Modelling of combustion and sorbent reactions in three-dimensional flow environment of a circulating fluidized bed furnace

This thesis presents a three-dimensional, semi-empirical, steady state model for simulating the combustion, gasification, and formation of emissions in circulating fluidized bed (CFB) processes. In a large-scale CFB furnace, the local feeding of fuel, air, and other input materials, as well as the limited mixing rate of different reactants produce inhomogeneous process conditions. To simulate the real conditions, the furnace should be modelled three-dimensionally or the three-dimensional effects should be taken into account. The only available methods for simulating the large CFB furnaces three-dimensionally are semi-empirical models, which apply a relatively coarse calculation mesh and a combination of fundamental conservation equations, theoretical models and empirical correlations. The number of such models is extremely small. The main objective of this work was to achieve a model which can be applied to calculating industrial scale CFB boilers and which can simulate all the essential sub-phenomena: fluid dynamics, reactions, the attrition of particles, and heat transfer. The core of the work was to develop the model frame and the required sub-models for determining the combustion and sorbent reactions. The objective was reached, and the developed model was successfully used for studying various industrial scale CFB boilers combusting different types of fuel. The model for sorbent reactions, which includes the main reactions for calcitic limestones, was applied for studying the new possible phenomena occurring in the oxygen-fired combustion. The presented combustion and sorbent models and principles can be utilized in other model approaches as well, including other empirical and semi-empirical model approaches, and CFD based simulations. The main achievement is the overall model frame which can be utilized for the further development and testing of new sub-models and theories, and for concentrating the knowledge gathered from the experimental work carried out at bench scale, pilot scale and industrial scale apparatus, and from the computational work performed by other modelling methods.

Identification of extractives and polysaccharides as foulants in membrane filtration of pulp and paper mill effluents

The search for new renewable materials has intensified in recent years. Pulp and paper mill process streams contain a number of potential compounds which could be used in biofuel production and as raw materials in the chemical, food and pharmaceutical industries. Prior to utilization, these compounds require separation from other compounds present in the process stream. One feasible separation technique is membrane filtration but to some extent, fouling still limits its implementation in pulp and paper mill applications. To mitigate fouling and its effects, foulants and their fouling mechanisms need to be well understood. This thesis evaluates fouling in filtration of pulp and paper mill process streams by means of polysaccharide model substance filtrations and by development of a procedure to analyze and identify potential foulants, i.e. wood extractives and carbohydrates, from fouled membranes. The model solution filtration results demonstrate that each polysaccharide has its own fouling mechanism, which also depends on the membrane characteristics. Polysaccharides may foul the membranes by adsorption and/or by gel/cake layer formation on the membrane surface. Moreover, the polysaccharides interact, which makes fouling evaluation of certain compound groups very challenging. Novel methods to identify wood extractive and polysaccharide foulants are developed in this thesis. The results show that it is possible to extract and identify wood extractives from membranes fouled in filtration of pulp and paper millstreams. The most effective solvent was found to be acetone:water (9:1 v/v) because it extracted both lipophilic extractives and lignans at high amounts from the fouled membranes and it was also non-destructive for the membrane materials. One hour of extraction was enough to extract wood extractives at high amounts for membrane samples with an area of 0.008 m2. If only qualitative knowledge of wood extractives is needed a simplified extraction procedure can be used. Adsorption was the main fouling mechanism in extractives-induced fouling and dissolved fatty and resin acids were mostly the reason for the fouling; colloidal fouling was negligible. Both process water and membrane characteristics affected extractives-induced fouling. In general, the more hydrophilic regenerated cellulose (RC) membrane fouled less that the more hydrophobic polyethersulfone (PES) and polyamide (PA) membranes independent of the process water used. Monosaccharide and uronic acid units could also be identified from the fouled synthetic polymeric membranes. It was impossible to analyze all monosaccharide units from the RC membrane because the analysis result obtained contained degraded membrane material. One of the fouling mechanisms of carbohydrates was adsorption. Carbohydrates were not potential adsorptive foulants to the sameextent as wood extractives because their amount in the fouled membranes was found to be significantly lower than the amount of wood extractives.

Modeling study of limestone reactions in fluidized bed conditions

Traditionally limestone has been used for the flue gas desulfurization in fluidized bed combustion. Recently, several studies have been carried out to examine the use of limestone in applications which enable the removal of carbon dioxide from the combustion gases, such as calcium looping technology and oxy-fuel combustion. In these processes interlinked limestone reactions occur but the reaction mechanisms and kinetics are not yet fully understood. To examine these phenomena, analytical and numerical models have been created. In this work, the limestone reactions were studied with aid of one-dimensional numerical particle model. The model describes a single limestone particle in the process as a function of time, the progress of the reactions and the mass and energy transfer in the particle. The model-based results were compared with experimental laboratory scale BFB results. It was observed that by increasing the temperature from 850 °C to 950 °C the calcination was enhanced but the sulfate conversion was no more improved. A higher sulfur dioxide concentration accelerated the sulfation reaction and based on the modeling, the sulfation is first order with respect to SO2. The reaction order of O2 seems to become zero at high oxygen concentrations.

Carbonation of Mg(OH)2 in a pressurised fluidised bed for CO2 sequestration

I takt med den ekonomiska tillväxten har CO2-utsläppen till atmosfären ständigt ökat, och utan kraftiga åtgärder kommer de att fortsätta att öka i allt snabbare takt. Konsekvenserna av en påtagligt förhöjd atmosfärisk CO2-halt är fortfarande osäkra (men eventuellt katastrofala) och fenomenet går under namnet global uppvärmning eller klimatförändring. CCS från engelskans ”carbon dioxide capture and storage” framstår som ett alternativ för att bekämpa de ständigt ökande CO2-utsläppen. Ett av de mer intressanta, och för Finlands del ända CCS-alternativet, baserar sig på naturens egna sätt att begränsa atmosfärisk CO2, nämligen vittring. Naturlig vittring, som förenklat innefattar nedbrytningen av sten/berg (även känd som erosion) och de därpå följande reaktionerna med CO2-mättat regnvatten. Slutresultatet är en utfällning av fasta mineraler som nu bundit CO2 i form av kalcium- och magnesiumkarbonat. Kalciumkarbonat är även bättre känt som kalksten, d.v.s. CO2 blir bundet i sten. Det gäller dock att snabba upp denna process, som i naturen är ytterst långsam, på ett ekonomiskt och miljömässigt hållbart sätt. Hittills har ett antal metoder för att påskynda naturlig vittring, eller med andra ord öka CO2-upptagningsförmågan av olika mineraler föreslagits. De mera etablerade uttrycken (lånade från engelskan) talar om mineralkarbonatisering och CO2-mineralisering. Till skillnad från många andra CO2-mineraliseringsalternativ är det alternativ som behandlas i denna avhandling i hög grad baserat på möjligheten att utnyttja den värme som frigörs vid karbonatisering. I teorin är det möjligt att föreställa sig en mineraliseringsprocess som inte kräver extern energi, men tillsvidare har man dock inte lyckats uppnå detta mål. Den process som presenteras i denna avhandling går ut på att man utvinner magnesium ur i naturen vanligt förekommande magnesiumrika mineraler, konverterar det till magnesiumhydroxid och därefter karbonatiserar det till magnesiumkarbonat. I rätta förhållanden kan magnesiumhydroxid reagera med CO2 mycket snabbt och i nuläget har processen potential att minska CO2-utsläppen från industri där spillvärme finns till förfogande (t.ex. cement- och stålindustrin). Fortsatt forskning är dock ett måste för att kunna påverka CO2-utsläppen i en globalt signifikant skala.

Behavior, performance and physiological parameters of pigs reared in deep bedding

An experiment was conducted to evaluate the behavior, performance and physiological parameters of pigs in different production systems. Twenty four animals in the growth phase were distributed in a randomized block design in three treatments: T1 - concrete floor, T2 - deep bedding with wood shaving, and T3 - deep bedding with coffee husks. The behavioral study was carried out by observing the animal behavior for an uninterrupted period of eight hours throughout seven weeks. The proportions of time spent in each behavior were characterized using the frequency histogram composition. Environmental (IBGTH), physiological (rectal and skin temperature and respiratory rate) and performance (weight gain, feed intake and feed conversion) parameters were measured in animals during the period. The production systems of deep bedding showed higher values of IBGTH. There was no effect of production systems evaluated on the performance parameters. Rectal temperature was higher in animals reared on deep bedding with coffee husks in relation to the concrete floor. The use of deep bedding benefited the behavior of piglets in the growth phase and it reduced the agonistic behavior among individuals.

Characterization and use of swine deep bedding ashes in cementitious composites

The deep bedding is a swine alternative production, especially in the finishing phase, whose byproduct can be recycled, reducing the environmental impact. The objectives of this study were to characterize the ash coming from the controlled burning of the swine deep bedding (SDBA) based on rice husk, and to evaluate their performance in composites as a partial substitute for Portland cement (PC). To measure the differences between SDBA and rice husk ash (RHA) as a reference, we have characterized: particle size distribution, real specific density, x-ray diffraction, electrical conductivity, scanning electron microscopy, chemical analysis and loss on ignition. Samples were prepared for two experimental series: control, and another one with the partial replacement of 30% of SDBA in relation to the mass of the Portland cement. According to the results obtained for physical and mechanical characterization, the composites with SDBA can be used as a constructive element in the rural construction.

Water treatment by multistage filtration system with natural coagulant from Moringa oleifera seeds

This study presents an evaluation of a pilot multistage filtration system (MSF) with different dosages, 131 mg L-1 and 106 mg L-1, of the natural coagulant extracted from Moringa oleifera seeds in pre-filtration and slow filtration stages, respectively. The system was comprised by a dynamic pre-filter unit, two upflow filters in parallel and four slow filters in parallel, and in one of the four filters had the filter media altered. The performance of the system was evaluated by monitoring some water quality parameters such as: turbidity, apparent color and slow filter load loss. The stages that have received the coagulant solution had better treatment efficiency compared with the steps without it. However, the direct application of the coagulant solution in the slow filter caused rapid clogging of the non-woven blanket and shorter career length.

Start-up of horizontal anaerobic reactors with sludge blanket and fixed bed for wastewater treatment from coffee processing by wet method

In this study it was evaluated the start-up procedures of anaerobic treatment system with three horizontal anaerobic reactors (R1, R2 and R3), installed in series, with volume of 1.2 L each. R1 had sludge blanket, and R2 and R3 had half supporter of bamboo and coconut fiber, respectively. As an affluent, it was synthesized wastewater from mechanical pulping of the coffee fruit by wet method, with a mean value of total chemical oxygen demand (CODtotal) of 16,003 mg L-1. The hydraulic retention time (HRT) in each reactor was 30 h. The volumetric organic loading (VOL) applied in R1 varied from 8.9 to 25.0 g of CODtotal (L d)-1. The mean removal efficiencies of CODtotal varied from 43 to 97% in the treatment system (R1+R2+R3), stabilizing above 80% after 30 days of operation. The mean content of methane in the biogas were of 70 to 76%, the mean volumetric production was 1.7 L CH4 (L reactor d)-1 in the system, and the higher conversions were around at 0.20 L CH4 (g CODremoved)-1 in R1 and R2. The mean values of pH in the effluents ranged from 6.8 to 8.3 and the mean values of total volatile acids remained below 200 mg L-1 in the effluent of R3. The concentrations of total phenols of the affluent ranged from 45 to 278 mg L-1, and the mean removal efficiency was of 52%. The start-up of the anaerobic treatment system occurred after 30 days of operation as a result of inoculation with anaerobic sludge with active microbiota.

Nitrogen fertilization by deep bedding swine production and its effects on dry matter production and accumulation of nutrients by maize

The goal of this study was to evaluate the nitrogen fertilization as deep litter for pigs in order to produce biomass and accumulate nutrients by the corn. A deep litter made of rice husk as organic compound, from a commercial pig farm during finishing phase, was used. After three consecutive batches of pigs, the deep litter was subjected to a maturation period of 50 days, and samples of this material were taken for analysis of agronomic value. The experimental design was completely randomized with five replicates. The treatments consisted of doses of 0, 75, 150 and 300mg dm-3 of N of deep litter, as well as an additional treatment with ammonium sulfate, with a dosage of 150mg dm-3 of N. After 45 days, corn plants were harvested in order to evaluate the total dry weight and nutrient concentrations of their aerial parts. Dry matter increases were found with more application of deep litter. Regarding control fertilization, the use of increasing dosages of deep litter allowed accumulation of K, reduced the availability of P, Ca, Mg, Zn and B and did not alter the concentrations of N, Cu, Fe and Mn.

Hydrogen production from cassava processing wastewater in an anaerobic fixed bed reactor with bamboo as a support material

Attempting to associate waste treatment to the production of clean and renewable energy, this research sought to evaluate the biological production of hydrogen using wastewater from the cassava starch treatment industry, generated during the processes of extraction and purification of starch. This experiment was carried out in a continuous anaerobic reactor with a working volume of 3L, with bamboo stems as the support medium. The system was operated at a temperature of 36°C, an initial pH of 6.0 and under variations of organic load. The highest rate of hydrogen production, of 1.1 L.d-1.L-1, was obtained with application of an organic loading rate of 35 g.L-1.d-1, in terms of total sugar content and hydraulic retention time of 3h, with a prevalence of butyric and acetic acids as final products of the fermentation process. Low C/N ratios contributed to the excessive growth of the biomass, causing a reduction of up to 35% in hydrogen production, low percentages of H2 and high concentrations of CO2in the biogas.

Software for design of experiments and response modelling of cake filtration applications

Filtration is a widely used unit operation in chemical engineering. The huge variation in the properties of materials to be ltered makes the study of ltration a challenging task. One of the objectives of this thesis was to show that conventional ltration theories are di cult to use when the system to be modelled contains all of the stages and features that are present in a complete solid/liquid separation process. Furthermore, most of the ltration theories require experimental work to be performed in order to obtain critical parameters required by the theoretical models. Creating a good overall understanding of how the variables a ect the nal product in ltration is somewhat impossible on a purely theoretical basis. The complexity of solid/liquid separation processes require experimental work and when tests are needed, it is advisable to use experimental design techniques so that the goals can be achieved. The statistical design of experiments provides the necessary tools for recognising the e ects of variables. It also helps to perform experimental work more economically. Design of experiments is a prerequisite for creating empirical models that can describe how the measured response is related to the changes in the values of the variable. A software package was developed that provides a ltration practitioner with experimental designs and calculates the parameters for linear regression models, along with the graphical representation of the responses. The developed software consists of two software modules. These modules are LTDoE and LTRead. The LTDoE module is used to create experimental designs for di erent lter types. The lter types considered in the software are automatic vertical pressure lter, double-sided vertical pressure lter, horizontal membrane lter press, vacuum belt lter and ceramic capillary action disc lter. It is also possible to create experimental designs for those cases where the variables are totally user de ned, say for a customized ltration cycle or di erent piece of equipment. The LTRead-module is used to read the experimental data gathered from the experiments, to analyse the data and to create models for each of the measured responses. Introducing the structure of the software more in detail and showing some of the practical applications is the main part of this thesis. This approach to the study of cake ltration processes, as presented in this thesis, has been shown to have good practical value when making ltration tests.

Incidence of deep vein thrombosis and quality of venous thromboembolism prophylaxis

OBJECTIVE: to determine the incidence of deep vein thrombosis and prophylaxis quality in hospitalized patients undergoing vascular and orthopedic surgical procedures. METHODS: we evaluated 296 patients, whose incidence of deep venous thrombosis was studied by vascular ultrasonography. Risk factors for venous thrombosis were stratified according the Caprini model. To assess the quality of prophylaxis we compared the adopted measures with the prophylaxis guidelines of the American College of Chest Physicians. RESULTS: the overall incidence of deep venous thrombosis was 7.5%. As for the risk groups, 10.8% were considered low risk, 14.9%moderate risk, 24.3% high risk and 50.5% very high risk. Prophylaxis of deep venous thrombosis was correct in 57.7%. In groups of high and very high risk, adequate prophylaxis rates were 72.2% and 71.6%, respectively. Excessive use of chemoprophylaxis was seen in 68.7% and 61.4% in the low and moderate-risk groups, respectively. CONCLUSION: although most patients are deemed to be at high and very high risk for deep vein thrombosis, deficiency in the application of prophylaxis persists in medical practice.

CO2 sparging for improving the filtration properties of iron ore slurries

Iron ore treatment processes are usually continuous and high tonnage and filtration equipment has to meet these requirements. In magnetite (Fe3O4) treatment process continuous rotary disc filters are often used for filtration. Carbon dioxide (CO2) treatment is a fairly novel and un-known filtration enhancing process. The interest to use CO2 is quite high because CO2 is a greenhouse gas that is abundant, readily available and capture and use of CO2 would be environmentally beneficial. The focus of this thesis was to investigate if CO2 could be used to enhance the filtration of magnetite with ceramic disc filter. Previous studies have suggested that CO2 could be used to enhance the filtration properties of different iron ores thus increasing the filtration capacity. In the literature part, the basic theory of filtration and the particle properties affecting filtration were discussed. The basic steps of a typical ore treatment process were presented. The reasons why CO2 might enhance the filtration properties of different ores were investigated. A literature survey of earlier studies of CO2 addition as a filter aid was presented and the basic chemical properties and reactions of CO2 were also discussed. The experimental part was done at the LUT Laboratory of Separation Technology using different magnetite samples from the industry. The filtration experiments indicated that CO2 had a positive influence on the filtration properties of magnetite slurry. Zeta potential of untreated and CO2 treated magnetite was measured and CO2 treated magnetite had lower zeta potential values than the untreated magnetite. The filtration capacity was increased while the cake moisture levels were only slightly increased.

Validation of a 3D model for oxygen combustion in a circulating fluidized bed

In this thesis, a model called CFB3D is validated for oxygen combustion in circulating fluidized bed boiler. The first part of the work consists of literature review in which circulating fluidized bed and oxygen combustion technologies are studied. In addition, the modeling of circulating fluidized bed furnaces is discussed and currently available industrial scale three-dimensional furnace models are presented. The main features of CFB3D model are presented along with the theories and equations related to the model parameters used in this work. The second part of this work consists of the actual research and modeling work including measurements, model setup, and modeling results. The objectives of this thesis is to study how well CFB3D model works with oxygen combustion compared to air combustion in circulating fluidized bed boiler and what model parameters need to be adjusted when changing from air to oxygen combustion. The study is performed by modeling two air combustion cases and two oxygen combustion cases with comparable boiler loads. The cases are measured at Ciuden 30 MWth Flexi-Burn demonstration plant in April 2012. The modeled furnace temperatures match with the measurements as well in oxygen combustion cases as in air combustion cases but the modeled gas concentrations differ from the measurements clearly more in oxygen combustion cases. However, the same model parameters are optimal for both air and oxygen combustion cases. When the boiler load is changed, some combustion and heat transfer related model parameters need to be adjusted. To improve the accuracy of modeling results, better flow dynamics model should be developed in the CFB3D model. Additionally, more measurements are needed from the lower furnace to find the best model parameters for each case. The validation work needs to be continued in order to improve the modeling results and model predictability.