Metal additive manufacturing of internal flow channels with powder bed fusion processes

This thesis studies the advantages, disadvantages and possibilities of additive manufacturing in making components with internal flow channels. These include hydraulic components, components with cooling channels and heat exchangers. Processes studied in this work are selective laser sintering and selective laser melting of metallic materials. The basic principles of processes and parameters involved in the process are presented and different possibilities of internal channel manufacturing and flow improvement are introduced

Three-dimensional modeling of biomass fuel flow in a circulating fluidized bed furnace

The reduction of greenhouse gas emissions in the European Union promotes the combustion of biomass rather than fossil fuels in energy production. Circulating fluidized bed (CFB) combustion offers a simple, flexible and efficient way to utilize untreated biomass in a large scale. CFB furnaces are modeled in order to understand their operation better and to help in the design of new furnaces. Therefore, physically accurate models are needed to describe the heavily coupled multiphase flow, reactions and heat transfer inside the furnace. This thesis presents a new model for the fuel flow inside the CFB furnace, which acknowledges the physical properties of the fuel and the multiphase flow phenomena inside the furnace. This model is applied with special interest in the firing of untreated biomass. An experimental method is utilized to characterize gas-fuel drag force relations. This characteristic drag force approach is developed into a gas-fuel drag force model suitable for irregular, non-spherical biomass particles and applied together with the new fuel flow model in the modeling of a large-scale CFB furnace. The model results are physically valid and achieve very good correspondence with the measurement results from large-scale CFB furnace firing biomass. With the methods and models presented in this work, the fuel flow field inside a circulating fluidized bed furnace can be modeled with better accuracy and more efficiently than in previous studies with a three-dimensional holistic model frame.

Drag reduction by polyethylene glycol in the tail arterial bed of normotensive and hypertensive rats

This study was designed to evaluate the effect of drag reducer polymers (DRP) on arteries from normotensive (Wistar) and spontaneously hypertensive rats (SHR). Polyethylene glycol (PEG 4000 at 5000 ppm) was perfused in the tail arterial bed with (E+) and without endothelium (E-) from male, adult Wistar (N = 14) and SHR (N = 13) animals under basal conditions (constant flow at 2.5 mL/min). In these preparations, flow-pressure curves (1.5 to 10 mL/min) were constructed before and 1 h after PEG 4000 perfusion. Afterwards, the tail arterial bed was fixed and the internal diameters of the arteries were then measured by microscopy and drag reduction was assessed based on the values of wall shear stress (WSS) by computational simulation. In Wistar and SHR groups, perfusion of PEG 4000 significantly reduced pulsatile pressure (Wistar/E+: 17.5 ± 2.8; SHR/E+: 16.3 ± 2.7%), WSS (Wistar/E+: 36; SHR/E+: 40%) and the flow-pressure response. The E- reduced the effects of PEG 4000 on arteries from both groups, suggesting that endothelial damage decreased the effect of PEG 4000 as a DRP. Moreover, the effects of PEG 4000 were more pronounced in the tail arterial bed from SHR compared to Wistar rats. In conclusion, these data demonstrated for the first time that PEG 4000 was more effective in reducing the pressure-flow response as well as WSS in the tail arterial bed of hypertensive than of normotensive rats and these effects were amplified by, but not dependent on, endothelial integrity. Thus, these results show an additional mechanism of action of this polymer besides its mechanical effect through the release and/or bioavailability of endothelial factors.

Hormonal therapy with estradiol and drospirenone improves endothelium-dependent vasodilation in the coronary bed of ovariectomized spontaneously hypertensive rats

Drospirenone (DRSP) is a progestin with anti-aldosterone properties and it reduces blood pressure in hypertensive women. However, the effects of DRSP on endothelium-dependent coronary vasodilation have not been evaluated. This study investigated the effects of combined therapy with estrogen (E2) and DRSP on endothelium-dependent vasodilation of the coronary bed of ovariectomized (OVX) spontaneously hypertensive rats. Female spontaneously hypertensive rats (n=87) at 12 weeks of age were randomly divided into sham operated (Sham), OVX, OVX treated with E2 (E2), and OVX treated with E2 and DRSP (E2+DRSP) groups. Hemodynamic parameters were directly evaluated by catheter insertion into the femoral artery. Endothelium-dependent vasodilation in response to bradykinin in the coronary arterial bed was assessed using isolated hearts according to a modified Langendorff method. Coronary protein expression of endothelial nitric oxide synthase and estrogen receptor alpha (ER-α) was assessed by Western blotting. Histological slices of coronary arteries were stained with hematoxylin and eosin, and morphometric parameters were analyzed. Oxidative stress was assessed in situ by dihydroethidium fluorescence. Ovariectomy increased systolic blood pressure, which was only prevented by E2+DRSP treatment. Estrogen deficiency caused endothelial dysfunction, which was prevented by both treatments. However, the vasodilator response in the E2+DRSP group was significantly higher at the three highest concentrations compared with the OVX group. Reduced ER-α expression in OVX rats was restored by both treatments. Morphometric parameters and oxidative stress were augmented by OVX and reduced by E2 and E2+DRSP treatments. Hormonal therapy with E2 and DRSP may be an important therapeutic option in the prevention of coronary heart disease in hypertensive post-menopausal women.

Weldability of powder bed fusion fabricated stainless steel 316L sheets to cold rolled sheet metal

Weldability of powder bed fusion (PBF) fabricated components has come to discussion in past two years due to resent developments in the PBF technology and limited size of the machines used in the fabrication process. This study concentrated on effects of energy input of welding on mechanical properties and microstructural features of welds between PBF fabricated stainless steel 316L sheets and cold rolled sheet metal of same composition by the means of destructive testing and microscopic analysis. Optical fiber diameter, laser power and welding speed were varied during the experiments that were executed following one variable at a time (OVAT) method. One of the problems of welded PBF fabricated components has been lower elongations at break comparing to conventionally manufactured components. Decreasing energy input of the laser keyhole welding decreased elongations at break of the welded specimens. Ultimate tensile strengths were not affected significantly by the energy input of the welding, but fracturing of the specimens welded using high energy input occurred from the weld metal. Fracturing of the lower energy input welds occurred from the PBF fabricated base metal. Energy input was found to be critical factor for mechanical properties of the welds. Multioriented grain growth and formation of neck at fusion zone boundary on the cold rolled side of the weld was detected and suspected to be result from weld pool flows caused by differences in molten weld pool behaviour between the PBF fabricated and cold rolled sides of the welds.

Introducing the concept of critical Fo in batch heat processing

The determination of the sterilization value for low acid foods in retorts includes a critical evaluation of the factory's facilities and utilities, validation of the heat processing equipment (by heat distribution assays), and finally heat penetration assays with the product. The intensity of the heat process applied to the food can be expressed by the Fo value (sterilization value, in minutes, at a reference temperature of 121.1 °C, and a thermal index, z, of 10 °C, for Clostridium botulinum spores). For safety reasons, the lowest value for Fo is frequently adopted, being obtained in heat penetration assays as indicative of the minimum process intensity applied. This lowest Fo value should always be higher than the minimum Fo recommended for the food in question. However, the use of the Fo value for the coldest can fail to statistically explain all the practical occurrences in food heat treatment processes. Thus, as a result of intense experimental work, we aimed to develop a new focus to determine the lowest Fo value, which we renamed the critical Fo. The critical Fo is based on a statistical model for the interpretation of the results of heat penetration assays in packages, and it depends not only on the Fo values found at the coldest point of the package and the coldest point of the equipment, but also on the size of the batch of packages processed in the retort, the total processing time in the retort, and the time between CIPs of the retort. In the present study, we tried to explore the results of physical measurements used in the validation of food heat processes. Three examples of calculations were prepared to illustrate the methodology developed and to introduce the concept of critical Fo for the processing of canned food.

Influence of the use of rice bran extract as a source of nutrients on xylitol production

Xylose-to-xylitol bioconversion using 2.5 or 10% (v/v) rice bran extract was performed to verify the influence of this source of nutrients on Candida guilliermondii metabolism. Semisynthetic medium (SM) and sugarcane bagasse hemicellulosic hydrolysate detoxified with ion-exchange resins (HIE) or with alteration in pH combined with adsorption onto activated charcoal (HAC) were fermented in 125 mL Erlenmeyer flasks at 30 ºC and 200 rpm for 72 hours. Activated charcoal supplemented with 2.5% (v/v) rice bran extract was fermented by C. guilliermondii in a MULTIGEN stirred tank reactor using pH 5.0 and 22.9/hour oxygen transfer volumetric coefficient. Higher values of xylitol productivity (0.70, 0.71, and 0.62 g.Lh-1) and xylose-to-xylitol conversion yield (0.71, 0.69, and 0.63 g.g-1) were obtained with 2.5% (v/v) rice bran in semisynthetic medium, ion-exchange resins, and activated charcoal, respectively. Moreover, during batch fermentation, the xylitol volumetric productivity and fermentation efficiency values obtained were 0.53 g.Lh-1 and 61.1%, respectively.

Effect of previous chilling storage on quality loss in frozen (–20 °C) sierra (Scomberomorus sierra) muscle packed with a low-density polyethylene film containing butylated hydroxytoluene

Rancidity development during frozen storage (–20 °C) of sierra fish (Scomberomorus sierra) was studied. Fillets were packed in low-density polyethylene films with and without butylated hydroxytoluene added (BHT-LDPE and LDPE respectively). Fillets stored with no package were used as control. Special attention was given to the effect of previous ice storage (0, 3, 6, 9 and 15 days) on the quality of the frozen fish. Physical (pH and texture) and chemical (peroxide value, PV and thiobarbituric acid index, TBA-i) analyses were carried out. Lipid oxidation increased with ice storage time in fish muscle without film packing, being greater than the film packed muscle (with and without antioxidant). An effect of previous ice storage time was observed on the frozen product (in all treatments). However, fish muscle with film packing containing antioxidant showed less lipid deterioration. Under the conditions applied in this study, the plastic films with antioxidant prevented the lipids oxidation during the cold handling of the sierra muscle.

Production of magnesium carbonates from serpentinites for CO2 mineral sequestration : optimisation towards industrial application

Global warming is one of the most alarming problems of this century. Initial scepticism concerning its validity is currently dwarfed by the intensification of extreme weather events whilst the gradual arising level of anthropogenic CO2 is pointed out as its main driver. Most of the greenhouse gas (GHG) emissions come from large point sources (heat and power production and industrial processes) and the continued use of fossil fuels requires quick and effective measures to meet the world’s energy demand whilst (at least) stabilizing CO2 atmospheric levels. The framework known as Carbon Capture and Storage (CCS) – or Carbon Capture Utilization and Storage (CCUS) – comprises a portfolio of technologies applicable to large‐scale GHG sources for preventing CO2 from entering the atmosphere. Amongst them, CO2 capture and mineralisation (CCM) presents the highest potential for CO2 sequestration as the predicted carbon storage capacity (as mineral carbonates) far exceeds the estimated levels of the worldwide identified fossil fuel reserves. The work presented in this thesis aims at taking a step forward to the deployment of an energy/cost effective process for simultaneous capture and storage of CO2 in the form of thermodynamically stable and environmentally friendly solid carbonates. R&D work on the process considered here began in 2007 at Åbo Akademi University in Finland. It involves the processing of magnesium silicate minerals with recyclable ammonium salts for extraction of magnesium at ambient pressure and 400‐440⁰C, followed by aqueous precipitation of magnesium in the form of hydroxide, Mg(OH)2, and finally Mg(OH)2 carbonation in a pressurised fluidized bed reactor at ~510⁰C and ~20 bar PCO2 to produce high purity MgCO3. Rock material taken from the Hitura nickel mine, Finland, and serpentinite collected from Bragança, Portugal, were tested for magnesium extraction with both ammonium sulphate and bisulphate (AS and ABS) for determination of optimal operation parameters, primarily: reaction time, reactor type and presence of moisture. Typical efficiencies range from 50 to 80% of magnesium extraction at 350‐450⁰C. In general ABS performs better than AS showing comparable efficiencies at lower temperature and reaction times. The best experimental results so far obtained include 80% magnesium extraction with ABS at 450⁰C in a laboratory scale rotary kiln and 70% Mg(OH)2 carbonation in the PFB at 500⁰C, 20 bar CO2 pressure for 15 minutes. The extraction reaction with ammonium salts is not at all selective towards magnesium. Other elements like iron, nickel, chromium, copper, etc., are also co‐extracted. Their separation, recovery and valorisation are addressed as well and found to be of great importance. The assessment of the exergetic performance of the process was carried out using Aspen Plus® software and pinch analysis technology. The choice of fluxing agent and its recovery method have a decisive sway in the performance of the process: AS is recovered by crystallisation and in general the whole process requires more exergy (2.48–5.09 GJ/tCO2sequestered) than ABS (2.48–4.47 GJ/tCO2sequestered) when ABS is recovered by thermal decomposition. However, the corrosive nature of molten ABS and operational problems inherent to thermal regeneration of ABS prohibit this route. Regeneration of ABS through addition of H2SO4 to AS (followed by crystallisation) results in an overall negative exergy balance (mainly at the expense of low grade heat) but will flood the system with sulphates. Although the ÅA route is still energy intensive, its performance is comparable to conventional CO2 capture methods using alkanolamine solvents. An energy‐neutral process is dependent on the availability and quality of nearby waste heat and economic viability might be achieved with: magnesium extraction and carbonation levels ≥ 90%, the processing of CO2‐containing flue gases (eliminating the expensive capture step) and production of marketable products.

Reducing auxiliary power of a fluid bed boiler island

The aim of this thesis is to find and analyze different methods which reduce fluid bed boilers’ auxiliary power consumption. The objective is to examine the effects and feasibility of these methods. The literature part explains how fluid bed boilers work and what are the main sources of auxiliary power consumption. Designs and operation of these equipment are presented. The literature part also discusses the basics of auxiliary power consumption reduction and introduces four low pressure drop constructions. The experimental part inspects six different methods. Effects of these methods on the auxiliary power consumption are calculated and their impacts on the operation of the boiler are modeled. Calculations show that reasonable changes can reduce fluid bed boiler’s auxiliary power consumption by 2,1-10,2 %. Biggest reductions come from lower air coefficients, smaller bed a-level pressures and lower primary/secondary air –ratios. Models showed no problems with the smaller bed a-level pressures. With the lower air coefficients and smaller primary/secondary air –ratios the models showed a significant increase in the carbon monoxide levels.

Dynamic Modelling of Circulating Fluidized Bed Plant with Gas Turbine Repowering

Increasing amount of renewable energy source based electricity production has set high load control requirements for power grid balance markets. The essential grid balance between electricity consumption and generation is currently hard to achieve economically with new-generation solutions. Therefore conventional combustion power generation will be examined in this thesis as a solution to the foregoing issue. Circulating fluidized bed (CFB) technology is known to have sufficient scale to acts as a large grid balancing unit. Although the load change rate of the CFB unit is known to be moderately high, supplementary repowering solution will be evaluated in this thesis for load change maximization. The repowering heat duty is delivered to the CFB feed water preheating section by smaller gas turbine (GT) unit. Consequently, steam extraction preheating may be decreased and large amount of the gas turbine exhaust heat may be utilized in the CFB process to reach maximum plant electrical efficiency. Earlier study of the repowering has focused on the efficiency improvements and retrofitting to maximize plant electrical output. This study however presents the CFB load change improvement possibilities achieved with supplementary GT heat. The repowering study is prefaced with literature and theory review for both of the processes to maximize accuracy of the research. Both dynamic and steady-state simulations accomplished with APROS simulation tool will be used to evaluate repowering effects to the CFB unit operation. Eventually, a conceptual level analysis is completed to compare repowered plant performance to the state-of-the-art CFB performance. Based on the performed simulations, considerably good improvements to the CFB process parameters are achieved with repowering. Consequently, the results show possibilities to higher ramp rate values achieved with repowered CFB technology. This enables better plant suitability to the grid balance markets.

A reaction engineering approach to homogeneously catalyzed glycerol hydrochlorination

The production of biodiesel through transesterification has created a surplus of glycerol on the international market. In few years, glycerol has become an inexpensive and abundant raw material, subject to numerous plausible valorisation strategies. Glycerol hydrochlorination stands out as an economically attractive alternative to the production of biobased epichlorohydrin, an important raw material for the manufacturing of epoxy resins and plasticizers. Glycerol hydrochlorination using gaseous hydrogen chloride (HCl) was studied from a reaction engineering viewpoint. Firstly, a more general and rigorous kinetic model was derived based on a consistent reaction mechanism proposed in the literature. The model was validated with experimental data reported in the literature as well as with new data of our own. Semi-batch experiments were conducted in which the influence of the stirring speed, HCl partial pressure, catalyst concentration and temperature were thoroughly analysed and discussed. Acetic acid was used as a homogeneous catalyst for the experiments. For the first time, it was demonstrated that the liquid-phase volume undergoes a significant increase due to the accumulation of HCl in the liquid phase. Novel and relevant features concerning hydrochlorination kinetics, HCl solubility and mass transfer were investigated. An extended reaction mechanism was proposed and a new kinetic model was derived. The model was tested with the experimental data by means of regression analysis, in which kinetic and mass transfer parameters were successfully estimated. A dimensionless number, called Catalyst Modulus, was proposed as a tool for corroborating the kinetic model. Reactive flash distillation experiments were conducted to check the commonly accepted hypothesis that removal of water should enhance the glycerol hydrochlorination kinetics. The performance of the reactive flash distillation experiments were compared to the semi-batch data previously obtained. An unforeseen effect was observed once the water was let to be stripped out from the liquid phase, exposing a strong correlation between the HCl liquid uptake and the presence of water in the system. Water has revealed to play an important role also in the HCl dissociation: as water was removed, the dissociation of HCl was diminished, which had a retarding effect on the reaction kinetics. In order to obtain a further insight on the influence of water on the hydrochlorination reaction, extra semi-batch experiments were conducted in which initial amounts of water and the desired product were added. This study revealed the possibility to use the desired product as an ideal “solvent” for the glycerol hydrochlorination process. A co-current bubble column was used to investigate the glycerol hydrochlorination process under continuous operation. The influence of liquid flow rate, gas flow rate, temperature and catalyst concentration on the glycerol conversion and product distribution was studied. The fluid dynamics of the system showed a remarkable behaviour, which was carefully investigated and described. Highspeed camera images and residence time distribution experiments were conducted to collect relevant information about the flow conditions inside the tube. A model based on the axial dispersion concept was proposed and confronted with the experimental data. The kinetic and solubility parameters estimated from the semi-batch experiments were successfully used in the description of mass transfer and fluid dynamics of the bubble column reactor. In light of the results brought by the present work, the glycerol hydrochlorination reaction mechanism has been finally clarified. It has been demonstrated that the reactive distillation technology may cause drawbacks to the glycerol hydrochlorination reaction rate under certain conditions. Furthermore, continuous reactor technology showed a high selectivity towards monochlorohydrins, whilst semibatch technology was demonstrated to be more efficient towards the production of dichlorohydrins. Based on the novel and revealing discoveries brought by the present work, many insightful suggestions are made towards the improvement of the production of αγ-dichlorohydrin on an industrial scale.

Control of Bubbling Fluidized Bed Conditions

The objectives of this master’s thesis were to understand the importance of bubbling fluidized bed (BFB) conditions and to find out how digital image processing and acoustic emission technology can help in monitoring the bed quality. An acoustic emission (AE) measurement system and a bottom ash camera system were evaluated in acquiring information about the bed conditions. The theory part of the study describes the fundamentals of BFB boiler and evaluates the characteristics of bubbling bed. Causes and effects of bed material coarsening are explained. The ways and methods to monitor the behaviour of BFB are determined. The study introduces the operating principles of AE technology and digital image processing. The empirical part of the study describes an experimental arrangement and results of a case study at an industrial BFB boiler. Sand consumption of the boiler was reduced by optimization of bottom ash handling and sand feeding. Furthermore, data from the AE measurement system and the bottom ash camera system was collected. The feasibility of these two systems was evaluated. The particle size of bottom ash and the changes in particle size distribution were monitored during the test period. Neither of the systems evaluated was ready to serve in bed quality control accurately or fast enough. Particle size distributions according to the bottom ash camera did not correspond to the results of manual sieving. Comprehensive interpretation of the collected AE data requires much experience. Both technologies do have potential and with more research and development they may enable acquiring reliable and real-time information about the bed conditions. This information could help to maintain disturbance-free combustion process and to optimize bottom ash handling system.

Spare Part Management of Bubbling Fluidized Bed Boiler

Energy generation industry is very capital-intensive industry. Productivity and availability requirements have increased while competition and quality requirement have increased. Maintenance has a significant role that these requirements can be reached. Even maintenance is much more than repairing faults nowadays, spare parts are important part of maintenance. Large power boilers are user-specific therefore features of boilers vary from project to project. Equipment have been designed to follow the customer’s requirements therefore spare parts are mainly user-specific also. The study starts with literature review introducing maintenance, failure mechanisms, and systems and equipment of bubbling fluidized bed boiler. At the final part spare part management is discussed from boiler technology point of view. For this part of the study science publications about spare part management are utilized also some specialist from a boiler technology company and other original equipment manufacturers were interviewed. Spare part management is challenging from the boiler supplier point of view and the end user of spare parts has a responsibility of stocking items. Criticality analysis can be used for finding most critical devices of the process and spare part management shall focus to those items. Spare parts are part of risk management. Stocking spare parts is increasing costs but then high spare part availability is decreasing delay time caused by fault of item.

A biochemical predictor of performance during mesophilic anaerobic fermentation of starch wastewater

The aim of this study was to determine the potential of biochemical parameters, such as enzyme activity and adenosine triphosphate (ATP) levels, as monitors of process performance in the Upflow Anaerobic Sludge Blanket (UASB) reactor utilizing a starch wastewater. The acid and alkaline phosphatase activity and the ATP content of the UASB sludge were measured in response to changes in flow rate and nutrient loading. Conventional parameters of process performance, such as gas production, acetic acid production, COD, phosphorus, nitrogen and suspended solids loadings and % COD removal were also monitored. The response of both biochemical and conventional parameters to changing process conditions was then compared. Alkaline phosphatase activity exhibited the highest activity over the entire study perioda A high suspended solids loading was observed to upset the system in terms of gas production, acetic acid production and % COD removala The initial rate of increase in alkaline phosphatase activity following an increase in loading was four times as great during process upset than under conditions of good performance. The change in enzyme actiVity was also more sensitive to process upset than changes in acetic acid production. The change in ATP content of the sludge with time suggested that enzyme actiVity was changing independently of the actual viable biomass present. The bacterial composition of the anaerobic sludge granules was similar to that of other sludge bed systems, at the light and scanning electron microscope level. Isolated serum bottle cultures produced several acids involved in anaerobic carbohydrate metabolism. The overall performance of the UASB system indicated that higher loadings of soluble nutrients could have been tolerated by the system.