Model based analysis of the post-combustion calcium looping process for carbon dioxide capture

This thesis presents a one-dimensional, semi-empirical dynamic model for the simulation and analysis of a calcium looping process for post-combustion CO2 capture. Reduction of greenhouse emissions from fossil fuel power production requires rapid actions including the development of efficient carbon capture and sequestration technologies. The development of new carbon capture technologies can be expedited by using modelling tools. Techno-economical evaluation of new capture processes can be done quickly and cost-effectively with computational models before building expensive pilot plants. Post-combustion calcium looping is a developing carbon capture process which utilizes fluidized bed technology with lime as a sorbent. The main objective of this work was to analyse the technological feasibility of the calcium looping process at different scales with a computational model. A one-dimensional dynamic model was applied to the calcium looping process, simulating the behaviour of the interconnected circulating fluidized bed reactors. The model incorporates fundamental mass and energy balance solvers to semi-empirical models describing solid behaviour in a circulating fluidized bed and chemical reactions occurring in the calcium loop. In addition, fluidized bed combustion, heat transfer and core-wall layer effects were modelled. The calcium looping model framework was successfully applied to a 30 kWth laboratory scale and a pilot scale unit 1.7 MWth and used to design a conceptual 250 MWth industrial scale unit. Valuable information was gathered from the behaviour of a small scale laboratory device. In addition, the interconnected behaviour of pilot plant reactors and the effect of solid fluidization on the thermal and carbon dioxide balances of the system were analysed. The scale-up study provided practical information on the thermal design of an industrial sized unit, selection of particle size and operability in different load scenarios.

Effect of additives, precursors and process conditions on particle morphology

The objective of the thesis was to develop methods to manufacture and control calcium carbonate crystal nucleation and growth in precipitation process. The work consists of experimental part and literature part that addresses theory of nucleation, crystallization and precipitation. In the experimental part calcium carbonate was precipitated using carbonization reaction. Precipitation was carried out in presence of known morphology controlling agents (anionic polymers and sodium silicate) and by using different operation conditions. Formed material was characterized using SEM images, and its thermal stability was assessed. This work demonstrates that carbon dioxide feeding rate and concentrations of calcium hydroxide and additives can be used to control size, shape and amount of precipitating calcium carbonate.

Thermal reactions of the major hydrocarbon components of biomass gasification gas

Gasification of biomass is an efficient method process to produce liquid fuels, heat and electricity. It is interesting especially for the Nordic countries, where raw material for the processes is readily available. The thermal reactions of light hydrocarbons are a major challenge for industrial applications. At elevated temperatures, light hydrocarbons react spontaneously to form higher molecular weight compounds. In this thesis, this phenomenon was studied by literature survey, experimental work and modeling effort. The literature survey revealed that the change in tar composition is likely caused by the kinetic entropy. The role of the surface material is deemed to be an important factor in the reactivity of the system. The experimental results were in accordance with previous publications on the subject. The novelty of the experimental work lies in the used time interval for measurements combined with an industrially relevant temperature interval. The aspects which are covered in the modeling include screening of possible numerical approaches, testing of optimization methods and kinetic modelling. No significant numerical issues were observed, so the used calculation routines are adequate for the task. Evolutionary algorithms gave a better performance combined with better fit than the conventional iterative methods such as Simplex and Levenberg-Marquardt methods. Three models were fitted on experimental data. The LLNL model was used as a reference model to which two other models were compared. A compact model which included all the observed species was developed. The parameter estimation performed on that model gave slightly impaired fit to experimental data than LLNL model, but the difference was barely significant. The third tested model concentrated on the decomposition of hydrocarbons and included a theoretical description of the formation of carbon layer on the reactor walls. The fit to experimental data was extremely good. Based on the simulation results and literature findings, it is likely that the surface coverage of carbonaceous deposits is a major factor in thermal reactions.

VVER-440 Thermal Hydraulics as a Computer Code Validation Challenge

This thesis concentrates on the validation of a generic thermal hydraulic computer code TRACE under the challenges of the VVER-440 reactor type. The code capability to model the VVER-440 geometry and thermal hydraulic phenomena specific to this reactor design has been examined and demonstrated acceptable. The main challenge in VVER-440 thermal hydraulics appeared in the modelling of the horizontal steam generator. The major challenge here is not in the code physics or numerics but in the formulation of a representative nodalization structure. Another VVER-440 specialty, the hot leg loop seals, challenges the system codes functionally in general, but proved readily representable. Computer code models have to be validated against experiments to achieve confidence in code models. When new computer code is to be used for nuclear power plant safety analysis, it must first be validated against a large variety of different experiments. The validation process has to cover both the code itself and the code input. Uncertainties of different nature are identified in the different phases of the validation procedure and can even be quantified. This thesis presents a novel approach to the input model validation and uncertainty evaluation in the different stages of the computer code validation procedure. This thesis also demonstrates that in the safety analysis, there are inevitably significant uncertainties that are not statistically quantifiable; they need to be and can be addressed by other, less simplistic means, ultimately relying on the competence of the analysts and the capability of the community to support the experimental verification of analytical assumptions. This method completes essentially the commonly used uncertainty assessment methods, which are usually conducted using only statistical methods.

Influence of thermal treatment of wood on the aroma of a sugar cane spirit (cachaça) model-solution

The aging process of alcoholic beverages is generally conducted in wood barrels made with species from Quercus sp. Due to the high cost and the lack of viability of commercial production of these trees in Brazil, there is demand for new alternatives to using other native species and the incorporation of new technologies that enable greater competitiveness of sugar cane spirit aged in Brazilian wood. The drying of wood, the thermal treatment applied to it, and manufacturing techniques are important tools in defining the sensory quality of alcoholic beverages after being placed in contact with the barrels. In the thermal treatment, several compounds are changed by the application of heat to the wood and various studies show the compounds are modified, different aromas are developed, there is change in color, and beverages achieve even more pleasant taste, when compared to non-treated woods. This study evaluated the existence of significant differences between hydro-alcoholic solutions of sugar cane spirits elaborated from different species of thermo-treated and non-treated wood in terms of aroma. An acceptance test was applied to evaluate the solutions preferred by tasters under specific test conditions.

Evaluation of antioxidants stability by thermal analysis and its protective effect in heated edible vegetable oil

In this work, through the use of thermal analysis techniques, the thermal stabilities of some antioxidants were investigated, in order to evaluate their resistance to thermal oxidation in oils, by heating canola vegetable oil, and to suggest that antioxidants would be more appropriate to increase the resistance of vegetable oils in the thermal degradation process in frying. The techniques used were: Thermal Gravimetric (TG) and Differential Scanning Calorimetry (DSC) analyses, as well as an allusion to a possible protective action of the vegetable oils, based on the thermal oxidation of canola vegetable oil in the laboratory under constant heating at 180 ºC/8 hours for 10 days. The studied antioxidants were: ascorbic acid, sorbic acid, citric acid, sodium erythorbate, BHT (3,5-di-tert-butyl-4-hydroxytoluene), BHA (2, 3-tert-butyl-4-methoxyphenol), TBHQ (tertiary butyl hydroquinone), PG (propyl gallate) - described as antioxidants by ANVISA and the FDA; and also the phytic acid antioxidant and the SAIB (sucrose acetate isobutyrate) additive, which is used in the food industry, in order to test its behavior as an antioxidant in vegetable oil. The following antioxidants: citric acid, sodium erythorbate, BHA, BHT, TBHQ and sorbic acid decompose at temperatures below 180 ºC, and therefore, have little protective action in vegetable oils undergoing frying processes. The antioxidants below: phytic acid, ascorbic acid and PG, are the most resistant and begin their decomposition processes at temperatures between 180 and 200 ºC. The thermal analytical techniques have also shown that the SAIB antioxidant is the most resistant to oxidative action, and it can be a useful choice in the thermal decomposition prevention of edible oils, improving stability regarding oxidative processes.

Thermal properties of defatted meal, concentrate, and protein isolate of baru nuts (Dipteryx alata Vog.)

Baru (Dipteryx alata Vog.), a species of legume found in the Brazilian savannas, was investigated in this study for the composition of its flesh and seed. Thermal analyses, Thermogravimetry (TG), and Differential Scanning Calorimetry (DSC) were used to investigate the proteins in defatted meal, concentrate, and protein isolate. The protein concentrate was extracted at pH 10, followed by a precipitation at the isoelectric point to obtain the isolate that was spray dried. The thermogravimetric curves were obtained under a nitrogen atmosphere with a 100 mL/minutes flow. The initial, final and peak temperatures and mass loss were analyzed. Within the performed temperature ranges studied, the defatted meal and concentrate presented four steps of mass loss, while the isolate showed only two steps. The protein content of defatted meal from Baru nuts was higher than that of the isolate. On the other hand, there was a reduction in enthalpy, which suggests that the process applied to obtain the baru concentrate and isolate led to protein denaturation.

Isolation and recovery of glycomacropeptide from milk whey by means of thermal treatment

During enzymatic process of cheese manufacturing, rennin cleaves κ-casein releasing two fractions: para-κ-casein and glycomacropeptide (GMP), which remains soluble in milk whey. GMP is a peptide with structural particularities such as chain carbohydrates linked to specific threonine residues, to which a great variety of biological activities is attributed. Worldwide cheese production has increased generating high volumes of milk whey that could be efficiently used as an alternative source of high quality peptide or protein in foodstuff formulations. In order to evaluate isolation and recovery on whey GMP by means of thermal treatment (90 °C), 18 samples (2 L each) of sweet whey, resuspended commercial whey (positive control) and acid whey (negative control) were processed. Indirect presence of GMP was verified using chemical tests and PAGE-SDS 15%. At 90 °C treated sweet whey, 14, 20 and 41 kDa bands were observed. These bands may correspond to olygomers of GMP. Peptide recovery showed an average of 1.5 g/L (34.08%). The results indicate that industrial scale GMP production is feasible; however, further research must be carried out for the biological and nutritional evaluation of GMP's incorporation to foodstuff as a supplement.

Antioxidant capacity of amaranth products: effects of thermal and enzymatic treatments

The effect of different process -defatting, protein concentration, thermal treatment, hydrolysis with Alcalase and in vitro digestion- on the antioxidant capacity of amaranth seeds was studied. The antioxidant capacity of the products was determined in methanolic and aqueous extracts and varied from 1.00 to 21.22 and 4.97 to 369.18 µ mol TE/g sample for DPPH and ORAC assays, respectively. The combination of protein concentration and hydrolysis with Alcalase led to products with higher antioxidant activity. However, after in vitro digestion, protein concentrate and its hydrolysate showed similar antioxidant capacity. A high correlation was observed between the antioxidant capacity and the total phenolic content for methanolic extracts, with r² values ranging from 0.6133 to 0.9352.

The kinetics and induced decomposition on the thermal decomposition of hydroperoxides /

This project is focussed on the thermsLl decomposition of t-butyl hydroperoxide and sec-butyl hydroperoxide at 120°C to 160°C in three alcohol solvents. These are methanol, ethajiol and isopropyl alcohol. The aim of the project was to examine the process of induced decomposition. Thermal decomposition of t-hutyl hydroperoxide and sec-butyl hydroperoxide indicate that these reactions have first-order kinetics with activation energies on the order of 20 to 28 K cal/mole, Styrene was used as a free radical trap to inhibit the induced decomposition. The results permitted calculation of how much induced decomposition occurred in its absence. The experimental resvilts indicate that the induced decomposition is important for t-butyl hydroperoxide in alcohol solvents, as shown by both the reaction rate suid product studies. But sec-butyl hydroperoxide results show that the concerted mechanism for the interaction of two sec-butylperoxy radicals occurs in addition to the induced decomposition. Di-sodium E.D,T.A. was added to reduce possible effects of trace transition metal ion .impurities. The result of this experiment were not as expected. The rate of hydroperoxide decomposition was about the same but was zero-order in hydroperoxide concentration.

The kinetics and mechanism of the thermal decomposition of bis diphenyl methyl and related peroxides in liquid phase /|nby C. Thankachan. -- 260 St. Catharines, Ont. : [s. n.],

Rates and products have been determined for the thermal decomposition of bis diphenyl methyl peroxide and diphenyl methyl tert* butyl peroxide at 110@~145@C* The decomposition was uniformly unimolecular with activation energies for the bis diphenyl methyl peroxide in tetrachloroethylene* toluene and nitrobenzene 26,6* 28*3f and 27 Kcals/mole respectively. Diphenyl methyl tert* butyl peroxide showed an activation energy of 38*6 Kcals/mole* About 80-90% of the products in the case of diphenyl methyl peroxide could be explained by the concerted process, this coupled with the negative entropies of activation obtained is a conclusive evidence for the reaction adopting a major concerted path* All the products in the case of diphenyl methyl peroxide could be explained by known reactions of alkoxy radicals* About 80-85% of tert butanol and benzophenone formed suggested far greater cage disproportionation than diffusing apart* Rates of bis triphenyl methyl peroxide have been determined in tetrachloroethylene at 100-120@C* The activation energy was found to be 31 Kcals/mole*

Infrared thermography: A non-invasive window into thermal physiology

Infrared thermography is a non-invasive technique that measures mid to long-wave infrared radiation emanating from all objects and converts this to temperature. As an imaging technique, the value of modern infrared thermography is its ability to produce a digitized image or high speed video rendering a thermal map of the scene in false colour. Since temperature is an important environmental parameter influencing animal physiology and metabolic heat production an energetically expensive process, measuring temperature and energy exchange in animals is critical to understanding physiology, especially under field conditions. As a non-contact approach, infrared thermography provides a non-invasive complement to physiological data gathering. One caveat, however, is that only surface temperatures are measured, which guides much research to those thermal events occurring at the skin and insulating regions of the body. As an imaging technique, infrared thermal imaging is also subject to certain uncertainties that require physical modeling, which is typically done via built-in software approaches. Infrared thermal imaging has enabled different insights into the comparative physiology of phenomena ranging from thermogenesis, peripheral blood flow adjustments, evaporative cooling, and to respiratory physiology. In this review, I provide background and guidelines for the use of thermal imaging, primarily aimed at field physiologists and biologists interested in thermal biology. I also discuss some of the better known approaches and discoveries revealed from using thermal imaging with the objective of encouraging more quantitative assessment.

STANDARDIZATION OF PROCESS PARAMETERS FOR READY TO EAT FISH PRODUCTS IN INDIGENOUS POLYMER COATED TIN FREE STEEL CANS

In the present work, Indigenous polymer coated Tin Free Steel cans were analyzed fortheir suitability for thermal processing and storage of fish and fish products following standard methods. The raw materials used for the development of ready to eat thermally processed fish products were found to be of fresh condition. The values for various biochemical and microbiological parameters of the raw materials were well within the limits. Based on the analysis of commercial sterility, instrumental colour, texture, WB-shear force and sensory parameters, squid masala processed to F0 value of 8 min with a total process time of 38.5 min and cook value of 92 min was chosen as the optimum for squid masala in tin free steel cans while shrimp curry processed to F0 7 min with total process time of 44.0 min and cook value of 91.1 min was found to be ideal and was selected for storage study. Squid masala and shrimp curry thermally processed in indigenous polymer coated TFS cans were found to be acceptable even after one year of storage at room temperaturebased on the analysis of various sensory and biochemical parameters. Analysis of the Commission Internationale d’ Eclirage L*, a* and b* color values showed that the duration of exposure to heat treatment influenced the color parameters: the lightness (L*) and yellowness (b*)decreased, and the redness (a*) significantly increased with the increase in processing time or reduction in processing temperature.Instrumental analysis of texture showed that hardness-1 & 2 decreased with reduction in retort temperature while cohesiveness value did not show any appreciable change with decrease in temperature of processing. Other texture profile parameters like gumminess, springiness and chewiness decreased significantly with increase of processing time. W-B shear force values of mackerel meat processed at 130 °C were significantly higher than those processed at 121.1 and 115 °C. HTST processing of mackerel in brine helped in reducing the process time and improving the quality.The study also indicated that indigenous polymer coated TFS cans with easy openends can be a viable alternative to the conventional tin and aluminium cans. The industry can utilize these cans for processing ready to eat fish and shell fish products for both domestic and export markets. This will help in reviving the canning industry in India.

Further studies on the process of coastal upwelling along the south west coast of India - possible correlations with biological productivity

An attempt is made to study the possible relationship between the process of upwelling and zooplankton biomass in the shelf weters along the south west coast of India between Cape comorin and Ratnagiri based on oceanographic and Zooplankton data collected by the erstwhile FAO/UNDP Pelagic Fishery Project,Cochin between 1973 and 1978. Different factors such as the depth from which the bottom waters are induced upwards during the process of upwelling,the depth to which the bottom waters are drawn, vertical velocity of upwelling and the resultant zooplankton productivity were considered while arriving at the deductions. Except for nutrients and phytoplankton productivity, for which simultaneous data is lacking, all the major factors were taken into consideration before cocluding- xon positive/negative correlation.

Studies on Electrical and Thermal Properties of Certain Selected Photonic Materials

The present thesis is centered around the study of electrical and thermal properties of certain selected photonic materials.We have studied the electrical conduction mechanism in various phases of certain selected photonic materials and those associated with different phase transitions occurring in them. A phase transition leaves its own impressions on the key parameters like electrical conductivity and dielectric constant. However, the activation energy calculation reveals the dominant factor responsible for conduction process.PA measurements of thermal diffusivity in certain other important photonic materials are included in the remaining part of the research work presented in this thesis. PA technique is a promising tool for studying thermal diffusivities of solid samples in any form. Because of its crucial role and common occurrence in heat flow problems, the thermal diffusivity determination is often necessary and knowledge of thermal diffusivity can intum be used to calculate the thermal conductivity. Especially,knowledge of the thermal diffusivity of semiconductors is important due to its relation to the power dissipation problem in microelectronic and optoelectronic devices which limits their performances. More than that, the thermal properties, especially those of thin films are of growing interest in microelectronics and microsystems because of the heat removal problem involved in highly integrated devices. The prescribed chapter of the present theis demonstrates how direct measurement of thermal diffusivity can be carried out in thin films of interest in a simple and elegant manner using PA techniques. Although results of only representative measurements viz; thermal diffusivity values in Indium, Aluminium, Silver and CdS thin films are given here, evaluation of this quantity for any photonic and / electronic material can be carried out using this technique in a very simple and straight forward manner.