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Novikov, Yehor. "1-Bromo-1-lithioethene as a building block for organic synthesis." [Kent, Ohio] : Kent State University, 2005. http://rave.ohiolink.edu/etdc/view?acc%5Fnum=kent1135388929.
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Thesis (Ph.D.)--Kent State University, 2005.Title from PDF t.p. (viewed July 25, 2006). Advisor: Paul Sampson. Keywords: organolithiums, Felkin-Anh diastereoselectivity, low temperatures, cryogenic reactor, carbohydrates, building blocks. Includes bibliographical references (p. 186-197).
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Muga, Julius N’gon’ga. "Design and implementation of IEC 61499 standard-based nonlinear controllers using functional block programming in distributed control platform." Thesis, Cape Peninsula University of Technology, 2015. http://hdl.handle.net/20.500.11838/2381.
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Thesis (DTech (Electrical Engineering))--Cape Peninsula University of Technology, 2016.Majority of the industrial systems encountered are significantly non-linear in nature, so if they are synthesised and designed by linear methods, then some of salient features characterising of their performance may not be captured. Therefore designing a control system that captures the nonlinearities is important. This research focuses on the control design strategies for the Continuous Stirred Tank Reactor (CSTR) process. To control such a process a careful design strategy is required because of the nonlinearities, loop interaction and the potentially unstable dynamics characterizing the system. In these systems, linear control methods alone may not perform satisfactorily. Three different control design strategies (Dynamic decoupling, Decentralized and Input-output feedback linearization controller) are proposed and implemented .in the Matlab/Simulink platform and the developed strategies are then deployed to the design of distributed automation control system configuration using the IEC 61499 standard based functional block programming language. Twin CAT 3.1 system real-time and Matlab/Simulink (www.mathworks.com) environment are used to test the effectiveness of the models The simulation results from the investigation done between Simulink and TwinCAT 3 software (Beckhoff Automation) platforms in the case of the model transformation and closed loop simulation of the process for the considered cases have shown the suitability and the potentials of merging the Matlab/Simulink control function blocks into the TwinCAT 3.1 function blocks in real-time. The merits derived from such integration imply that the existing software and software components can be re-used. This is in line with one of the IEC 6144 standard requirements such as portability and interoperability. Similarly, the simplification of programming applications is greatly achieved. The investigation has also shown that the integration the of Matlab/Simulink models running in the TwinCAT 3.1 PLC do not need any modification, hence confirming that the TwinCAT 3.1 development platform can be used for the design and implementation of controllers from different platforms. Also, based on the steps required for model transformation the between the Matlab/Simulink to the TwinCAT 3 functional blocks, the algorithms of the control design methodologies developed, simulation results are used to verify the suitability of the controls to find whether the effective set-point tracking control and disturbance effect minimisation for the output variables can be achieved in real-time using the transformed Simulink blocks to the TwinCAT 3 functional blocks, then downloaded to the Beckhoff CX5020 PLC for real-time execution. Good set-point tracking control is achieved for the MIMO closed loop nonlinear CSTR process for the considered cases of the developed control methodologies. Similarly, the effects of disturbances are investigated. TwinCAT functional modules achieved good set-point tracking with these disturbances minimization under all the cases considered.
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Северин, Валерій Петрович. "Моделі і методи оптимізації показників якості систем автоматичного управління енергоблоку атомної електростанції." Thesis, СПДФО Ізрайлев Є. М, 2007. http://repository.kpi.kharkov.ua/handle/KhPI-Press/32677.
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Дисертація на здобуття вченого ступеня доктора технічних наук за спеціальністю 05.13.07 – Автоматизація технологічних процесів. – Національний технічний університет "Харківський політехнічний інститут", Харків, 2007.
Дисертація присвячена розробці перспективної концепції синтезу систем автоматичного управління енергоблоку атомної електростанції на основі математичних моделей і чисельних методів векторної оптимізації показників якості. Розроблені методи обчислення прямих показників якості й покращених інтегральних квадратичних оцінок, що мають високу точність і швидкодію. Обґрунтований покроковий принцип переходу до області стійкості системи, запропоновані векторні цільові функції, що включають умови стійкості і враховують пріоритети показників якості. Розроблені надійні методи оптимізації векторних цільових функцій. Отримані математичні моделі в просторі станів для систем автоматичного управління ядерним реактором, парогенератором та паровою турбіною. Виконана оптимізація показників якості систем управління енергоблоку, яка дозволила оцінити ефективність різних регуляторів.Thesis for a doctor’s degree in speciality 05.13.07 – automation of technological processes. – National Technical University "Kharkiv Polytechnic Institute", Kharkiv, 2007. The thesis is devoted to the development of a perspective concept of atomic station power block automatic control systems synthesis on the basis of mathematical models and numeric methods of vector optimization of systems quality indexes. The methods for calculation of direct quality indexes and improved integral quadratic estimates have been created. The step-by-step principle of transition to the domain of system stability has been based. There have also been suggested vector goal functions including stability conditions and taking into consideration quality indexes priorities. The reliable optimization methods of vector goal functions have been suggested. Mathematical models in the state space for automatic control systems of nuclear reactor, steam generator and steam turbine have been worked out. The quality indexes optimization of power block control systems has been carried out, which allowed to estimate various regulator types efficiency.
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Северин, Валерий Петрович. "Модели и методы оптимизации показателей качества систем автоматического управления энергоблока атомной электростанции." Thesis, СПДФЛ Израйлев Е. М, 2007. http://repository.kpi.kharkov.ua/handle/KhPI-Press/33459.
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Диссертация на соискание ученой степени доктора технических наук по специальности 05.13.07 – автоматизация технологических процессов. – Национальный технический университет "Харьковский политехнический институт", Харьков, 2007. Диссертация посвящена разработке перспективной концепции синтеза систем автоматического управления энергоблока атомной электростанции на основе математических моделей и численных методов векторной оптимизации показателей качества. Разработаны методы вычисления прямых показателей качества и улучшенных интегральных квадратичных оценок, имеющих высокую точность и быстродействие. Обоснован пошаговый принцип перехода в область устойчивости системы, предложены векторные целевые функции, включающие условия устойчивости и учитывающие приоритеты показателей качества. Разработаны надежные методы оптимизации векторных целевых функций. Получены математические модели в пространстве состояний для систем автоматического управления ядерным реактором, парогенератором и паровой турбиной. Проведена оптимизация показателей качества систем управления энергоблока, позволившая оценить эффективность различных регуляторов.Thesis for a doctor’s degree in speciality 05.13.07 – automation of technological processes. – National Technical University "Kharkov Polytechnic Institute", Kharkov, 2007. The thesis is devoted to the development of a perspective concept of atomic station power block automatic control systems synthesis on the basis of mathematical models and numeric methods of vector optimization of systems quality indexes. The methods for calculation of direct quality indexes and improved integral quadratic estimates have been created. The step-by-step principle of transition to the domain of system stability has been based. There have also been suggested vector goal functions including stability conditions and taking into consideration quality indexes priorities. The reliable optimization methods of vector goal functions have been suggested. Mathematical models in the state space for automatic control systems of nuclear reactor, steam generator and steam turbine have been worked out. The quality indexes optimization of power block control systems has been carried out, which allowed to estimate various regulator types efficiency.
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Tricàs, Rosell Núria. "Plasma modification on carbon black surface: From reactor design to final applications." Doctoral thesis, Universitat Ramon Llull, 2007. http://hdl.handle.net/10803/9288.
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El present treball es basa en l'estudi de la modificació de la superfície del negre de carboni (NC) per mitjà de tècniques de plasma. Tot i que aquest tipus de tractament s'utilitza de manera comú sobre superfícies planes, tanmateix encara existeixen problemes a l'hora de treballar en materials en pols degut a la dificultat que suposa la seva manipulació. En aquest treball s'ha modificat NC tant per tècniques de plasma a baixa pressió com per mitjà de tècniques de plasma atmosfèric. Per tal d'assolir aquest objectiu s'han posat a punt tres reactors de plasma capaços de modificar aquest tipus de material; dos reactors treballen a baixa pressió mentre que el tercer es tracta d'un equip a pressió atmosfèrica.Els sistemes de plasma a baixa pressió utilitzats han estat un reactor down-stream i un reactor de llit fluiditzat. Ambdós sistemes utilitzen un generador de radio freqüències a 13,56MHz per tal de general el plasma. Tots dos sistemes han estat optimitzats per la modificació de materials en pols. En el cas del reactor down-stream, s'ha estudiat a posició d'entrada del gas reactiu, la potència del generador i el temps de modificació per a tres tipus de tractament: oxigen, nitrogen i amoníac. En el cas del reactor de llit fluiditzat, els paràmetres que s'han estudiat han estat la distància entre la pols i la zona de generació de plasma, la mida de la partícula i la porositat de la placa suport.
Pel que fa a la modificació mitjançant la utilització de plasma atmosfèric, s'ha dissenyat un sistema que permet utilitzar una torxa de plasma atmosfèric comercial (Openair® de Plasmatreat GmbH) per tal de modificar materials en pols. Aquest sistema consisteix en un reactor adaptable a la torxa de plasma atmosfèric on té lloc la modificació, un sistema d'introducció de la pols dins de la zona de reacció així com també un sistema de refredament i col·lecció del material modificat que conjuntament permeten un funcionament quasi-continu del tractament.
S'ha utilitzat el reactor down-stream i el reactor a pressió atmosfèrica per tal de modificar tres tipus diferents de negre de carboni (N134, XPB 171 i Vulcan XC-72). D'altra banda, s'ha grafititzat i extret el N134 prèviament a la modificació per tal de realitzar un estudi sobre la influència de l'estructura superficial així com també de la presència d'impureses sobre la superfície del NC. L'oxidació i l'augment de nitrogen en superfície han estat les dues modificacions que s'han estudiat principalment per tal de comparar el resultat obtingut per les tècniques presentades.
El NC s'ha caracteritzat mitjançant diverses tècniques analítiques per tal de poder obtenir informació sobre els canvis produïts durant la modificació per plasma. Aquestes tècniques inclouen superfície específica, XRD, WAXS, STM per tal d'estudiar els canvis en la seva morfologia i estructura de la superfície. D'altra banda, per tal d'estudiar els canvis en la composició química s'han emprat mesures de pH, valoracions àcid/base i XPS.
Finalment, alguns dels negres de caboni modificats han estat seleccionats per tal de ser avaluats en aplicacions finals tal i com són el reforçament d'elastòmers i la seva activitat vers la reducció d'oxigen utilitzada en les PEMFC per tal d'eliminar els metalls nobles. En el primer cas, s'ha estudiat l'efecte sobre la cinètica i el mecanisme de vulcanització del negre de carboni modificat mitjançant el plasma atmosfèric. Aquest estudi s'ha dut a terme utilitzant dues tècniques complementaries com són les corbes reomètriques i la vulcanització de molècules model (MCV). També s'han realitzat mesures d'adsorció de polímer sobre el NC i Bound Rubber per tal d'estudiar la interacció polímer-càrrega la qual presenta una gran influència en les propietats finals dels materials. D'altra banda, s'ha estudiat també la capacitat del NC modificat vers a la reducció d'oxigen a partir de voltametria cíclica i s'han determinat les propietats del NC que poden influir de manera rellevant en l'activitat cataítica final del NC per a aquesta reacció. Tot i que es necessari fer una preparació posterior al tractament de plasma per a aquesta aplicació, el material final pot contribuir notablement a la eliminació de metalls nobles com a catalitzadors de reducció d'oxigen en les Piles de Combustible.
The present works deals with plasma modification of carbon black (CB). Although this type of treatment is widely used on flat surfaces handling problems should be overcome in order to treat powders as CB. In this study CB has been modified both by means of low-pressure and atmospheric pressure non-equilibrium plasmas. In order to accomplish this objective three different plasma reactors have been set-up; two at low pressure and one at atmospheric pressure working conditions.
Low pressure plasma reactors utilised in this work consist in a down-stream and a fluidised bed system working at Radio Frequency generation power (RF 13,56 MHz). Both reactors have been optimized to treat powder materials. For the down-stream reactor, position of the reactive gas inlet, and treatment conditions such as generator power and time have been studied for oxygen, nitrogen and ammonia treatments. For the fluidized bed reactor the distance of the powder sample to the plasma generation zone, particle size and support porosity have been taken into account.
Concerning atmospheric plasma, a device has been set up in order to adapt a commercial plasma torch (Openair® from Plasmatreat GmbH), for powder modification. An adaptable reactor, a method to introduce the powder in the plasma zone as well as a collecting system had been developed in order to obtain a quasi-continuous modification treatment.
Three types of CBs, N134, XPB 171 and Vulcan XC-72 have been modified in both the down-stream and the atmospheric plasma system. Graphitization and extraction of N134 were also carried out before plasma modification in order to study the effect of both impurities and surface structure of the CB during plasma modification. Surface oxidation and nitrogen enrichment were the two main studied treatments in both systems which allowed comparing their performances.
Unmodified and Modified CBs have been characterised from several points of view. Specific surface area, XRD, WAXS and STM have been used in order to study morphological and surface structure changes. On the other hand, pH measurements, acid/base titration and XPS were employed in order to study the surface chemistry composition changes that had taken place during plasma modification.
Some of the modified CB grades were selected in order to be tested in final applications such as rubber reinforcement and oxygen reduction non-noble metal catalyst for PEMFC. In the first case, the effect of atmospheric plasma treatment on the vulcanization kinetics and mechanism has been evaluated both by rheometre curves and the model compounding approach. Studies about the polymer-filler interaction have been also carried out by calculating bound rubber and adsorption from polymer solution. Last but not least, plasma modification capacity to enhance the oxygen reduction activity to obtain non-noble metal catalysts for PEMFC has been evaluated after the correspondent preparation. Oxygen reduction activity has been studied by means of cyclic voltammetry. The main CB properties which could play an important role in such applications have been analyzed.
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Connolly, Kevin John. "A coarse mesh radiation transport method for prismatic block thermal reactors in two dimensions." Thesis, Georgia Institute of Technology, 2011. http://hdl.handle.net/1853/44823.
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In this paper, the coarse mesh transport method is extended to hexagonal geometry. This stochastic-deterministic hybrid transport method calculates the eigenvalue and explicit pin fission density profile of hexagonal reactor cores. It models the exact detail within complex heterogeneous cores without homogenizing regions or materials, and neither block-level nor core-level asymmetry poses any limitations to the method. It solves eigenvalue problems by first splitting the core into a set of coarse meshes, and then using Monte Carlo methods to create a library of response expansion coefficients, found by expanding the angular current in phase-space distribution using a set of polynomials orthogonal on the angular half-space defined by mesh boundaries. The coarse meshes are coupled by the angular current at their interfaces. A deterministic sweeping procedure is then used to iteratively construct the solution.
The method is evaluated using benchmark problems based on a gas-cooled, graphite-moderated high temperature reactor. The method quickly solves problems to any level of detail desired by the user. In this paper, it is used to explicitly calculate the fission density of individual fuel pins and determine the reactivity worth of individual control rods. In every case, results for the core multiplication factor and pin fission density distribution are found within several minutes. Results are highly accurate when compared to direct Monte Carlo reference solutions; errors in the eigenvalue calculations are on the order of 0.02%, and errors in the pin fission density average less than 0.1%.
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Kamal, Rajit. "CFD simulation of mixing in a carbon black reactor : optimum geometry and momentum ratio." Diss., Georgia Institute of Technology, 2000. http://hdl.handle.net/1853/11254.
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Price, Richard D. "S-block metal chemistry of iminophosphoranes, phosphonium ylides and related systems : a synthetic and structural investigation." Thesis, Durham University, 1999. http://etheses.dur.ac.uk/4564/.
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This thesis details the synthesis and characterisation of s-block metal (lithium, sodium and magnesium) phosphonium ylide, R(_3)PCHR', and iminophosphorane complexes, R(_3)PNR', together with some related phosphine oxide, R(_3)PO, and sulfide, R(_3)PS, species, where R= Ph or Me(_2)N and R' = H, Me or Ph. The first three chapters of the thesis provide an introduction to the topic, with details of the experimental methods employed and results obtained. Chapter 4 presents a systematic study of Lewis base complexed s-block metal aryloxides, (ArOM L)(_2) where Ar = C(_6)H(_3)Ph(_2) or MeC(_6)H(_2)((^1)Bu)(_2), L = R(_3)PCHR', R(_3)PNR', R(_3)PO or R(_3)PS, and M = Li, Na, and (ArO)(_2)Mg(L)(_2) where Ar = MeC(_6)H(_2)(^1)Bu)(_2) and L = R(_3)PCHR’ or R(_3)PNR'. This includes a discussion of the single crystal XRD structures of the eight neutral ligands used, L, and ten new complexes containing either lithium or sodium. Chapter 5 describes the application of some related s-block metal ylide complexes, e.g. Ph(_3)PCHMe-LiN(CH(_2)Ph(_2))(_2) and Ph(_3)PCHMe-NaN(SiMe(_3))(_2), to the Wittig reaction, together with some solution-state and solid-state discussions (two single crystal XRD structures) of s-block metal amide-phosphonium ylide complexes, R(_3)PCHR'.MNR'(_2) where R = Ph or Me(_2)N, R’ = H or Me, and R" = SiMe(_3) or CH(_2)Ph Chapter 6 details a range of N-s-block metallated iminophosphorane complexes (e.g. Ph(_3)PNLi-LiBr.2thf and R(_3)PNMgX-L where R = Ph or Me(_2)N and L = Lewis base) their application to transmetallation reactions with copper(I) compounds, solution-state and solid-state NMR studies and six new single- crystal XRD structures. Chapter 7 describes some very recent work involving alkyldiphenylphosphonium ylides, MePh(_2)PCHPh, and imines, MePh(_2)PNPh, including a single crystal XRD structural study of the latter and three of its lithium derivatives, e.g. [CH(_2)LiPh(_2)PNPh](_4). Chapter 8 is concerned with a number of unexpected results, including the synthesis, solid-state structure and proposed mechanism of a novel A^-phosphino- iminophosphorane, Ph(_2)(C(_3)H(_4)Ph)PNP(C(_3)H(_5))Ph, and two aminophosphonium salts, [R(_3)PNH(_2)](^+)[OC(_6)H(_3)Ph(_2)]" where R = Ph or Me(_2)N.
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Patel, Nikhil. "Studies On The Combustion And Gasification Of Concentrated Distillery Effluent." Thesis, Indian Institute of Science, 2000. https://etd.iisc.ac.in/handle/2005/274.
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The need for effective disposal of huge volumes of industrial waste is becoming more challenging due to expected imposition of stringent pollution control regulations in the near future. Thermochemical conversion, particularly gasification of organics in the waste is considered the best route from the perspective of volume reduction and prevalent eco-friendly concept of waste-to-energy transformation. It is considered imperative to have adequate understanding of basic combustion features as a part of the thermochemical conversion process, leading to gasification. The aim of this thesis is to understand the fundamental combustion processes associated with one of the top listed hazardous wastes from distilleries (Biochemical Oxygen Demand (BOD) ~ 40,000 - 50,000 mg/L), commonly known as vinasse, stillage or spent wash, through experiments and modeling efforts. Specially designed experiments on distillery effluent combustion and gasification are conducted in laboratory scale reactors.
As an essential starting point of the studies on ignition and combustion of distillery effluent containing solids consisting of 62 ± 2 % organics and 38 ± 2 % inorganics (primarily sugarcane derivatives), the roles of solids concentration, drop size and ambient temperature were investigated through experiments on (1) liquid droplets of 65 % and 77 % solids (remaining water) and (2) spheres of dried effluent (100 % solids) of size 0.5 mm to 20 mm diameter combusted at ambient temperatures of 773 to 1273 K. The investigation reveals that the droplets burn with two distinct regimes of combustion, flaming and char glowing. The ignition delay ‘t1’ of the droplets increased with size as is in the case of non-volatile droplets, while that of bone-dry spheres was found to be independent of size. The ‘t1’ decreased with increase in solids concentration. The ignition delay has showed an Arrhenius dependence on temperature. The initial ignition of the droplets and the dry spheres led to either homogeneous (flaming) or heterogeneous (flameless) combustion, depending on the ambient temperature in the case of sphere and on solid concentration and the ambient temperature, in the case of liquid droplets. The weight loss during the flaming combustion was found to be 50 - 80 % while during the char glowing it was 10-20 % depending on the ambient temperature. The flaming time tc is observed as tc~ d2c , as in the case of liquid fuel droplets and wood spheres. The char glowing time tc' is observed as tc ~ d2c as in the case of wood char, though the inert content of effluent char is as large as 50 % compared to 2 - 3 % in wood char. In the case of initial flameless combustion, the char combustion rate is observed to be lower. The heterogeneous char combustion in quiescent air in controlled temperature conditions has been studied and modeled using one-dimensional, spherico-symmetric conservation equations and the model predicts most of the features of char combustion satisfactorily. The measured surface and core temperatures during char glowing typically are in the range of 200 to 400 K and are higher than the controlled temperature of
the furnace.
Based on the results of single droplet combustion studies, combustion experiments were conducted in a laboratory scale vertical reactor (throughput ranging from 4 to 10 g/s) with the primary aim of obtaining sustained combustion. Spray of effluents with 50 % and 60 % solids (calorific value 6.8 - 8.2 MJ/kg), achieved by an air blast atomizer, was injected into a hot oxidizing environment to determine the parameters (ambient temperature and air-fuel ratio) at which auto-ignition could occur and subsequently studies were continued to investigate pre-ignition, ignition and combustion processes. Effluent with lower solids concentration was considered first from the point of view of the less expensive evaporator required in the field conditions for concentration and a spin-off in terms of better atomization consequently. Three classes of experiments were conducted: 1) Effluent injection from the wall with no auxiliary heat input, 2) Effluent injection with auxiliary heat input and 3) effluent injection within kerosene enveloping flame. Though individual particles in the spray periphery were found to combust, sustained spray combustion was not achieved in any of the three sets of experiments even with fine atomization. While conducting the third class of experiments in an inclined metallic reactor, sustained combustion of the pool resulting of accumulated spray seemed to result in large conversion of carbon. This led to the adoption of a new concept for effluent combustion in which the residence time is controlled by varying reactor inclination and the regenerative heat transfer from the product gases supplies heat for endothermic pre-ignition process occurring on the bed.
Combustion and gasification experiments were conducted in an inclined plate reactor with rectangular cross section (80 mm x 160 mm) and 3000 mm long. A support flame was found necessary in the injection zone in addition to the regenerative heat transfer. Effluent with 60% solids was injected as film on the reactor bed. This film disintegrated into fine particles due to induced aerodynamic stretching and shear stripping. Combustion of individual particles provided exothermic heat profile and resulted into high carbon
conversion. However, effluent clogging in the cold injection zone hindered system from attaining steady state. Effluent injected directly on the hot zone caused it to remain mobile due to the spheroidal evaporation and thus assuaging this problem. Improved mass distribution was achieved by displacing nozzle laterally in a cycle, actuated by a mechanism. Consistent injection led to sustained effluent combustion with resulting carbon conversion in excess of 98 %. The typical gas fractions obtained during gasification condition (air ratio = 0.3) were CO2 = 14.0 %, CO = 7.0 %, H2 = 12.9 %, CH4 - 1 % H2S = 0.6 - 0.8 % and about 2 % of saturated moisture. This composition varied due to variation in temperature (± 30 K) and is attributed to combined effect of local flow variations, shifting zones of endothermic processes due to flowing of evaporating effluent over a large area. In order to minimize this problem, experiments were conducted by injecting effluent at higher solids (73 % solids is found injectable). The effluent was found to combust close to the injection location-due to the reduced ignition delay and lower endothermic evaporation load helped raising the local temperature. This caused the pyrolysis to occur in this hottest zone of the reactor with higher heating rates resulting in larger yield of devolatilized products and improved char conversion. Effluent combustion was found to sustain temperature in the reactor under sub-stoichiometric conditions without support of auxiliary heat input and achieved high carbon conversion. These results inspired the use of higher concentration effluent, which is also known in the case of wood to have improved gasification efficiency due to reduction in moisture fraction. In addition, the recent studies on the sulfur emission in the case of black liquor combustion in recovery boilers have revealed that with increase in solids concentration, release of sulfur in gas phase is reduces. The required concentration can be carried out using low-grade waste heat from the reactor itself. It was found through experiments that, even though spray ignition occurred at this concentration, the confined reactor space prevented the spray from attaining sustained combustion. This led to the conduct of experiments in a new vertical reactor with adequate thermal inertia, essential to prevent variations in local temperature to reach a steady state gasification and required space to accommodate the spray.
The results of the experiments conducted in the vertical reactor in which effluents with 73 % solids, heated close to the boiling point and injected as fine spray in a top-down firing mode are consolidated and reported in the thesis in detail. Single particle combustion with enveloping faint flame was seen unlike stable flame found in coal water slurry spray combustion. Sustained gasification of gas-entrained particles occurred at reactor temperature in the range of 950 K - 1000 K and sub-stoichiometric air ratio 03 - 0.35 without the support of auxiliary fuel. The typical gas fractions obtained during gasification condition (air ratio = 0.3) were CO2 = 10.0 -11.5 %, CO - 10.0 - 12.0 %, H2 - 6.7 - 8.0 %, CH4 = 1.75 % H2S = 0.2 - 0.4 % and about 2 % of saturated moisture. The carbon conversion obtained was in the range of 95 - 96 %. These experiments have provided the conditions for gasification. The extraction of potassium salts (mostly sulfates, carbonate and chloride) from the ash, using a simple water leaching process, was found to recover these chemicals to as high an extent as 70 - 75 % of total ash.
In summary it is concluded that increasing the solid concentrations to as high levels as acceptable to the system (~ 75 %) and introducing as a fine spray of heated material (~ 363 K) into furnace with air at sub-stoichiometric conditions in a counter current combustion reactor will provide the frame work for the design of a gasification system for vinasse and similar effluent material.
The thesis consists of seven chapters. Chapter 1 introduces the problem and motivation of the work presented in the thesis. Literature review is presented in Chapter 2. The Chapter 3 deals with the single particle combustion studies. The results of effluent spray combustion experiments conducted in a laboratory scale vertical reactor are presented in Chapter 4. The results of combustion and gasification experiments conducted in another variant of a reactor, namely, inclined flat plate rectangular reactor is consolidated in Chapter 5. The results of gas-entrained spray gasification experiment of higher concentration effluent injected as spray in the vertical reactor are presented in Chapter 6. The general conclusions and scope for the future work are presented in the concluding chapter 7.
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Patel, Nikhil. "Studies On The Combustion And Gasification Of Concentrated Distillery Effluent." Thesis, Indian Institute of Science, 2000. http://hdl.handle.net/2005/274.
Full textAbstract:
The need for effective disposal of huge volumes of industrial waste is becoming more challenging due to expected imposition of stringent pollution control regulations in the near future. Thermochemical conversion, particularly gasification of organics in the waste is considered the best route from the perspective of volume reduction and prevalent eco-friendly concept of waste-to-energy transformation. It is considered imperative to have adequate understanding of basic combustion features as a part of the thermochemical conversion process, leading to gasification. The aim of this thesis is to understand the fundamental combustion processes associated with one of the top listed hazardous wastes from distilleries (Biochemical Oxygen Demand (BOD) ~ 40,000 - 50,000 mg/L), commonly known as vinasse, stillage or spent wash, through experiments and modeling efforts. Specially designed experiments on distillery effluent combustion and gasification are conducted in laboratory scale reactors.
As an essential starting point of the studies on ignition and combustion of distillery effluent containing solids consisting of 62 ± 2 % organics and 38 ± 2 % inorganics (primarily sugarcane derivatives), the roles of solids concentration, drop size and ambient temperature were investigated through experiments on (1) liquid droplets of 65 % and 77 % solids (remaining water) and (2) spheres of dried effluent (100 % solids) of size 0.5 mm to 20 mm diameter combusted at ambient temperatures of 773 to 1273 K. The investigation reveals that the droplets burn with two distinct regimes of combustion, flaming and char glowing. The ignition delay ‘t1’ of the droplets increased with size as is in the case of non-volatile droplets, while that of bone-dry spheres was found to be independent of size. The ‘t1’ decreased with increase in solids concentration. The ignition delay has showed an Arrhenius dependence on temperature. The initial ignition of the droplets and the dry spheres led to either homogeneous (flaming) or heterogeneous (flameless) combustion, depending on the ambient temperature in the case of sphere and on solid concentration and the ambient temperature, in the case of liquid droplets. The weight loss during the flaming combustion was found to be 50 - 80 % while during the char glowing it was 10-20 % depending on the ambient temperature. The flaming time tc is observed as tc~ d2c , as in the case of liquid fuel droplets and wood spheres. The char glowing time tc' is observed as tc ~ d2c as in the case of wood char, though the inert content of effluent char is as large as 50 % compared to 2 - 3 % in wood char. In the case of initial flameless combustion, the char combustion rate is observed to be lower. The heterogeneous char combustion in quiescent air in controlled temperature conditions has been studied and modeled using one-dimensional, spherico-symmetric conservation equations and the model predicts most of the features of char combustion satisfactorily. The measured surface and core temperatures during char glowing typically are in the range of 200 to 400 K and are higher than the controlled temperature of
the furnace.
Based on the results of single droplet combustion studies, combustion experiments were conducted in a laboratory scale vertical reactor (throughput ranging from 4 to 10 g/s) with the primary aim of obtaining sustained combustion. Spray of effluents with 50 % and 60 % solids (calorific value 6.8 - 8.2 MJ/kg), achieved by an air blast atomizer, was injected into a hot oxidizing environment to determine the parameters (ambient temperature and air-fuel ratio) at which auto-ignition could occur and subsequently studies were continued to investigate pre-ignition, ignition and combustion processes. Effluent with lower solids concentration was considered first from the point of view of the less expensive evaporator required in the field conditions for concentration and a spin-off in terms of better atomization consequently. Three classes of experiments were conducted: 1) Effluent injection from the wall with no auxiliary heat input, 2) Effluent injection with auxiliary heat input and 3) effluent injection within kerosene enveloping flame. Though individual particles in the spray periphery were found to combust, sustained spray combustion was not achieved in any of the three sets of experiments even with fine atomization. While conducting the third class of experiments in an inclined metallic reactor, sustained combustion of the pool resulting of accumulated spray seemed to result in large conversion of carbon. This led to the adoption of a new concept for effluent combustion in which the residence time is controlled by varying reactor inclination and the regenerative heat transfer from the product gases supplies heat for endothermic pre-ignition process occurring on the bed.
Combustion and gasification experiments were conducted in an inclined plate reactor with rectangular cross section (80 mm x 160 mm) and 3000 mm long. A support flame was found necessary in the injection zone in addition to the regenerative heat transfer. Effluent with 60% solids was injected as film on the reactor bed. This film disintegrated into fine particles due to induced aerodynamic stretching and shear stripping. Combustion of individual particles provided exothermic heat profile and resulted into high carbon
conversion. However, effluent clogging in the cold injection zone hindered system from attaining steady state. Effluent injected directly on the hot zone caused it to remain mobile due to the spheroidal evaporation and thus assuaging this problem. Improved mass distribution was achieved by displacing nozzle laterally in a cycle, actuated by a mechanism. Consistent injection led to sustained effluent combustion with resulting carbon conversion in excess of 98 %. The typical gas fractions obtained during gasification condition (air ratio = 0.3) were CO2 = 14.0 %, CO = 7.0 %, H2 = 12.9 %, CH4 - 1 % H2S = 0.6 - 0.8 % and about 2 % of saturated moisture. This composition varied due to variation in temperature (± 30 K) and is attributed to combined effect of local flow variations, shifting zones of endothermic processes due to flowing of evaporating effluent over a large area. In order to minimize this problem, experiments were conducted by injecting effluent at higher solids (73 % solids is found injectable). The effluent was found to combust close to the injection location-due to the reduced ignition delay and lower endothermic evaporation load helped raising the local temperature. This caused the pyrolysis to occur in this hottest zone of the reactor with higher heating rates resulting in larger yield of devolatilized products and improved char conversion. Effluent combustion was found to sustain temperature in the reactor under sub-stoichiometric conditions without support of auxiliary heat input and achieved high carbon conversion. These results inspired the use of higher concentration effluent, which is also known in the case of wood to have improved gasification efficiency due to reduction in moisture fraction. In addition, the recent studies on the sulfur emission in the case of black liquor combustion in recovery boilers have revealed that with increase in solids concentration, release of sulfur in gas phase is reduces. The required concentration can be carried out using low-grade waste heat from the reactor itself. It was found through experiments that, even though spray ignition occurred at this concentration, the confined reactor space prevented the spray from attaining sustained combustion. This led to the conduct of experiments in a new vertical reactor with adequate thermal inertia, essential to prevent variations in local temperature to reach a steady state gasification and required space to accommodate the spray.
The results of the experiments conducted in the vertical reactor in which effluents with 73 % solids, heated close to the boiling point and injected as fine spray in a top-down firing mode are consolidated and reported in the thesis in detail. Single particle combustion with enveloping faint flame was seen unlike stable flame found in coal water slurry spray combustion. Sustained gasification of gas-entrained particles occurred at reactor temperature in the range of 950 K - 1000 K and sub-stoichiometric air ratio 03 - 0.35 without the support of auxiliary fuel. The typical gas fractions obtained during gasification condition (air ratio = 0.3) were CO2 = 10.0 -11.5 %, CO - 10.0 - 12.0 %, H2 - 6.7 - 8.0 %, CH4 = 1.75 % H2S = 0.2 - 0.4 % and about 2 % of saturated moisture. The carbon conversion obtained was in the range of 95 - 96 %. These experiments have provided the conditions for gasification. The extraction of potassium salts (mostly sulfates, carbonate and chloride) from the ash, using a simple water leaching process, was found to recover these chemicals to as high an extent as 70 - 75 % of total ash.
In summary it is concluded that increasing the solid concentrations to as high levels as acceptable to the system (~ 75 %) and introducing as a fine spray of heated material (~ 363 K) into furnace with air at sub-stoichiometric conditions in a counter current combustion reactor will provide the frame work for the design of a gasification system for vinasse and similar effluent material.
The thesis consists of seven chapters. Chapter 1 introduces the problem and motivation of the work presented in the thesis. Literature review is presented in Chapter 2. The Chapter 3 deals with the single particle combustion studies. The results of effluent spray combustion experiments conducted in a laboratory scale vertical reactor are presented in Chapter 4. The results of combustion and gasification experiments conducted in another variant of a reactor, namely, inclined flat plate rectangular reactor is consolidated in Chapter 5. The results of gas-entrained spray gasification experiment of higher concentration effluent injected as spray in the vertical reactor are presented in Chapter 6. The general conclusions and scope for the future work are presented in the concluding chapter 7.
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Young, Christopher Michael. "Pressure Effects on Black Liquor Gasification." Diss., Georgia Institute of Technology, 2006. http://hdl.handle.net/1853/11539.
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Gasification of black liquor is an alternative to the combustion of black liquor, which is currently the dominant form of chemical recovery in the paper industry. Gasification of black liquor offers the possibility of higher thermal efficiencies than combustion, reducing manufacturing costs and creating new revenue streams through a forest biorefinery. Pressurizing the gasification reactor further enhances the efficiency advantage of gasification over combustion.
This study uses a pressurized entrained flow reactor (PEFR) to study black liquor gasification behavior under pressures, temperatures, and heating rates similar to those of next-generation high-temperature black liquor gasifiers. The effects of pressure on black liquor char morphology, gasification rates, pyrolysis carbon yields, and sulfur phase distribution were studied. These characteristics were investigated in three main groups of experiments at 900oC: pyrolysis (100% N2), gasification with constant partial pressure (0.25 bar H2O and 0.50 bar CO2), and gasification with constant mole fraction (10% CO2, 2% H2O, 1.7% CO, 0.3% H2), under five, ten, and fifteen bar total pressure.
It was found that pressure had an impact on the char physical characteristics immediately after the char entered the reactor. Increasing pressure had the effect of decreasing the porosity of the chars. Pressure also affected particle destruction and reagglomeration mechanisms. Surface areas of gasification chars decreased with increasing pressures, but only at low carbon conversions.
The rate of carbon conversion in gasification was shown to be a function of the gas composition near the particle, with higher levels of inhibiting gases slowing carbon conversion. The same phenomenon of product gas inhibition observed in gasification was used to explain carbon conversions in pyrolysis reactions.
Sulfur distribution between condensed and gas phases was unaffected by increasing total pressure in the residence times investigated. Significant amounts of sulfur are lost during initial devolatilization. With water present this gas phase sulfur forms H2S and did not return to the condensed phase.
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Watts, Mark. "Anterior-posterior ground reaction force characteristics for post-block foot contacts in sprint running /." St. Lucia, Qld, 2004. http://adt.library.uq.edu.au/public/adt-QU20041103.152436/index.html.
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Le, Nôtre Yvan. "Etude de la réponse dynamique du Bloc Réacteur soumis à une sollicitation extrême : Co-simulation implicite/explicite multi-échelle en temps pour la dynamique du contact." Electronic Thesis or Diss., Lyon, INSA, 2023. http://www.theses.fr/2023ISAL0055.
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Les centrales nucléaires sont une source de production d'énergie importante en France. Cependant, suite aux différents accidents et aux risques encourus avec cette technologie, la sûreté nucléaire est une préoccupation mondiale. En France, des normes sont imposées continuellement sur les installations nucléaires existantes et sur les prochaines générations en développement. Parmi les nombreux aspects de la sûreté nucléaire, le dimensionnement des structures mécaniques est un sujet important pour les acteurs industriels. L'activité principale de l'entreprise Framatome concerne le dimensionnement et la justification des centrales nucléaires. Celles-ci doivent être conçues pour résister à des conditions extrêmes d'utilisation telles que des séismes, des crashs d'avion ou encore des ruptures de tuyauterie. La modélisation numérique de ce type de chargement passe par des analyses dynamiques temporelles afin de considérer ces phénomènes multi-échelles en temps. Cependant, réaliser ces analyses demande beaucoup de temps CPU et de mémoire. L'objectif de la thèse est le développement d'un nouvel intégrateur hétérogène (différents schémas d'intégration) asynchrone (différents pas de temps), basé sur la méthode de couplage GC, ayant de meilleures propriétés relatives à la conservation énergétique. En effet, les phénomènes multi-échelles en temps présents dans le bloc réacteur sont des cas d'usages favorables aux méthodes multi-échelles en temps, avec un intégrateur explicite pour les zones de contact, comportant une discrétisation temporelle fine, et un intégrateur implicite pour le reste de la structure, discrétisé par des pas de temps plus gros. Un démonstrateur de co-simulation est développé entre les logiciels Code Aster et Europlexus pour se rapprocher d'un développement industriel et ainsi montrer le gain de performance, pour un modèle tridimensionnel de bloc réacteur, apporté par les approches de co-simulation multi-échelles en tempsNuclear power plants are an important source of energy production in France. However, following the various accidents and risks associated with this technology, nuclear safety is a global concern. In France, standards are continually being imposed on existing nuclear facilities and on the next generations under development. Among the many aspects of nuclear safety, the dimensioning of mechanical structures is an important subject for industrial players. Framatome's core business is the design and justification of nuclear power plants. These must be designed to withstand extreme operating conditions, such as earthquakes, plane crashes or pipe ruptures. Numerical modeling of this type of loading requires dynamic temporal analyses to consider these multi-scale phenomena. However, such analyses are CPU and memory intensive. The aim of this thesis is to develop a new heterogeneous (different integration schemes) and asynchronous (different time steps) integrator, based on the GC coupling method, with improved energy conservation properties. The multi-scale phenomena present in the reactor block are simulated using an explicit integrator with small time steps for the contact zones and an implicit integrator with large time steps for the rest of the structure. A co-simulation demonstrator is developed between the Code Aster and Europlexus software packages in order to get closer to an industrial development and thus demonstrate the performance gain, for a three-dimensional reactor block model, provided by the multi-time-scale co-simulation approaches
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Marklund, Magnus. "Pressurized entrained-flow high temperature black liquor gasification : CFD based reactor scale-up method and spray burner characterization /." Luleå : Division of Fluid Mechanics, Luleå University of Technology, 2006. http://epubl.ltu.se/1402-1544/2006/42LTU-DT-0642-SE.pdf.
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Pirgalioglu, Saltuk. "Catalytic Ozonation Of Dye Solutions In A Semi-batch Reactor." Master's thesis, METU, 2008. http://etd.lib.metu.edu.tr/upload/3/12610158/index.pdf.
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Treatment of textile wastewaters containing dye materials using the conventional methods based on biological treatment is not possible. In order to overcome this problem, ozonation based on the oxidation of organic pollutants with ozone gas dissolved in aqueous phase have been studied widely. Catalytic ozonation and advanced oxidation processes (AOP) are also used in order to increase the efficiency of sole ozonation
In this work, catalytic ozonation processes in the presence of Copper Sulfide (CuS) powder and a synthesized catalyst by the impregnation of iron on alumina (Fe/Al2O3) were studied separately in the treatment of dye solutions, namely Remazol Brilliant Blue-R (RBBR) and Reactive Black-5 (RB-5). Besides catalytic ozonation runs, ozonation parameters and ozonation mechanism were also studied and a model was developed for the semi-batch ozonation.
Both catalysts increased the oxidation of side products measured by the decrease in the amount of total organic carbon (TOC) in the treated dye solutions. Dye removal rates were also enhanced in the treatment of RB-5 dye solutions while no significant effect was observed on dye removal rates of RBBR solutions.
TOC removals above 90% were observed in the catalytic ozonation using CuS for both of the dye solutions at pH =10 having initial dye concentration of 100 mg/L. The most significant effect of the catalyst addition was observed at pH = 3 where the TOC removals of non-catalytic ozonation were the lowest. CuS addition increased percent TOC removal at the end of the reaction period of 80 min by 123% in the treatment of 100 mg/L RBBR solution, and by 65% in the treatment of 100 mg/L RB-5 solution at pH = 3. On the other hand, addition of Fe/Al2O3 catalyst increased TOC removal of 100 mg/L RB-5 solution by 52 % at pH = 3.
In addition, volumetric mass transfer coefficients (kLa) of ozone in the absence and in the presence of a chemical reaction between dye and ozone were estimated from modeling. A correlation for the enhancement factor of ozone absorbed into dye solutions in terms of initial dye concentration was obtained and reported.
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Buquoi, John Quentin III. "Exploration Using Reaction Temperature to Tailor the Degree of Order in Micro-Block Copolymer Proton Exchange Membranes." Wright State University / OhioLINK, 2010. http://rave.ohiolink.edu/etdc/view?acc_num=wright1274493418.
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Doseděl, Jakub. "Parní turbína pro biomasový blok." Master's thesis, Vysoké učení technické v Brně. Fakulta strojního inženýrství, 2020. http://www.nusl.cz/ntk/nusl-417844.
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The aim of this diploma thesis is a design of a condensing steam turbine based on technical specification of inlet steam - maximal mass flow 120 t/h, temperature 440 °C; on temperature in deaerator 125 °C; on mass flow 0 – 60 t/h and pressure 3,0 bar(a) of regulated steam extraction and on ambient temperature in the vicinity 25 °C. The result contains steam turbine with reaction blading, work output 28,76 MWe and efficiency 82 %.
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Bergin, Cathy. "Resistance and reaction : Black American fictional representations of the Communist Party, 1940-1952." Thesis, University of Sussex, 2004. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.402678.
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The thesis is an investigation into representations of the Communist Party in black American fiction from 1940 to 1952. The focal texts are Richard Wright's Native Son (1940), Chester Himes's Lonely Crusade (1947) and Ralph Ellison's Invisible Man (1952). I examine the impact of Communism on a generation of black writers and consider how black identity in the novels is constructed in relation to the political ideology of the Communist Party. Placing the novels in their socio-historical context I take issue with many of the literary-critical assumptions about the "anti- Communism" of the three novels and focus rather on the historically specific nature of their engagement with the Communist Party. I argue that where negative Communist Party fictional representation is apparent, Communism is not dismissed as incapable of meeting the demands of black political identity but castigated for its refusal to do so. A detailed focus on the political milieu in which these texts operate therefore challenges many of the presumptions, about the "inability" of Communism to comprehend racial oppression, which dominate literary critical approaches to these novels. The textual analysis of the three novels which follows is informed by the complex formations of black political agency presumed and reproduced by American Communism during the Depression
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Cowan, Jonathan Glenn. "Geochemistry of reaction zone source rocks and black smoker fluids in the Troodos ophiolite." Thesis, University of Newcastle Upon Tyne, 1989. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.417479.
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Uppenkamp, Daniel Alan. "Two Fundamental Building Blocks to Provide Quick Reaction Capabilities for the Department of Defense." Wright State University / OhioLINK, 2013. http://rave.ohiolink.edu/etdc/view?acc_num=wright1367247524.
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Medvecz, Patrick J. "Spectroscopic evaluation of the gas phase above a burning black liquor char bed." Diss., Georgia Institute of Technology, 1991. http://hdl.handle.net/1853/5759.
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Chen, Xiaowen. "Kinetics of the Direct Causticizing Reaction between Black Liquor and Titanates During Low Temperature Gasification." Fogler Library, University of Maine, 2005. http://www.library.umaine.edu/theses/pdf/ChenX2005.pdf.
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Clauser, James Donald. "A comparison of the reaction to a colorized film over its black and white counterpart." Instructions for remote access. Click here to access this electronic resource. Access available to Kutztown University faculty, staff, and students only, 1991. http://www.kutztown.edu/library/services/remote_access.asp.
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Thesis (M.S.)--Kutztown University of Pennsylvania, 1991.Source: Masters Abstracts International, Volume: 45-06, page: 2706. Abstract precedes thesis as [1] preliminary leaf. Typescript. Includes bibliographical references (leaves 66-67).
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Severin, Erik Jon. "Array-based vapor sensing using conductive carbon black-polymer composite thin film detectors : thesis /." Caltech Library System, electronic theses, 1999. http://etd.caltech.edu/etd/available/etd-12272004-162841/.
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Thesis (Ph.D.)--California Institute of Technology, 1999."UMI number: 9941121"--T.p. verso. Includes bibliographical references. Also available on microfilm. On-line version available via Caltech Library System.
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Larson, Shawn E. "Enantioselective Brønsted and Lewis Acid-Catalyzed Reaction Methodology: Aziridines as Building Blocks for Catalytic Asymmetric Induction." Scholar Commons, 2012. http://scholarcommons.usf.edu/etd/4357.
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Chiral molecules as with biological activity are plentiful in nature and the chemical literature; however they represent a smaller portion of the pharmaceutical drug market. As asymmetric methodologies grow more powerful, the tools are becoming available to synthesize chiral molecules in an enantioselective and efficient manner.
Recent breakthroughs in our understanding of phosphoric acid now allow for Lewis acid catalysis via pairing with alkaline earth metals. Using alkaline earth metals with chiral phosphates is an emerging approach to asymmetric methodology, but already has an influential record.
The development of new conditions for the phosphoric acid-catalyzed highly enantioselective ring-opening of meso-aziridines with a series of functionalized aromatic thiol nucleophiles is described in this thesis. This methodology utilizes commercially available aromatic thiols, a series of meso-aziridines, and a catalytic amount of VAPOL calcium phosphate to explore the substrate scope of this highly enantioselective reaction.
Additionally, the development of new conditions for a catalytic asymmetric aza-Darzens aziridine synthesis mediated by a vaulted biphenanthrol (VAPOL) magnesium phosphate salt is described in this thesis. Using simple substrates, this methodology explores the scope and reactivity of a new magnesium catalyst for an aziridination reaction capable of building chirality and complexity simultaneously.
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Joseph, Bertlyn Elvira. "Stress as a reaction to racism." Thesis, National Library of Canada = Bibliothèque nationale du Canada, 1999. http://www.collectionscanada.ca/obj/s4/f2/dsk1/tape10/PQDD_0015/MQ55114.pdf.
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Boucard, Hélène. "Contributions to the understanding of hydrothermal processes : application to black liquor." Thesis, Ecole nationale des Mines d'Albi-Carmaux, 2014. http://www.theses.fr/2014EMAC0018/document.
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La liqueur noire, sous-produit de l’industrie papetière, est convertie par un processus hydrothermal. Elle a été choisie pour son contenu élevé en eau (80 wt%), matière organique (14 wt%) et minéraux (6 wt%) qui font d'elle une biomasse à haute valeur ajoutée bien qu'encore peu exploitée. L'étude en batch, balayant une large gamme de température (350°C-600°C), permet d'identifier deux flux sortant : une proportion d'hydrogène élevée dans la phase gazeuse (600°C), ainsi qu'une phase solide, appelée coke, générée quelques soient les conditions opératoires utilisées. La génération de solide modifie la composition du milieu réactionnel en procédé batch et peut poser problème en cas de transposition en réacteur continu. Il est donc important de comprendre sa formation pour pallier ces verrous. L'analyse du résidu montre qu'à 350°C, pour des temps de réaction courts (<2h), de microparticules carbonées se forment. Leur taille est influencée par les vitesses de montée et descente en température. Pour des températures plus hautes, le solide ne présente pas d'intérêt morphologique et sa proportion massique augmente avec la température. Ainsi, une production d'hydrogène significative s'accompagnera d'un dépôt solide dans le réacteur. Une étude catalytique a donc été menée en vue d'augmenter la quantité d'hydrogène et de diminuer la formation de coke tout en travaillant à plus basse température. Cette étude, menée à 350°C et 450°C, montre que les réactions d'hydrogénation et d'oxydation mises en jeu par le catalyseur conduisent aux résultats escomptés. La conversion de molécules modèles de la liqueur noire, menée dans les mêmes conditions d'expériences, a permis d'appréhender les mécanismes majeurs mises en jeu lors de la conversion hydrothermale. Les microparticules à 350°C peuvent être valorisées. Cependant, le changement de taille et de morphologie au cours du temps interroge sur la possibilité de passer en réacteur continu. La formation de solide peut être évitée à partir de 450°C en présence de catalyseur, favorisant en parallèle la production d'hydrogène. De ce fait, ce travail de thèse aborde les verrous scientifiques, techniques et technologiques liés à la conversion hydrothermale de la liqueur noire et notamment de la formation du solide, en présence ou non de catalyseurBlack liquor, a by-product of paper industry, is converted by hydrothermal process. It was chosen for its high water content (80 wt%), organic material (14 wt%) and minerals (6 wt%) that make it a high-value biomass while still untapped. The study in batch, screening a wide temperature range (350°C-600°C), used to identify two outgoing flows: a high proportion of hydrogen in the gas phase (600°C) and a solid phase, called coke, generated regardless the operating conditions used. The generation of solid changes the composition of the reaction medium in batch process and can be problematic in case of transposition in continuous reactor. Thus it is important to understand its formation to overcome these obstacles. Analysis of the residue shows that at 350°C, for short reaction times (< 2h), carbonaceous micro-particles are formed. Their size is influenced by the temperature rates of rise and fall. For higher temperatures, the solid is of no morphological interest and its weight proportion increased with temperature. Thus, a significant production of hydrogen will be associated with a solid deposit in the reactor. A catalytic study was conducted to increase the amount of hydrogen and reduce the formation of coke while working at lower temperature. This study, conducted at 350°C and 450°C, shows that hydrogenation and oxidation reactions involved with the catalyst, lead to the expected results. Converting models molecules of black liquor, conducted with the same experimental conditions, helped to understand the major mechanisms involved during the hydrothermal conversion. The micro-particles at 350°C can be valorized. However, the change in size and morphology over time wondered about the possibility of implement in continuous reactor. The solid formation can be prevented from 450°C in the presence of catalyst, favoring in parallel hydrogen production. Therefore, this thesis deals with scientific, technical and technological locks related to hydrothermal conversion of black liquor and especially the solid formation, with or without catalyst
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Melomedov, Jascha [Verfasser]. "Novel porphyrin amino acids as building blocks for artificial photosynthetic reaction centers : photoinduced energy and electron transfer / Jascha Melomedov." Mainz : Universitätsbibliothek Mainz, 2014. http://d-nb.info/1052697038/34.
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Williams, Georgia Dill. "Atlanta's reaction to the first black mayor, Maynard H. Jackson, as seen through its major newspaper, The Atlanta Constitution." DigitalCommons@Robert W. Woodruff Library, Atlanta University Center, 1990. http://digitalcommons.auctr.edu/dissertations/639.
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This thesis investigates the reaction to Maynard H. Jackson’s election as the first black mayor of a major southern city, Atlanta, through selected articles of its major newspaper, The Atlanta Constitution, covering the period of Jackson’s announcement of his candidacy through the end of his first two years in office. This particular paper was chosen because it was the dominant day-time newspaper and because of its moderate viewpoints and its emphasis on political news. While The Atlanta Constitution was aware of race as a factor, it was able to be objective in its treatment of Jackson. For example, the articles did not elaborate on Jackson’s race, but rather his qualifications and platform which made him eligible to be mayor of Atlanta. One would expect more criticism, and more emphasis on the race issue, but there was very little of such in the newspaper’s reporting of events during the Jackson era.
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Brunson, Kennard. "POLYURETHANE-BASED POLYMER SURFACE MODIFIERS WITH ALKYL AMMONIUM CO-POLYOXETANE SOFT BLOCKS: REACTION ENGINEERING, SURFACE MORPHOLOGY AND ANTIMICROBIAL BEHAVIOR." VCU Scholars Compass, 2010. http://scholarscompass.vcu.edu/etd/2258.
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Concentrating quaternary (positive) charge at polymer surfaces is important for applications including layer-by-layer polyelectrolyte deposition and antimicrobial coatings. Prior techniques to introduce quaternary charge to the surface involve grafting of quaternary ammonium moieties to a substrate or using polyurethanes with modified hard segments however there are impracticalities involved with these techniques. In the case of the materials discussed, the quaternary charge is introduced via polyurethane based polymer surface modifiers (PSMs) with quaternized soft segments. The particular advantage to this method is that it utilizes the intrinsic phase separation between the hard and soft segments of polyurethanes. This phase separation results in the surface concentration of the soft segments. Another advantage is that unlike grafting, where modification has to take place after device fabrication, these PSMs can be incorporated with the matrix material during device fabrication. The soft segments of these quaternized polyurethanes are produced via ring opening copolymerization of oxetane monomers which possess either a trifluoroethoxy (3FOx) side chains or a quaternary ammonium side chain (C12). These soft segments are subsequently reacted with 4,4’-(methylene bis (p-cyclohexyl isocyanate)), HMDI and butanediol (BD) to form the PSM. It was initially intended to increase the concentration of quaternary ammonium charge by increasing PSM soft segment molecular weight. Unexpectedly, produced blends with surface microscale phase separation. This observation prompted further investigation of the effect of PSM soft segment molecular weight on phase separation in PSM-base polyurethane blends and the subsequent effects of this phase separation on the biocidal activity. Analysis of the surface morphology via tapping mode atomic force microscopy (TMAFM) and scanning electron microscopy (SEM) revealed varying complexities in surface morphology as a function of the PSM soft segment molecular weight and initial annealing temperature. Many of these features include what are described as nanodots (100-300 nm), micropits (0.5-2 um) and micropeaks (1-10 um). It was also observed that surface morphology continued to coarsen with time and that the larger features were typically observed in blends containing PSMs with low molecular weight soft segments. This appearance of surface morphological feature correlates with decreased biocidal activity of the PSM blends, that is, the PSM blends exhibit little to no activity upon development of phase separated features. A model has been developed for phase separation and concomitant reduction of surface quaternary charge. This model points the way to future work that will stabilize surface charge and provide durability of surface modification.
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Jacobsen, Elisabeth Egholm. "Synthesis of enantiopure building blocks for biologically active compounds by enzyme catalysis. Optimizing reaction conditions for increased enantioselectivity and activity." Doctoral thesis, Norwegian University of Science and Technology, Department of Chemistry, 2004. http://urn.kb.se/resolve?urn=urn:nbn:no:ntnu:diva-2098.
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Efficient methods for synthesis of enantiomerically pure enantiomers of a series of secondary alcohols and butanoates have been performed by kinetic resolution of the racemic alcohols and esters catalyzed by lipase B from Candida antarctica (Novozym 435). The effect of the substrate structure on E was different for transesterifications of alcohols in organic media as compared to hydrolysis of esters in buffer. The influence of different acyl donors on the enantioselectivity has also been investigated.
Derivatives of 1-phenoxy-2-alkanols have been kinetically resolved by esterification with irreversible and reversible acyl donors using lipase B from Candida antarctica (Novozym 435) as catalyst. Esterifications in eight different solvents with different water activity have been performed. For 3-bromo-1-phenoxy-2-propanol the E-values in all of the solvents were higher when the water activity was increased. The water content of the various reaction media at the same water activity was also determined.
In esterifications of secondary alcohols catalyzed by immobilized lipase B from Candida antarctica (Novozym 435) the E-values decreased during the reaction. Hydrolysis of the corresponding butanoates showed the opposite effect. When an enantiopure (R)-alcohol, related but different, was added to the transesterification reaction, the E-value was significantly enhanced.
Decreasing enantioselectivity (E-value) by conversion has also been observed in transesterification reactions of secondary alcohols catalyzed by a pure protein formulation of lipase B from Candida antarctica (Novozym 525 F). It can be concluded that the immobilization of Novozym 435 not was the reason for the decrease in E-value which was observed. Addition of a range of enantiopure alcohols caused a temporary increase in enzyme selectivity in the transesterification reaction of 3-chloro-1-phenoxy- 2-propanol with vinyl butanoate.
Enantioselective hydrolyses and ammonolyses of diethyl 3-hydroxyglutarate and dimethyl 3-hydroxyglutarate gave a maximum of 91 and 98 % enantiomeric excess, respectively, with use of immobilized lipase B from Candida antarctica (Novozym 435). Ee´s were determined using chiral GLC of the mono amides and achiral GLC of diastereomeric derivatives of the monoesters. The catalyst was re-used more than ten times with retention of high activity and selectivity.
Biocatalytic asymmetrizations of diethyl 3-hydroxyglutarate furnish a route to enantiomers of ethyl 4-cyano-3-hydroxybutanoate. The enantiopreference of different enzymes has been established by chiral chromatography. Conclusive evidence for absolute configurations has been provided by X-ray crystallographic structure determination of co-crystals of the predominant monoester (3S)-3-hydroxy pentanedioic monoethyl ester with (R)-phenylethylamine. The predominant enantiopure monoester produced by ammonolysis of diethyl 3-hydroxyglutarate catalyzed by immobilized lipase B from Candida antarctica (Novozym 435) was ethyl (3S)-4-carbamoyl-3- hydroxybutanoate. It was converted to ethyl (3S)-4-cyano-3-hydroxybutanoate in high yield and enantiomeric excess.
Paper III, IV, V, and VI are reproduced with kind permission of Elsevier, sciencedirect.com
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Engel, Tom [Verfasser], and Guido [Akademischer Betreuer] Kickelbick. "Inorganic building blocks for the synthesis of self-healing nanocomposites based on Diels-Alder reaction / Tom Engel. Betreuer: Guido Kickelbick." Saarbrücken : Saarländische Universitäts- und Landesbibliothek, 2015. http://d-nb.info/1078503354/34.
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Oetting, Andrew Henry. "Bastardizing Black-Scholes: The Recovery of Option-Implied Probability Distributions and How They React to Corporate Take Announcement." Scholarship @ Claremont, 2012. http://scholarship.claremont.edu/cmc_theses/465.
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The purpose of this paper is threefold. First, the paper builds on the work done previously done in the area of option implied probability distribution functions (PDFs) by extending the methods described by Breeden and Litzenberger (1978) to individual equity options. Second, it describes a closed-form, onto mapping from a two-dimensional volatility surface to the risk-neutral PDF. Lastly the paper performs an event study on the implied risk-neutral PDFs of companies which are the target of corporate takeover. While there was not sufficient data to determine any statistical relationship, there is observational evidence that option market implied PDFs may be predictive of future takeovers.
34
Bouxin, Florent. "Solvolyse des lignines : production de synthons aromatiques de faibles masses." Thesis, Reims, 2011. http://www.theses.fr/2011REIMS004/document.
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Les lignines ne sont pas suffisamment considérées dans les procédés de bioraffinerie. Pourtant, elles sont une source abondante de synthons aromatiques, et éléments essentiels de la rentabilité de transformation des lignocelluloses. A ce jour, les perspectives de production de synthons à partir des lignines se heurtent aux réactions de condensations des lignines, limitant leurs conversions en produits de faibles masses. Cette étude nous a permis de cerner les conditions propices à l’hydrolyse et/ou aux condensations grâce à l’étude de différentes lignines modèles soumises aux conditions d’acidolyse. D’une part, les conditions propices à l’hydrolyse des liaisons -O-4 sont l’utilisation d’une catalyse homogène (HCl), pour des températures comprises entre 120 et 140°C et une acidité de l’ordre de 0.05 M. A l’inverse, l’emploi d’une catalyse hétérogène (Montmorillonite K10) est peu efficace car elle doit s’affranchir des phénomènes d’adsorption du substrat tout en lui permettant d’accéder à ses sites actifs. D’autre part, les réactions de condensation secondaires sont exacerbées par l’emploi de l’argile de Montmorillonite, mais aussi par l’augmentation de l’acidité et de la température, elles mêmes nécessaires pour une bonne hydrolyse. La substitution de l’alcool coniférylique par le coniféraldéhyde permet de minimiser ces condensations secondaires du fait de sa forte stabilité dans les conditions d’acidolyse. Toutefois, l’incorporation de ce type de précurseur dans les lignines provoque une diminution de la fréquence des liaisons -O-4. Cette réduction du potentiel d’hydrolyse des lignines est compensée par l’exacerbation des réactions de rétroaldolisation. Pour les condensations primaires, l’acidolyse des lignines pures -O-4 nous permet d’affirmer que celles-ci, constantes face à l’augmentation de la concentration en acide et en nucléophiles aromatiques, seraient plutôt de type intramoléculaireLignins are not sufficiently considered in the biorefinery processes. However, they are a rich source of aromatic building blocks, and essential elements of lignocellulose processing viability. Although the production prospects of building blocks from lignins exist, their strong affinities for condensation reactions limit the conversion into low molecular weight products. This study allowed us to identify hydrolysis or condensation suitable conditions by studying different models lignins subjected to acidolysis conditions. On the one hand, suitable conditions for the -O-4 bonds hydrolysis are the use of homogeneous catalysis (HCl), for temperatures and HCl concentration ranged from 120 to 140 ° C and from 0.05 M to 0.1M. In contrast, the use of heterogeneous catalysis (Montmorillonite K10) is inefficient because it has to overcome the substrate adsorption and allow an access to its active sites. On the other hand, secondary condensation reactions are exacerbated by the use of Montmorillonite clay, but also by acidity and temperature increases, themselves necessary for an efficient hydrolysis.The substitution of coniferyl alcohol by coniferaldehyde minimizes these condensation reactions due to its high stability in acid conditions. However, the incorporation of this precursor in lignin leads to a decrease of -O-4 bond frequency. This reduction of lignin hydrolysis potential is compensated for the exacerbation of retroaldolisation reactions. About primary condensations, pure -O-4 lignins acidolysis allows us to claim that this kind of reactions, unchanged at the hand of acid or aromatic nuclei concentration increase, are intramolecular
35
Steffen, Julien Verfasser], Bernd [Akademischer Betreuer] [Hartke, and Carolin [Gutachter] König. "Towards High-Quality Black-Box Chemical Reaction Rates with System-Specific Potential Energy Surfaces / Julien Steffen ; Gutachter: Carolin König ; Betreuer: Bernd Hartke." Kiel : Universitätsbibliothek Kiel, 2020. http://nbn-resolving.de/urn:nbn:de:gbv:8-mods-2020-00061-7.
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Nohlgren, Ingrid. "Recovery of kraft black liquor using the titanate process : kinetics of the direct causticization reaction between sodium tri-titanate and sodium carbonate." Licentiate thesis, Luleå tekniska universitet, 1999. http://urn.kb.se/resolve?urn=urn:nbn:se:ltu:diva-18189.
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The solid state reaction between sodium tri-titanate and sodium carbonate, forming mainly sodium penta-titanate, was investigated. Experiments were carried out in a micro-differential reactor made of quartz glass at various temperatures between 800°C and 880°C and in a pilot fluidized bed reactor operated in a semi-batch mode. In the micro-differential reactor, basic kinetic data was obtained by measuring the release of carbon dioxide during the reaction. Different kinetic models were considered to describe the conversion, such as the Valensi-Carter model for diffusion controlled reaction rates and the phase-boundary model for first-order reaction kinetics. Furthermore, a model that included both diffusion in the solid material and the chemical kinetics was derived. This model described the experimental data obtained in the micro-differential reactor very well. Finally, rating models describing the conversion obtained in a fluidized bed and in an entrained flow reactor were developed.Godkänd; 1999; 20070403 (ysko)
37
Steffen, Julien [Verfasser], Bernd [Akademischer Betreuer] Hartke, and Carolin [Gutachter] König. "Towards High-Quality Black-Box Chemical Reaction Rates with System-Specific Potential Energy Surfaces / Julien Steffen ; Gutachter: Carolin König ; Betreuer: Bernd Hartke." Kiel : Universitätsbibliothek Kiel, 2020. http://d-nb.info/1205735372/34.
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Thompson, Laura M. "The depletion of nitric oxide by reaction with molten sodium carbonate and sodium carbonate/sodium sulfide mixtures." Diss., Georgia Institute of Technology, 1995. http://hdl.handle.net/1853/5797.
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Bellini, Clément. "Complexes de baryum et autres métaux divalents du bloc principal pour la catalyse homogène de couplages déshydrogénants." Thesis, Rennes 1, 2016. http://www.theses.fr/2016REN1S057/document.
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Les complexes organométalliques de métaux alcalino-terreux lourds (Ca, Sr, Ba), ont émergé ces deux dernières décennies en tant que précatalyseurs efficaces, biocompatibles et disponibles à bas coûts pour des réactions d'hydroélémention d'oléfine ou de polymérisation de cycloesters. Cette thèse décrit la synthèse de complexes de métaux du groupe 2 (Ca, Sr, Ba) et leur utilisation en catalyse de couplage déshydrogénant N-H/H-Si. Le précatalyseur Ba[CH(SiMe3)2]2(THF)3 s'est montré le plus efficace pour le couplage d'amines avec des hydrosilanes, présentant une activité catalytique parmi les plus élevées à ce jour (TOF jusqu' 3600 h-1 ; TON jusqu'à 396). La combinaison de résultats théoriques (calculs DFT en collaboration avec le Dr. Sven Tobisch) et expérimentaux ont permis de comprendre les mécanismes opératoires de ces réactions. Le développement de procédés de synthèse pour la production d'oligo- ou polysilazanes a été mené par l'intermédiaire de ces couplages déshydrogénants. Des structures macromoléculaires linéaires ou cycliques de type polycarbosilazane, présentant de nombreuses applications en chimie des matériaux, ont notamment été synthétisées par polycondensation catalysée par Ba[CH(SiMe3)2]2(THF)3. Dans un dernier temps, la synthèse de complexes innovants de métaux des groupes 12 (Zn, Cd, Hg) et 14 (Pb) a été effectuée en collaboration avec l'équipe du Pr. Silvestru de l'université de Babeş-Bolyai (Cluj-Napoca, Roumanie)In the past two decades, heavier alkaline-earth (Ca, Sr, Ba) complexes have emerged as highly efficient and biocompatible precatalyst for hydroelementation or polymerisation reactions. This PhD thesis describes the synthesis and characterisation of heavier alkaline-earth complexes and their applications as precatalyst for cross-dehydrocoupling of hydrosilanes and amines. The homoleptic precatalyst Ba[CH(SiMe₃)₂]₂(THF)3 displayed high catalytic activity (TOF up to 3600 h⁻¹ ; TON up to 396), with excellent chemoselectivity in reaction of (di)amines with (di)hydrosilanes. Combination of experimental and DFT investigations (collaboration with Dr. Sven Tobisch) revealed the reactions proceed by nucleophilic attack of a metal amide at the incoming silane and subsequent turnover-limiting hydrogen transfer to the metal center. Development of synthesis of oligo- and polysilazanes was performed using our best barium precatalysts. Cyclic or linear polycarbosilazanes (Mw up to 10 000 g.mol⁻¹) were also produced by fast and controlled barium-catalyzed N-H/H-Si polycondensation. In a collaboration with Prof. Silvestru from Babeş-Bolyai University (Cluj-Napoca, Roumanie), synthesis of interesting zinc, cadmium, mercury and lead complexes were achieved in complement of this work
40
Smith, Catherine Joyce. "New tools for organic chemistry : proof-of-concept studies using new reactors, reagents and techniques for the laboratory scale synthesis of small molecule building blocks in flow." Thesis, University of Cambridge, 2011. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.609683.
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Leymarie, Ludovic. "Étude de la synthèse à l’état fondu de copolymères contenant des blocs de polydiméthylsiloxane à l’aide de la réaction époxy-amine." Thesis, Lyon 1, 2012. http://www.theses.fr/2012LYO10055.
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Les copolymères à blocs contenant une partie souple et une partie dure constituent aujourd'hui une classe de matériaux très attractifs en raison de leurs propriétés résultant de la combinaison de deux homopolymères de nature différente. Dans le cadre des copolymères à blocs à forte teneur en polydiméthylsiloxane (PDMS), une méthode de synthèse originale en deux étapes, compatibilisation puis extension, a été développée. Respectueuse de l'environnement grâce à l'utilisation du procédé d'extrusion réactive, cette approche ouvre une nouvelle voie vers le développement d'élastomères thermoplastiques. L'objectif de cette thèse est d'élaborer à l'état fondu des copolymères à blocs à base de PDMS silicone à partir de la réaction époxy-amine puis, par une réaction d'allongement d'obtenir un matériau avec une forte proportion en PDMS. Dans un premier temps, une étude de la réaction époxy-amine sur molécules modèles a été réalisée à partir d'oligodiméthylsiloxanes α,ω- fonctionnalisés époxy et d'une alkylamine. Indépendamment de la température et du ratio molaire, la réaction a permis d'obtenir des copolymères greffés de type (A2B2)n. Dans un deuxième temps, cette stratégie a ensuite été appliquée à des systèmes polymères tels que le polyéthylène et le polyamide. A cette échelle, la réaction s'est produite et conduit à des produits de type (A2B2)n. Dans un troisième temps, l'ensemble des copolymères synthétisés ont été étudiés lors de la réaction d'allongement, basée sur l'insertion de siloxanes cycliques à l'aide d'une superbase. Dépendante de la température et de la quantité de catalyseur, cette réaction a été étudiée sur molécules modèles et sur des systèmes polymèresNowadays hard-soft block copolymers consist of a very attractive material class because of their properties resulting of the combination of two different homopolymers. In the case of block copolymers with on a high polydiméthylsiloxane (PDMS) content, an innovative 2-step synthesis method, compatibilization and extension, has been developed. Using an environmental friendly route such as a reactive extrusion process, this approach opens a new synthesis pathway towards the development of thermoplastic elastomers. The goal of this thesis is to develop mass block copolymers based on PDMS using the epoxy-amine reaction, followed by an extension reaction to reach a material with a high percent of silicone. Firstly, a study of the epoxy-amine reaction on model molecules was carried out between a low molecular weight PDMS and an alkylamine. Independently of the temperature and the molar ratio, the reaction allowed to obtain graft copolymers with an (A2B2)n type structures. Secondly, this strategy has then been applied in polymer systems such as polyethylene and polyamide. At this scale, the reaction occurred and lead to products with (A2B2)n type structures. Thirdly, all synthesized copolymers were studied during the extension reaction, based on the insertion of cyclic siloxanes using a catalysis system. Depending of the temperature and the catalyst quantity, this reaction was investigated on model molecules and polymer systems
42
Bryant, Isaac Mbir [Verfasser], and Marion [Gutachter] Martienssen. "Development of single-stage solar-supported hyper-thermophilic anaerobic reactor for biogas production and disinfection of black water : a pilot case study of Terterkessim slum, Elmina – Ghana / Isaac Mbir Bryant ; Gutachter: Marion Martienssen." Cottbus : BTU Cottbus - Senftenberg, 2019. http://d-nb.info/1182993583/34.
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Yin, Quanyi. "Thiol-para-fluoro modified PPFS as building blocks for the design of silica-based nanocomposite and layer by layer self-assembled thin films." Thesis, Lyon, 2018. http://www.theses.fr/2018LYSEI025/document.
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Ce travail de thèse décrit la préparation de deux types de films de polymères : i) des films nanocomposites à base de silice pyrogénée aux propriétés superhydrophobes et ii) des films LbL auto-assemblés, incluant tous deux des dérivés de poly(2,3,4,5,6-pentaflurostyrene) (PPFS), utilisés comme briques élémentaires. La stratégie utilisée ici consiste à exploiter les nombreux avantages que présente la réaction de substitution du fluor en position para du PPFS avec un thiol, pour générer de nouveaux dérivés aux propriétés ajustables. Ainsi, le premier volet de la thèse a consisté à introduire des chaînes de PPFS de façon covalente à la surface de silice pyrogénée par une stratégie dite de «grafting through» en utilisant la polymérisation radicalaire contrôlée par le voir nitroxydes, en présence de PS-DEPN comme macroamorceur. La cinétique de polymérisation du PFS avec et sans particules silice a été étudiée dans divers solvants, différentes particules hybrides de silices modifiées en surface par une couronne de PPFS ont été préparé. Ensuite, un thiol perfluoré (perfluorodecanethiol:PFDT) a été utilisé pour modifier le PPFS, considéré dans ce cadre comme matrice hôte pour la préparation des nanocomposites et pour modifier le PPFS présent à la surface des particules de silice. A partir de là, un large panel de films nanocomposite a été préparé à partir des différentes combinaisons possibles de polymère hôte (PPFS ou PPFS-PFDT) et de charges inorganiques de silice (modifiées par le PPFS ou par le PPFS-PFDT). Les propriétés de mouillabilité ainsi que la morphologie de surface de chaque film ont été analysées et il en résulte que certains films présentent un caractère superhydrophobe. Le deuxième volet de la thèse a porté sur la modification du PPFS par des thiols porteurs de fonctions acide carboxylique, toujours par la réaction de substitution décrite précédemment. Différents dérivés de PPFS carboxylés de DS variés ont été synthétisés. Leur habilité à développer des liaisons hydrogène avec un polymère modèle accepteur de liaison H (la poly(4-vinyl pyridine) (P4VP)) a été étudiée. Il en ressort que dépendamment de la nature du solvant, des mélanges miscibles ou des complexes interpolymères ont ensuite été formés. Des solutions de complexes préformés ont été successivement déposées par spin-coating pour construire des films. De plus, des films multicouches LbL stabilisés par des liaisons H entre le PPFS carboxylé et la P4VP ont été élaborés and il a été démontré que la nature du solvant de dépôt, ainsi que le taux de modification du PPFS, impactent fortement le mécanisme de croissance, l’épaisseur du film et les caractéristiques de surface, en termes de topologie et de mouillabilitéThis work describes the preparation of two kinds of thin polymer films : i) self-cleaning silica-based (nano)composites films and ii) LbL self-assembling films, both including poly(2,3,4,5,6-pentaflurostyrene) (PPFS) derivatives, as building blocks. The cornerstone of the approach is to exploit the thiol-para fluoro substitution reaction to PPFS chains in order to generate derivatives with tailored properties. In this frame, PPFS chains were anchored onto the surface of vinyl-functionalized fumed silica nanoparticles by nitroxide-mediated polymerization (NMP) in presence of PS-DEPN as macro-initiator via a “grafting through” strategy. The kinetics of NMP of PFS were investigated in presence and without silica in various solvents and well-characterized hybrid silica particles containing different polymer grafting weight were declined. Then, perfluorodecanethiol (PFDT) was employed to modify PPFS, considered as the host polymer matrix, and to functionalize PPFS chains tethered to silica particles. A large panel of (nano)composite films from the different possible host matrix/silica particles combinations was prepared. The wettability and the surface morphology of each film were discussed, as a function of the host structure (PPFS or PPFS-PFDT with different DS) and silica (modified with PPFS or PPFS-PFDT), as well as the silica content. It results that superhydrophobic features can be reached. Subsequently, PPFS was modified by using carboxylic acid mercapto modifier via the thiol-para fluoro coupling. Various carboxylated PPFS derivatives differing in the degree of substitution (DS) were prepared and their ability to develop H-bonds in solution with a model strong H-bond acceptor partner (poly(4-vinyl pyridine) (P4VP)) was investigated. Dependently on the nature of the solvent, a miscible blend or interpolymer complexes (IPC) were achieved. IPC-containing solutions were used to successfully fabricate spin-assisted films. Furthermore, H-bonds mediated LbL self-assembly multilayer films involving carboxylated PPFS and P4VP were prepared and it was evidenced that the nature of the deposition solvent as well as the extent of the modification (quantified by the DS), impact the growth mechanism, the thickness and the surface features, in terms of topology and wettability
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Heuken, Maria. "Fullerenhaltige Donor-Akzeptor-Blockcopolymere als Additive für organische Bulk-Heterojunction-Solarzellen." Doctoral thesis, Saechsische Landesbibliothek- Staats- und Universitaetsbibliothek Dresden, 2012. http://nbn-resolving.de/urn:nbn:de:bsz:14-qucosa-100244.
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Fullerenhaltige Bulk-Heterojunction-Solarzellen auf Polymerbasis zeigen derzeit eine geringe Langzeitstabilität, die unter anderem auf der Entmischung der Bulkphasen beruht. In dieser Arbeit wurden daher auf neuartige Weise Blockcopolymere entwickelt, die zur Stabilisierung der Phasen dienen können. Ausgehend von Poly-3-hexylthiophen-Makroinitiatoren wurde ein zweiter Block mit reaktivem Comonomer polymerisiert, das zur Anbindung von reinem Fullerens bzw. von Fullerenderivaten diente. Die fullerenfunktionalisierten Polymere wurden in Modell-Systeme eingemischt und zeigten erste Verbesserungen bezüglich der Phasenstabilisierung.
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Yigiterhan, Oguz. "Trace Metal Composition Of Particulate Matter In The Water Column And Sediments Of The Black Sea And Regional Rivers." Phd thesis, METU, 2005. http://etd.lib.metu.edu.tr/upload/12606507/index.pdf.
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The Black Sea, with its oxic, suboxic and anoxic layers, provides a unique environment for studying how biological and geochemical processes affect the composition of particulate matter. The elemental composition of particles in the Black Sea is controlled by their origin and sources. Particles from rivers are dominated by aluminosilicate material that has compositions similar to the earth&rsquos crust. In general this material is relatively unreactive. Biological processes in the upper oxic and suboxic layers of the water column result in enrichments of elements which used as nutrients. Cu, Ba and Mo have been proposed as tracers for planktonic material and new production. Geochemical processes like manganese and iron recycling between oxidized and reduced forms, metal sulfide formation, and biogenic matter decomposition can have a large impact on the composition of particles in the suboxic and anoxic zones. The aim of this thesis was to study the composition of particles suspended in the water column of the Black Sea, in regional rivers draining into the Black Sea, and of particles deposited in these rivers and Black Sea sediments. The objectives were to determine the chemical composition and distribution of particles supplied by rivers and produced in the Black Sea, and compare with those particles buried in the sediments. The chemical distributions can help us to understand the biogeochemical processes taking place. The ultimate goal is to understand if there is a chemical signature that characterizes sediments deposited in anoxic basins that can be used to determine if ancient sedimentary rocks were deposited under such conditions. Water column filter samples were collected from the central western basin and along transects to the SW shelf regions during several research cruises of R/V Bilim and R/V Knorr in the Black Sea. Samples were taken by using both in situ large volume filtration systems and on deck vacuum filtration of discrete samples. River samples were collected by hand from the bank of four Turkish rivers and the Danube River. Sediment samples were obtained from 0 - 25 cm interval of a box core from the deep western basin. All samples were digested and analyzed by inductively coupled plasma - mass spectrometry and combination of atomic absorption (flame &
graphite furnace) instruments. The elements analyzed included Al, Ti, V, Cr, Mn, Fe, Ni, Co, Cu, Zn, Mo, Ag, Cd, Ba, Pb, and U. Great care was taken to avoid contamination and to obtain the highest level of precision and accuracy. The precision was typically about 5% for most elements. The accuracy, determined using standard reference materials, was also usually better than 5%. Another goal of this research was to determine the metal concentrations and best digestion methods using different types of filter materials. Blank filters were digested and analyzed and the analyses of various filter blanks are presented in the thesis. The analyses showed that the particulate matter data from Turkish Rivers were very similar to the composition of global average riverine particulate material and global average crust. The Danube River had elevated concentrations for some elements that were probably due to anthropogenic contamination. The Turkish river samples were closer to (but still higher than) the averages for the world&rsquo
s rivers but many elements in the Danube were much higher. These high values determined for major elements in the Danube samples strongly suggest considerable contamination of the Danube as compared to the Turkish Rivers. The Danube River samples were especially enriched in Pb, Zn, Ag, Cu, Cd, and Mn and slightly enriched with Cr and Ni. The first five elements, in particular, are well known indicators of pollution. The particulate matter in the water column of the Black Sea was influenced by lithogenic input from rivers, biological processes and geochemical processes. In order to examine the biogeochemical processes extensively, all the data were plotted as Metal/Al (Me/Al) ratios and compared with the ratios of the average crust and Turkish Rivers. Deviations were used to examine the anomalies due to biological and geochemical processes. In addition, the Al content of individual sample and the Me/Al ratio of crust or rivers were used to subtract the lithogenic component from the total composition. Enrichments due to biological processes were observed for Ba >
Fe >
Cr >
Mn >
Zn >
Ni >
Cu >
Mo >
V >
Co >
Cd >
U for the overall biogenic composition. Enrichments due to biology are most evident for Ba, Fe, Cr and Mn. This is a unique data set as there have been few previous analyses of biological enrichment for most of these elements. The results of particulate matter analyses showed that some elements including U, V, Cr, Ni, Cu, Co, Zn, Ba and Mo were enriched in the set of samples from the euphotic zone. Redox cycling in the suboxic zone was observed, as expected, for Mn and Fe, whose oxides play an important role in scavenging processes. The redox dependent processes in the suboxic &ndash
anoxic interface influence the vertical distribution of U, Ni, Co, Cu, Zn, Ba and possibly Mo, Cr and V. Elements influenced by sulfide formation in the anoxic layer are Fe, Cr, Ni, Co, Mo, and presumably Ag. The sediment data were also examined based on the same approaches. The elements Zn, Pb, U and Cd decreased with sediment depth over the top 5 cm suggesting that they were remobilized out of the sediments. In general the sediments from the Black Sea have Me/Al ratios very similar to local Turkish Rivers and average crust. There is no unique sediment signature (except possibly for Mo) indicating that these sediments were deposited under sulphidic conditions. This study does not support the hypothesis that the composition of ancient rocks can be used to characterize the environment of deposition.
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Ritter, Patxi. "Ondes gravitationnelles et calcul de la force propre pour un astre compact en mouvement autour d'un trou noir super-massif." Thesis, Orléans, 2013. http://www.theses.fr/2013ORLE2038/document.
Full textAbstract:
Cette thèse s'inscrit dans le cadre de la modélisation des ondes gravitationnelles et du mouvement relativiste associés aux systèmes binaires à grand rapport de masses (Extreme Mass Ratio Inspiral - EMRI). Ces systèmes sont formés d'un trou noir super massif autour duquel gravite un objet compact de masse stellaire. Dans le formalisme de la théorie perturbative des trous noirs, on développe une méthode numérique qui calcule les formes d'ondes produites par une particule ponctuelle en orbite autour d'un trou noir de Schwarzschild. Il s'agit de résoudre l'équation d’onde de Regge-Wheeler-Zerilli dans le domaine temporel dont la solution, invariante de jauge, peut être reliée aux modes de polarisation, à l'énergie et au moment cinétique emporté par les ondes gravitationnelles. En réaction à l'énergie et au moment perdu, la trajectoire de la particule est affectée au cours du temps. Dans le cadre du formalisme de MiSATaQuWa, on calcule la force propre agissant sur une particule, initialement au repos, est en chute libre sur un trou noir de Schwarzschild. Nous montrons comment cette quantité est définie dans la jauge de Regge-Wheeler par le biais de la régularisation mode-sum. L'effet de la force propre sur le mouvement de la particule est ensuite pris en compte de façon itérative et auto-consistante grâce à un algorithme utilisant une méthode d'orbites osculatrices que nous avons développé. Nous quantifions cet effet en calculant soit la déviation orbitale par rapport au mouvement géodésique, soit les formes d'ondes perturbées et l'énergie rayonnée associéeThis thesis focuses on modelling the gravitational waves and the relativistic motion associated to Extreme Mass Ratio Inspiral (EMRI) systems. These systems consist of a stellar mass compact object gravitationally captured by a super-massive black hole. In black hole perturbation theory, we further develop a numerical method which computes waveforms generated by a point mass particle orbiting a Schwarzschild black hole. The Regge-Wheeler-Zerilli wave equation is solved in time domain. The gauge invariant solution is related to the polarisation modes, the energy and the angular momentum carried by the gravitational waves. In reaction to the energy and the moment lost, the trajectory is modified all along. In the MiSaTaQuWa formalism, we compute the self-force acting upon a point particle which is initially at rest, and then falling into a Schwarzschild black hole. We show how this quantity is defined in the Regge-Wheeler gauge by using the mode-sum regularisation technique. We take into account the self-force effect on the motion of the particle by using an iterative and osculating orbit method conceived herein. We quantify the orbital deviation with respect to the geodesic motion, but also the perturbed wave forms and the associated radiated energy
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Ciccolini, Cecilia. "Synthesis of Mono and Poly-Heterocycles starting from 1,2-Diaza-1,3-Dienes (or precursors) as Building Blocks." Doctoral thesis, Urbino, 2020. http://hdl.handle.net/11576/2674162.
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Chen, Hui. "Atmospheric chemical processes : reaction of ozone with 2- and 3-carene, evolution of internal mixed combustion particles." Thesis, Orléans, 2014. http://www.theses.fr/2014ORLE2064/document.
Full textAbstract:
Dans cette thèse, nous présentons des travaux complémentaires conduits à ICARE-CNRS (Orléans), partie A et à l’Université de Fudan (Shanghai), partie B. Partie A : les 2-et 3-carène sont deux composés organiques volatils biogéniques importants présents dans l’atmosphère dont les voies de dégradation sont encore mal connues. Afin de déterminer les constantes de vitesse des réactions de ces espèces avec l’ozone, nous avons utilisé trois systèmes expérimentaux complémentaires : des chambres de simulation d’ICARE de 7300L et 80000L (HELIOS) et un réacteur à flux laminaire. Les rendements de certains produits de réactions, le radical hydroxyle (OH), le formaldéhyde (HCHO) et le monoxyde de carbone (CO) ont aussi été déterminés. D’autre part, pour avoir une meilleure compréhension d’intermédiaires de réaction formés lors de l’ozonolyse, appelés intermédiaires de Criegee, un réacteur à flux laminaire à deux étages a été mis en place pour mesurer leurs constantes de vitesse de réaction avec SO2, NO2 et O3. Partie B : les impacts du “black carbon (BC)” et du “brown carbon (BrC)” constituent une incertitude majeure dans les modèles climatiques actuels. Des rapports récents indiquent que la morphologie et l’évolution des BC et BrC dans l’atmosphère jouent un rôle important sur la capacité d’absorption de ces particules. Afin d’étudier leurs comportements, des mélanges de particules (BC-BrC) ont été exposés en chambre de simulation atmosphérique à l'acide sulfurique, au mélange ammoniac / triéthylamine, et à la vapeur d'eau de manière séquentielleIn this thesis, we present a complementary work conducted at ICARE-CNRS (Orléans), Part A and at Fudan University (Shanghai), Part B. Part A: 2-and 3-carene are two important biogenic volatile organic compounds present in the atmosphere. The knowledge on their degradation pathways and the corresponding products are still poor. Using complementary reaction systems-ICARE 7300 L and HELIOS 80000 L simulation chambers, vertical laminar flow reactor, their kinetic rate constants for reaction with ozone were determined. Additionally, important product formation yields, hydroxyl radical (OH), formaldehyde (HCHO) and carbon monoxide (CO) have been determined with indication to their corresponding formation routes from the ozonolysis of carene. To have a better understanding on reactions of Criegee intermediates (CIs) generated through ozonolysis in the atmosphere, a horizontal 2-stage laminar flow reactor was set up to measure the rate constants of CIs with SO2, NO2 and O3. Part B: Radiative forcing of black carbon (BC) in the atmosphere, as well as that of brown carbon (BrC), remains to be a major uncertainty in current climate models. Recent reports indicate that the absorption enhancement of BC and BrC particles is determined by evolution of morphology and mixing state during the atmospheric processing. Laboratory-generated BC-BrC mixture particles (BC-BrC) were exposed to sulfuric acid, ammonia/triethylamine, and water vapor sequentially to investigate the alternation in light absorption, morphology and mixing state during simulated atmospheric processing
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Griffith, Kent Joseph. "Atomic and electronic structure of complex metal oxides during electrochemical reaction with lithium." Thesis, University of Cambridge, 2018. https://www.repository.cam.ac.uk/handle/1810/271191.
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Lithium-ion batteries have transformed energy storage and technological applications. They stand poised to convert transportation from combustion to electric engines. The discharge/charge rate is a key parameter that determines battery power output and recharge time; typically, operation is on the timescale of hours but reducing this would improve existing applications and open up new possibilities. Conventionally, the rate at which a battery can operate has been improved by synthetic strategies to decrease the solid-state diffusion length of lithium ions by decreasing particle sizes down to the nanoscale. In this work, a different approach is taken toward next-generation high-power and fast charging lithium-ion battery electrode materials. The phenomenon of high-rate charge storage without nanostructuring is discovered in niobium oxide and the mechanism is explained in the context of the structure–property relationships of Nb2O5. Three polymorphs, T-Nb2O5, B-Nb2O5, and H-Nb2O5, take bronze-like, rutile-like, and crystallographic shear structures, respectively. The bronze and crystallographic shear compounds, with unique electrochemical properties, can be described as ordered, anion-deficient nonstoichiometric defect structures derived from ReO3. The lessons learned in niobia serve as a platform to identify other compounds with related structural motifs that apparently facilitate high-rate lithium insertion and extraction. This leads to the synthesis, characterisation, and electrochemical evaluation of the even more complicated composition–structure–property relationships in ternary TiO2–Nb2O5 and Nb2O5–WO3 phases. Advanced structural characterisation including multinuclear solid-state nuclear magnetic resonance spectroscopy, density functional theory, X-ray absorption spectroscopy, operando high-rate X-ray diffraction, and neutron diffraction is conducted throughout to understand the evolution of local and long-range atomic structure and changes in electronic states.
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Florêncio, Thaíla de Mello. "Degradação anaeróbia de efluente têxtil simulado com corante azo Direct Black 22 na presença de íons sulfato em reator anaeróbio de leito estruturado com fluxo ascendente." Universidade de São Paulo, 2018. http://www.teses.usp.br/teses/disponiveis/18/18138/tde-27092018-162456/.
Full textAbstract:
Avaliou-se o emprego de sistema biológico de tratamento em reator anaeróbio de leito estruturado em fluxo ascendente (RAnLE) para remoção do corante Direct Black 22 (DB22) e íons sulfato (65 e 200 mg.L-1, respectivamente), principais constituintes de efluente têxtil de indústrias de jeans da região de Caruaru, PE. Etanol foi utilizado como doador de elétrons na concentração de 1000 mg.DQO.L-1. As médias de remoção de DQO, sulfato e corante foram respectivamente 80,28 ± 6,62%, 78,66 ± 4,04% e 68 ± 5%. Cerca de 3% do sulfeto produzido foi identificado em solução, 10% esteve presente na forma gasosa e aproximadamente 87% precipitou em forma de cristais metálicos inorgânicos ou em enxofre elementar por exposição ao ar atmosférico ou por ação redutora do corante DB22, contribuindo para remoção de cor na transformação do corante em aminas aromáticas. Os ácidos graxos presentes no efluente tratado totalizaram 121 ± 34 mg.L-1, com predominância de ácido acético (95 ± 17 mg.L-1), sem prejuízo da capacidade tamponante do sistema, que apresentou aumento na alcalinidade pela ocorrência da sulfetogênese e pela característica básica das aminas aromáticas, produzidas por meio da quebra da ligação azo do corante, revelando absorção em diferentes comprimentos de onda na região do ultravioleta, denotando a produção de diferentes estruturas aromáticas. O efluente têxtil simulado foi mais tóxico do que seu correspondente tratado para ambas as situações (crônico e agudo) nos testes de toxicidade com Ceriodaphnia dúbia (crônica) e Daphnia magna (aguda), atestando o potencial dos reatores anaeróbios na destoxificação do corante azo Direct Black 22 para as espécies abordadas. Os testes de citotoxicidade in vitro empregando células McCoy (linhagem contínua de fibroblastos) em exposição ao efluente têxtil sintético tratado no RAnLE apresentaram um comportamento dose-dependente. O efluente diluído 3 vezes inibiu 50% das células. Por outro lado, não foi possível verificar um comportamento dose-dependente considerando as diferentes concentrações de DB22. Entretanto, houve diferença estatística significativa na viabilidade celular para as concentrações de DB22 de 0,016, 0,065, 0,2 e 0,26 mg.mL-1. Os resultados demonstram a necessidade do uso de diferentes testes de toxicidade a vários organismos, de forma a complementar os resultados obtidos pelos testes convencionais. Eletromicrografias da biomassa revelaram a presença de arqueias metanogênicas, demonstrando a capacidade de coexistência de comunidades sulfetogênicas e metanogênicas, dado o valor observado de DQO/sulfato de 5. O sequenciamento metagenômico em apontou grande abundância relativa de bactérias redutoras de sulfato (BRS), superior a 50%. Os bioensaios em batelada com o lodo de fundo e o lodo em suspensão do RAnLE apontaram que a biomassa aderida foi mais apta a suportar a carga tóxica proveniente do corante e das aminas aromáticas. A estrutura do RAnLE permitiu o estabelecimento de biomassa aderida e biomassa suspensa, concorrendo ambas para melhor desempenho do sistema.The present work assessed the employment of an anaerobic up-flow fixed-structured bed (AUFFSB) reactor, which aimed to remove the main constituents of a simulated textile effluent with azo dye Direct Black 22 (DB22) and sulphate ions (65 and 200 mg.L-1, respectively), main constituents in residual waters generated by denim industry in Caruaru, PE. Ethanol was employed as electron donor (1000 mg.COD.L-1). Medium removals for COD, sulphate and dye concentration were respectively 80.28 ± 6.62%, 78.66 ± 4.04% and 68 ± 5%. Circa 3% of produced sulphide was identified in the effluent, 10% in gaseous state and approximately 87% precipitated either as metallic inorganic crystals, as elemental sulphur due to exposition to atmosphere, or due to the azo bound reduction of DB22, which contributed to colour removal in the generation of aromatic amines from the azo dye. The volatile fatty acids totalized 121 ± 34 mg.L-1 while acetic acid was the predominant one (95 ± 17 mg.L-1). Nevertheless, such concentrations did not impair the buffering capacity of the system, which had increased alkalinity due to the occurrence of sulphidogenesis and of the alkaline characteristic of the aromatic amines, which were produced from azo bound cleavage, revealing absorption in different wavelengths in the UV zone, inferring that different aromatic structures were formed. As for the toxicity, the simulated textile effluent was more toxic before treatment than after treatment for both bioessays employing Ceriodaphnia dubia and Daphnia magna, (chronic and acute toxicity), attesting the potential of anaerobic reactors to detoxify azo dye DB22. The in vitro cytotoxicity tests using McCoy cells (fibroblasts of a continuous lineage) exposed to simulated textile effluent treated on the anaerobic bioreactor presented a dose-dependent behaviour. The effluent diluted 3 times showed inhibition to 50% of the cells. On the other hand, it was not possible to verify a dose-dependent behaviour considering the different concentrations of DB22. However, there was significant statistical difference on cell viability for DB22 concentrations of 0.016, 0.065, 0.2 and 0.26 mg.mL-1. The results pointed to the need of diverse toxicity tests to various organisms in order to complement the results obtained by conventional used ones. Micrographs revealed the presence of methanogenic archeas, denoting the possibility of coexistence between sulphidogenic and methanogenic communities, considering the observed COD/sulphate ration of 5. Metadata obtained from metagenomic sequencing revealed high relative abundance of sulphate-reducing bacteria (SRB), which was superior to 50%. Batch bioessays showed that biomass in supporting material is more capable of enduring the toxic load from DB22 and aromatic amines. The AUFFSB structure enabled that suspended biomass developed along with fixed biomass, thus both collaborated for a better system performance.