162). Supplementation was started at the 8th to 16th weeks of pregnancy, 6 capsules per day (dose of 3 g), and continued until the cessation of breastfeeding. It was thereafter followed by direct supplementation to infants of 1 ml (1 g) of oil per day until the age of two years. Atopic dermatitis and its severity (SCORAD index) were evaluated, serum total IgE was measured and skin prick tests were performed at the age of 3, 12 and 24 months. Peripheral blood mononuclear cell (PBMC) samples were taken at the age of 3 and 12 months and breast milk samples were collected during the first 3 months of breastfeeding. Parental atopy was common (81.7%) in the studied infants, making them infants with increased atopy risk. There was a significantly lower prevalence of atopic dermatitis in the BCSO group (33%) than in the olive oil group (47%) at the age of 12 months. Also, SCORAD was lower in the BCSO group than in the olive oil group. Dietary intervention with BCSO had immunomodulatory effects on breast milk, inducing cytokine production from Th2 to Th1 immunodeviation. It decreased the level of IL-4 and elevated the level of IFN-γ. BCSO intervention did not affect cytokines in the children’s PBMC. However, children of smoking parents in the combined BCSO and olive oil group had significantly elevated levels of Th2 type cytokines IL-4, IL-5 and the proinflammator cytokine TNF. Dietary supplementation with BCSO is safe. It is well tolerated and transiently reduces the prevalence of atopic dermatitis at the age of 12 months. It can possibly become a potential tool in prevention of atopic symptoms when used at the early stages of life.

Membrane development for oil contaminated water treatments

The aim of this Master’s thesis study was to develop a membrane for oil contaminated water treatments. Oily wastewaters are a big problem to environment and therefore it is important to find an efficient method for their treatment. There are several treatment methods, but one of the most promising methods is membrane filtration. In the theoretical part of this study the membrane technology and polymeric membrane preparation with phase inversion and membrane modification methods was discussed. It was also told about the most important properties of the membranes. Oily waters, their treatment methods and oily wastewater sources were discussed more specifically. In the experimental part membranes from cellulose acetate were prepared and membranes were modified with two different methods. Modification methods were surface modification and polymer mixing. The modification purpose was to make membranes more hydrophilic and increase surface charge, which can reduce fouling. Membranes were characterized by determining zeta potential, contact angle, oil retention, pure water permeability, pressure-normalized flux and fouling. It were used both synthetic and real spent oil-water emulsion in membrane filtration. Surface modification resulted membranes, which had better properties than unmodified membrane. The amount of substance used in surface modification affected a lot to membrane properties, so it would be necessary to try different amounts of substance to develop the best membrane for oil-water emulsion treatment.

Flow in porous media of oil-water systems

Fluid flow behaviour in porous media is a conundrum. Therefore, this research is focused on filtration-volumetric characterisation of fractured-carbonate sediments, coupled with their proper simulation. For this reason, at laboratory rock properties such as pore volume, permeability and porosity are measured, later phase permeabilities and oil recovery in function of flow rate are assessed. Furthermore, the rheological properties of three oils are measured and analysed. Finally based on rock and fluid properties, a model using COMSOL Multiphysics is built in order to compare the experimental and simulated results. The rock analyses show linear relation between flow rate and differential pressure, from which phase permeabilities and pressure gradient are determined, eventually the oil recovery under low and high flow rate is established. In addition, the oils reveal thixotropic properties as well as non-Newtonian behaviour described by Bingham model, consequently Carreau viscosity model for the used oil is given. Given these points, the model for oil and water is built in COMSOL Multiphysics, whereupon successfully the reciprocity between experimental and simulated results is analysed and compared. Finally, a two-phase displacement model is elaborated.

Preparation and Investigation of Bio-coal Mixture Fuels Used in Large Diesel Engines

Coal slurry was of vital interest during the last century due to its potential as an alternative fuel where liquid fuels were necessary. Recently, environmental impacts of the traditional fuels, similarities of bio-coal to that of coal, and huge bio-coal supply has attracted the attention to prepare bio-coal slurries as a new fuel. Rudolf Diesel who invented the diesel engine on 1895 was of the opinion that diesel engines are capable to use different kinds of fuels due to the special design. He tried some kind of vegetable oil to operate on his IC engine. Recently, due to high energy density and more environmentally friendly fuel, researchers believe that bio-coal slurries could act as a new alternative fuel in large diesel engines. Loads of research on different kinds of bio-coal slurry were done by the other researchers worldwide and a lot of progress to boost slurry’s quality were achieved recently. The present study aims to achieve the ideal condition of different factors affecting on the quality of bio-coal slurry. One charcoal sample and two kinds of torrefied wood were used to investigate and compare the reaction of various factors. The results show a great gap between the quality of slurries made of different samples and more researches are necessary to fully understand the impact of the different parameter and improving the quality.