Academic literature on the topic 'Radikal <Chemie>'

Enzymatic hydrolysates were prepared from bee bread using three proteases. The antioxidant properties of these hydrolysates were measured using four different methods. These had remarkable antioxidant activity similar or superior to that of 1 mm α-tocopherol. They also had high scavenging activities against active oxygen species as the superoxide anion radical and hydroxyl radicals. Moreover, they showed angiotensin I-converting enzyme inhibitory activities and the activities were similar to those from various fermented foods such as fish sauce, sake, vinegar, cheese, miso, and natto. The present studies reveal that enzymatic hydrolysates from bee bread are of benefit not only for the materials of health food diets, but also for in patients undergoing various diseases such as cancer, cardiovascular diseases, diabetes, and hypertension.

Im Rahmen dieser Arbeit wird die Regio- und Stereoselektivität der 1,2-Umlagerung von 1,3-Cylopentandiyl-Radikalkationen und den entsprechenden Carbokationen untersucht. Die 1,3-Radikalkationen werden dabei durch Elektronentransfer (ET) mit Tris(p-bromphenyl)-ammoniumhexachlorantimonat (TBA•+SbCl6-) aus den Tricyclo[3.3.0.02,4]octanen (Hausanen) I generiert, die Carbokationen können durch Protonierung mit TFA und HClO4 erhalten werden. Ein mechanistisches Bild wird gezeichnet wie durch das Wechselspiel aus konformationellen, sterischen und elektronischen Faktoren ein stereochemischer Erinnerungseffekt die Produktselektivität der 1,2-Umlagerung bestimmt. Das Produktverhältnis der Umlagerungsprodukte II und III spiegelt nicht die unterschiedlichen Wanderungstendenzen der Substituenten R wider. Es wird gezeigt, wie durch strukturelle Variation der Ringanellierung in den 1,3-Radikalkationen das Umlagerungsverhalten derart manipuliert werden kann, dass entweder sterereochemische Kontrolle (stereochemischer Erinnerungseffekt) oder Curtin / Hammett-Verhalten zutrifft. In der Elektrontransfer-induzierten 1,2-Umlagerung der usane I entstehen regioselektiv die beiden Cyclopentene II (Wanderung der CH3-Gruppe) und III (Wanderung der R-Gruppe) durch eine 1,2-Verschiebung der beiden Methylenbrückensubstituenten zum Methylterminus (Schema A). Für alle Hausanderivate I ist das Verhältnis der beiden Umlagerungsprodukte II und III annähernd gleich und reflektiert nicht die zu erwartende Wanderungstendenz Methyl < Ethyl < Benzyl, Allyl (Tabelle A). Der Grund für diesen stereochemischen Erinnerungseffekt liegt darin, dass die Wanderung der CH3-Gruppe schneller erfolgt als die konformationelle Äquilibrierung der beiden Radikalkationkonformere anti-I•+ syn-I•+. Die säurekatalysierte Umsetzung mit TFA ergibt eine ähnliche Regio- und Stereoselektivität wie in der ET-induzierten Umlagerung, es entstehen ausschließlich die Cyclopentene II und III. Die Umsetzung mit HClO4 führt zu einer kompletten Umkehr der zuvor beobachteten Produktselektivitäten (Tabelle A). Die Unterschiede in den Produktselektivitäten werden mit dem Auftreten der drei unterschiedlichen Intermediate I•+, I(edge-H)+ und I(corner-H)+ in der Umlagerung erklärt. Bei der ET-induzierten Umlagerung und der Säurekatalyse mit TFA werden die gewinkelten Intermediate I•+ und I(edge-H)+ durchlaufen, wohingegen bei der Protonierung mit HClO4 direkt das offene Carbokation I(corner-H)+ gebildet wird. Für alle Umlagerungsmodi findet jedoch bevorzugt Wanderung der CH3-Gruppe statt, so dass die Produktselektivität durch einen stereochemischen Erinnerungseffekt bestimmt wird. Um den Einfluss einer zusätzlichen Ringanellierung auf das Umlagerungsverhalten zu untersuchen, wird ebenfalls die ET-induzierte Umlagerung für das tetracyclischen Hausan IV untersucht (Tabelle B). Die Umsetzung des Phenyl-substituierten Hausans IV mit TBA•+SbCl6- resultiert regioselektiv die beiden diquinanverwandten Umlagerungsprodukte V (55%) und VI (45%) durch Wanderung der CH3-Gruppe und des CH2-Fragments des anellierten Ringes. Die Umlagerung des Methyl-substituierten Derivats IV verläuft hingegen weder regio- noch stereoselektiv zu den drei Isomeren V (37%), VI (25%) und VII (43%). Für die Umsetzung mit HClO4 wird im Fall von Hausan IVeine komplette Umkehr der Regioselektivität beobachtet und es entsteht hauptsächlich das Produkt VII (67%), sowohl die beiden Regioisomeren V (24%) und VI (9%). Das Methyl-substituierte Derivat IV ergibt bei der Umsetzung mit HClO4 regio- und stereoselektiv ausschließlich das Cyclopenten V (> 95%). Die Produktselektivität der 1,2-Umlagerung des Hausans IV lässt sich durch die Viskosität ( des verwendeten Lösungsmittels steuern. Mit zunehmender Viskosität nimmt der Anteil an Methylwanderungsprodukt V zu, so dass sich das V/VI Verhältnis beim Übergang von Dichlormethan ( = 0.36 cP) zu 1,4-Butandiol ( = 89.2 cP) fast verdoppelt. Im Gegensatz dazu zeigt das Produktverhältnis II / III der Umlagerung von den diastereomeren Hausanen anti-I und syn-I keine Viskositätsabhängigkeit. Anhand der für die Umlagerung beobachteten Produktverhältnissen wird, ausgehend vom Hausanisomer anti-I einerseits und Hausanisomer syn-I andererseits, das Ausmaß an Stereoselektivität der 1,2-Umlagerung durch eine detaillierte Kinetikanalyse quantifiziert Die CD3-Wanderung (k2), ausgehend vom vom anti-I•+(verdrillt) Konformer, erfolgt ca. sieben Mal schneller als die konformationelle anti-zu-syn (k1) Transformation zum Radikalkationkonformer syn-I•+(verdrillt). Wohingegen die CD3-Wanderung (k3), ausgehend vom syn-I•+(verdrillt) Konformer, nur ca. drei Mal schneller ist als die syn-zu-anti Transformation (k-1) zum Radikalkation anti-I•+(verdrillt). Für die Umlagerung der aus den Hausanen I generierten Radikalkationen und Carbokationen wird ein stereochemischer Erinnerungseffekt beobachtet. Die Wanderungsselektivität wird durch konformationelle und sterische Effekte bestimmt und ist unabhängig von der Wanderungstendenz des Substituenten R. Die konformationellen Effekte der 1,2-Umlagerung von 1,3-Cyclopentandiyl-Radikalkationen können durch eine geeignete Variation der Ringanellierung so gesteuert werden, dass entweder ein stereochemischer Erinnerungseffekt (tricyclische Hausane I) oder ein Curtin/Hammett-Verhalten (tetracyclische Hausane IV) beobachtet wird. Die zusätzliche Cyclohexananellierung im Hausan IV löscht den stereochemischen Erinnerungseffekt und bewirkt eine für radikalkationische Intermediate erstmalig beobachtete Viskositätsabhängigkeit der Produktselektivität in der Umlagerung
The present study provides valuable mechanistic insight into the intricacies and complexities in the rearrangement of the 1,3 radical cations [generated by electron transfer with tris(p-bromo)phenylaminium hexachloroantimonate (TBA•+SbCl6-)] and the corresponding carbocations [formed by protonation with trifluoroacetic (TFA) and perchloric acid (HClO4)]. This elaborate comparative study provides a mechanistic assessment of the interplay of conformational, electronic and steric effects on the product selectivity in the rearrangement of radical cations and the corresponding carbocation intermediates as required by stereoelectronic control. For all activation modes in the rearrangement of the housanes I stereochemical memory operates, which is imposed by the conformational requirements that are dictated by the stereoelectronics of the 1,2 migration. As a consequence, the ratio of the rearrangement products II/III is insensitive to the migratory aptitude of the R substituent in the housanes I. Additionally, it has been demonstrated that structural changes allow to manipulate the conformational effects in the rearrangement of 1,3-cyclopentandiyl radical cations that either stereochemical memory or Curtin / Hammett behavior is observerd. The electron-transfer-catalyzed rearrangement of the housanes I affords regioselectively exclusively the two cyclopentenes II (CH3 migration) and III (R migration) by 1,2 shift of the two groups at the methano bridge to the methyl terminus For all derivatives, the 1,2 shift of the CH3 group prevails and the rearrangement ratio is relatively insensitive to the migratory aptitude of the R substituent. The TFA-catalyzed rearrangement leads to a similar regio- and stereoselectivity as in the case of electron transfer. Thus, only the cyclopentenes II and III are produced with predominant CH3 migration.The rearrangement catalyzed by HClO4 leads to complete reversal in product distribution compared to the above-desribed rearrangements. The bridged structures I•+, I(edge-H)+ and I(corner-H)+ are suggested as key intermediates. In the electron-transfer and TFA-catalyzed rearrangements, the two puckered intermediates I•+and I(edge-H)+ intervene, whereas the open structure I(corner-H)+, formed by direct cornerwise protonation of the housane I, is suggested. In all cases, the CH3 group migrates in preference, the stereochemical memory effect accounts for the observed product selectivity. To probe the influence of ring annelation on the product selectivity, also the tetracyclic housanes IV were subjected to the electron-transfer oxidation by TBA•+SbCl6- (Table B). The electron-transfer rearrangement of the housanes IV on treatment with TBA•+SbCl6- affords regioselectively the two isomeric products V (55%) and VI (45%) by migration of the two groups at the methano bridge. In contrast, the methyl derivative IV is neither regio- nor stereoselective and leads to the three isomeric cyclopentenes V (37%), VI (25%), and VII (43%). Acid-catalyzed rearrangement of the housane IV gives in addition to V (24%) and VI (9%), the regiosiomer VII (67%) as major product. Acid-catalyzed rearrangement of the methyl-substituted housane IV yields regio- and stereoselectively the quinane V(> 95%). For the housane IV a mechanistically pertinent viscosity dependence is disclosed on the product selectivity. Whereas at low viscosity the two cyclopentenes V and VI are formed in nearly equal amounts, the methyl migration product V dominates more than twofold at higher viscosity. In contrast, the electron-transfer-induced rearrangement of the isomeric housanes anti-I and syn-I does not depend on the solvent viscosity (Scheme B). To evaluate quantitatively the extent of stereochemical memory, the ratios k2/k1 and k3/k-1 serve as a quantitative measure of the stereoselectivity, that is, for the case k2 >> k1 and k3 >> k-1 perfect stereochemical memory applies, whereas for the case k2 << k1 and k3 << k-1 complete Curtin-Hammett behavior operates. Thus, the CD3 migration in the anti-I•+(twisted) conformer (k2) proceeds ca. seven times faster than the conformational anti-to-syn change (k1) to the conformer syn-I•+(twisted), whereas the CD3 transfer in the syn-I•+(twisted) conformer (k3) is only ca. three times faster than the syn-to-anti conformational change (k-1) to the anti-I•+(twisted) species. The present study reveals that the product selectivity of the 1,2 migration in the electron-transfer as well as in the acid-catalyzed rearrangement of the housanes I is decisively determined by conformational and steric factors. For all activation modes, the stereochemical memory effect operates. As a consequence, the ratio of rearrangement products is essentially insensitive to the migratory aptitude of the R substituent in the housanes I. This stereochemical memory effect derives from the conformational imposition on the stereoelectronic requirements during the 1,2 migration of the 1,3-radical-cation intermediates. Appropriate ring annelation in the intermediary 1,3-cyclopentandiyl radical cation allows to change the stereochemical course of the rearrangement from stereochemical memory (tricycylic housanes I) to complete loss of sterecontrol through Curtin/Hammett behavior (tetracyclic housanes IV); thus, cyclohexane annelation erases the stereochemical memory effect. Such structural manipulation of the conformational control in radical-cation rearrangements has hitherto not been documented. The observed Curtin/Hammett behavior of the housane IV represents the first case for which conformational equilibration precedes competing product formation through 1,2 migration, which could have hardly been anticipated

AbstractRecent advances in intramolecular hydrogen-atom transfer (HAT) have demonstrated significant utility in C—H functionalization through highly reactive open-shell intermediates. The intramolecular transposition of radical reactivity from select functional groups to generate more stable carbon-centered radicals often proceeds with high regioselectivity, providing novel bond disconnections at otherwise inert and largely indistinguishable positions. This chapter explores the functional groups capable of intramolecular HAT to generate remote radicals and the transformations currently available to the synthetic chemist.

O-Centered radicals have been little used for C-O ring formation. Glenn M. Sammis of the University of British Columbia showed (Organic Lett. 2008, 10, 5083) that O-centered radicals could be generated efficiently, and that they cyclized with high diasterecontrol. Liming Zhang of the University of Nevada, Reno, continuing his studies of Au-activation of alkynes, uncovered (J. Am. Chem. Soc. 2008, 130, 12598) the bimolecular condensation of polarized alkynes such as 3 with aldehydes and ketones, including 4, to give the dihydrofuran with high diastereocontrol. Margarita Brovetto of the Universidad de la República, Montevideo, Uruguay, prepared (J. Org. Chem. 2008, 73, 5776) the precursor to the enantiomercially triol 6 by fermentation of bromobenzene with Pseudomonas putida 39/D. Cyclization of 6 gave 7 with high diastereocontrol. Petri M. Pihko of the University of Jyväskylä, Finland, found (Organic Lett . 2008, 10, 4179) that cyclization of 8, prepared by Sharpless asymmetric epoxidation followed by Sharpless asymmetric dihydroxylation, also proceeded with high diastereocontrol. Vincent Aucagne of the Université d’Orléans observed (Tetrahedron Lett. 2008, 49, 4750) that brief exposure of the sulfone 10 to t -BuOK at low temperature gave clean conversion to the kinetic diastereomer 11. At room temperature, similar conditions delivered the other, more stable diastereomer. Angeles Martín and Ernesto Suárez of the C. S. I. C., La Laguna, took advantage (Tetrahedron Lett. 2008, 49, 5179) of the facile generation of O-centered radicals in converting 12 to 14, having a stereocontrolled quaternary center. The transformation is thought to be proceeding by H-atom abstraction, then diastereocontrolled trapping of the C-radical so formed with the allyl stannane 13. Much of the effort toward alkylated cyclic ether construction has been focused on alkyl group attachment adjacent to the ring oxygen. Torsten Linker of the University of Potsdam developed (J. Am. Chem. Soc. 2008, 130, 16003) a complementary approach, stereocontrolled oxidative radical addition of malonate 16 to glycals such as 15 to give the 3-alkyl substituted 17.

Lean premixed combustion is one of the widely used methods for NOx reduction in gas turbines (GT). When this method is used combustion takes place under low Equivalence Ratio (ER) and at relatively low combustion temperature. While reducing temperature decreases NOx formation, lowering temperature reduces the reaction rate of the hydrocarbon–oxygen reactions and deteriorates combustion stability. The objective of the present work was to study the possibility to decrease the lower limit of the stable combustion regime by the injection of free radicals into the combustion zone. A lean premixed gaseous combustor was designed to include a circumferential concentric pilot flame. The pilot combustor operates under rich fuel to air ratio, therefore it generates a significant amount of reactive radicals. The experiments as well as CFD and CHEMKIN simulations showed that despite of the high temperatures obtained in the vicinity of the pilot ring, the radicals’ injection from the pilot combustor has the potential to lower the limit of the global ER (and temperatures) while maintaining stable combustion. Spectrometric measurements along the combustor showed that the fuel-rich pilot flame generates free radicals that augment combustion stability. In order to study the relevant mechanisms responsible for combustion stabilization, CHEMKIN simulations were performed. The developed chemical network model took into account some of the basic parameters of the combustion process: ER, residence time, and the distribution of the reactances along the combustor. The CHEMKIN simulations showed satisfactory agreement with experimental results.

The need for NOx reduction in gas turbine (GT) stimulates research for new combustion methods. Lean combustion is a method in which combustion takes place under low equivalence ratio and relatively low combustion temperatures. As such, it has the potential to lower the effect of the relatively high activation energy nitrogen-oxygen reactions which are responsible for substantial NOx formation during combustion processes. Moreover, lowering temperature reduces the reaction rate of the hydrocarbon-oxygen reactions and deteriorates combustion stability. The objective of the present study is to reduce the lower equivalence ratio limit of the stable combustion operational boundary in lean GT combustors. A lean premixed gaseous combustor was equipped with a surrounding concentric pilot flame operating under rich conditions, thus generating a significant amount of reactive radicals. The main combustor’s mixture composition was varied from stoichiometric to lean mixtures. The pilot’s mixture composition varied by changing the air flow rate, within a limited reach mixtures range. The pilot gas flow rate was always lower than five percent of the total gas supply at the specific stage of the experiments. The experiments and simulation showed that despite the high temperatures obtained in the vicinity of the pilot ring, the radicals’ injection by the pilot combustion has the potential to lower the limit of the global equivalence ratio (and temperatures) while maintaining stable combustion. Therefore the amount of generated NOx is expected to be significantly reduced as compared to a similar combustor of identical inlet and exit temperatures. In order to study the relevant mechanisms responsible for combustion stabilization, CFD and CHEMKIN simulations were performed to reveal the detailed flow characteristics and their spatial distribution within the combustor. Based on the CFD results, the CHEMKIN model was developed. The CHEMKIN simulations for atmospheric pressure showed satisfactory agreement with experimental results. Further simulation confirmed the advantageous of the technique also at elevated pressures. It is therefore important to understand the relevant mechanisms responsible for combustion stabilization and their spatial distribution within the combustor. The present work discusses an experimental- CFD-CHEMKIN combined approach aimed at studying the influence of radicals generated in the pilot ring combustion on the processes taking place in the main combustor.

Abstract Detailed chemical kinetics was implemented into an engine CFD code to study the combustion process in Homogeneous Charge Compression Ignition (HCCI) engines. The CHEMKIN code was implemented into KIVA-3V such that the chemistry and flow solutions were coupled. Effects of turbulent mixing on the reaction rates were also considered. The model was validated using experimental data from a direct-injection Caterpillar engine operated in the HCCI mode using gasoline. The results show that good levels of agreement were obtained using the present KIVA/CHEMKIN model for a wide range of engine conditions including various injection timings, engine speeds, and loads. It was found that the effects of turbulent mixing on the reaction rates needed to be considered to correctly simulate the combustion phasing. It was also found that the presence of residual radicals could enhance the mixture reactivity and hence shorten the ignition delay time. The NOx emissions were found to increase as the injection timing was retarded, in agreement with experimental results.

The technological objective of this work is the development of a lean-premixed burner for natural gas. Sub-ppm NOx emissions can be accomplished by shifting the lean blowout limit (LBO) to slightly lower adiabatic flame temperatures than the LBO of current standard burners. This can be achieved with a novel burner concept utilizing periodic flue gas recirculation: Hot flue gas is admixed to the injected premixed fresh mixture with a mass flow rate of comparable magnitude, in order to achieve self-ignition. The subsequent combustion of the diluted mixture again delivers flue gas. A fraction of the combustion products is then admixed to the next stream of fresh mixture. This process pattern is to be continued in a cyclically closed topology, in order to achieve stable combustion of e.g. natural gas in a temperature regime of very low NOx production. The principal ignition behavior and NOx production characteristics of one sequence of the periodic process was modeled by an idealized adiabatic system with instantaneous admixture of partially or completely burnt flue gas to one stream of fresh reactants. With the CHEMKIN-II package a reactor network consisting of one perfectly stirred reactor (PSR, providing ignition in the first place) and two plug flow reactors (PFR) has been used. The effect of varying burnout and the influence of the fraction of admixed flue gas have been evaluated. The simulations have been conducted with the reaction mechanism of Miller and Bowman and the GRI-Mech 3.0 mechanism. The results show that the high radical content of partially combusted products leads to a massive decrease of the time required for the formation of the radical pool. As a consequence, self-ignition times of 1 ms are achieved even at adiabatic flame temperatures of 1600 K and less, if the flue gas content is about 50%–60% of the reacting flow after mixing is complete. Interestingly, the effect of radicals on ignition is strong, outweighs the temperature deficiency and thus allows stable operation at very low NOx emissions.

Abstract This study focused on the comparative analysis about the production of ozone and active radicals in presence of nanopulsed plasma discharge on air and on fuel/air mixture to investigate its effect on combustion enhancement. This analysis is based on numerical modeling of air and methane/air plasma discharge with different repetition rates (100 Hz, 1000 Hz and 10000 Hz). To this purpose, a two-step approach has been proposed based on two different chemistry solvers: a 0-D plasma chemistry solver (ZDPlasKin toolbox) and a combustion chemistry solver (CHEMKIN software suite). Consequently, a comprehensive chemical kinetic scheme was generated including both plasma excitation reactions and gas phase reactions. Validation of air and methane/air mechanisms was performed with experimental data. Kinetic models of both air and methane/air provides good fitting with experimental data of O atom generation and decay process. ZDPlasKin results were introduced in CHEMKIN in order to analyze combustion enhancement. It was found that the concentrations of O3 and O atom in air are higher than the methane/air activation. However, during the air activation peak concentration of ozone was significantly increased with repetition rates and maximum was observed at 10000 Hz. Furthermore, ignition timings and flammability limits were also improved with air and methane/air activation but the impact of methane/air activation was comparatively higher.

Introduction: Carcinoma cervix is the second most common female carcinoma. Every year in India, 1,22,844 women are diagnosed with carcinoma cervix and of them 67,477 die. Carcinoma cervix rates among women in the age group between 30-64 has decreased by 1.8% per year on average but still date account for 16%. Of these, advanced carcinoma are about 80% and early are only 20%. Case Series: We are reporting 5 consecutive early carcinoma cervix cases who presented with pyometra and got treated at our hospital from April 2015-September 2015. Cases of early carcinoma cervix presented with pyometra were treated by pyometra drainage, intravenous antibiotics and appropriate treatment in the form of surgery (4 cases underwent Wertheim’s hysterectomy and 1 case had radical chemo radiation as she opted for same in view of high cardiac risk for anaesthesia). All 5 of them are disease free at the end of treatment with follow up of minimum 4 months duration (range 4-10). Conclusion: The idea is to emphasize that all carcinoma cervix with pyometra are not necessarily advanced and can still be given radical treatment like surgery or radiotherapy after pyometra drainage.

An investigation on the central-pilot stage of a Siemens Industrial Turbomachinery 4th Generation DLE prototype test burner has been performed to understand the emission performance and operability. The core section, which is defined as RPL (Rich premixed lean) plays an important role for full burner combustion operation by stabilizing the main and pilot flames at different operating condition. Optimal fuel-air flow through the RPL is critical for multiple stages mixing and main flame anchoring. Heat and radical production from the central stage provides the ignition source and required heat for burning the main flame downstream of the RPL section. Surrounding the RPL outside wall cooling air has been blown through an annular passage. The cooling air protects the RPL wall from overheating and provides the oxygen source for the secondary combustion downstream of the RPL. At rich operation unburned hydrocarbon/radicals can pass the RPL and burns by the co-flow air entrainment. To determine the flame stabilization and operability, an atmospheric pressure test has been accomplished using methane as a fuel. Primary flame zone can be identified by a thermocouple placed outside the RPL wall and secondary combustion zone at the exit has been examined by chemiluminescence imaging. Emission measurement and LBO (Lean blow out) limits have been determined for different equivalence ratios from 1.8 to LBO limit. Co-flow air temperature was changed from 303 K to 573 K to evaluate the secondary combustion and RPL wall heat transfer effect on flame stability/emission. It is found that equivalence ratio has strong effect on the RPL flame stabilization (primary/secondary flame). Emissions/radical generation were also influenced by the chemical reaction inside the RPL. It can be noticed that co-flow air temperature has a significant role on emission, LBO and flame stabilization for the central-pilot stage burner due to the heat loss from the flame zone and RPL wall. A chemical kinetic network (Chemkin™) and CFD modelling approaches (Fluent) are employed to understand in detail the chemical kinetics, heat transfer effect and flow field inside the RPL (combustion and heat loss inside and emission capability). Experiment shows that the low CO and NOx levels can be achieved at lean and rich condition due to lower flame temperature. Present experimental results by changing equivalence ratio, residence time and co-flow temperature, creates a complete map for the RPL combustion, which is key input for full 4th Generation DLE burner design.

A generic novel injector was designed for multi-Lean Direct Injection (M-LDI) combustors. One of the drawbacks of the conventional pressure swirl and prefilming type airblast atomizers is the difficulty of obtaining a uniform symmetric spray under all operating conditions. Micro-channels are needed inside the injector for uniformly distributing the fuel. The problem of non-uniformity is magnified in smaller sized injectors. The non-uniform liquid sheet causes local fuel rich/lean zones leading to higher NOx emissions. To overcome these problems, a novel fuel injector was designed to improve the fuel delivery to the injector by using a porous stainless steel material with 30 μm porosity. The porous tube also acts as a prefilming surface. Liquid and gaseous fuels can be injected through the injector. In the present study, gaseous fuel was injected to investigate injector fuel-air mixing performance. The gaseous fuel was injected through a porous tube between two radial-radial swirling air streams to facilitate fuel-air mixing. The advantage of this injector is that it increases the contact surface area between the fuel-air at the fuel injection point. The increased contact area enhances fuel-air mixing. Fuel-air mixing and combustion studies were carried out for both gaseous and liquid fuel. Flame visualization, and emissions measurements were carried out inside the exit of the combustor. The measurements were carried out at atmospheric conditions under fuel lean conditions. Natural gas was used as a fuel in these experiments. Fuel-air mixing studies were carried out at different equivalence ratios with and without confinement. The mass fraction distributions were measured at different downstream locations from the injector exit. Flame characterization was carried out by chemiluminescence at different equivalence ratios and inlet air temperatures. Symmetry of the flame, flame length and heat release distribution were analyzed from the flame images. The effects of inlet air temperature and combustion flame temperature on emissions was studied. Emissions were corrected to 15% O2 concentration. NOx emissions increase with inlet air temperature and flame temperature. Effect of flame temperature on NOx concentration is more significant than effect of inlet air temperature. Fuel-air mixing profile was used to obtain mass fraction Probability Density Function (pdf). The pdfs were used for simulations in Chemkin Pro. The measured emissions concentrations at the exit of the injector was compared with simulations. In Chemkin model, a network model with several PSRs (perfectly stirred reactor) were utilized, followed by a mixer and a PFR (plug flow reactor). The comparison between the simulations and the experimental results was investigated.

The present work is concerned with the thermodynamic and chemical kinetics of gas turbine combustor operating in the Moderate or Intense Low-oxygen Dilution (MILD) combustion regime. The objective of the present study is to evaluate analytically the effect of the recirculation rate of combustion products within the FLOXCOM gas turbine combustor on a number of combustion parameters, mainly on the ignition delay time, NOx and CO emission, minimum ignition temperature, rate of pollutant formation and the dilution rate. The study also refers to the mechanism of influence of the recirculation rate on these values. Combustion pressure and inlet air temperature are used as parameters. The gas turbine is fueled with methane. The analysis is mainly based on CHEMKIN simulations where the calculation scheme of the combustion process in the combustor is modeled by a combination of plug reactors and mixers. Due to the unique characteristics of gas turbines, inlet air temperature is directly linked to combustion pressure while assuming conventional adiabatic compression efficiencies. It is shown that free radicals, which are part of the reaction products and exists for only a short period of time within the recirculated gases, decrease ignition delay time. The importance of shortening the ignition delay is further highlighted because of the adverse effect oxygen dilution has on this parameter (dilution of the reactants by the reaction products). It was found that there is an optimal recirculation rate, which corresponds to maximum heat density. In addition, results indicate that CO emission values rise with the recirculation rate, however the NOX values are more complicated. NOX depends on recirculation rate when flame temperatures are kept held constant. The NOX emission increases and the CO emission decreases with compressor pressure ratio. The CO concentration that is evaluated in the combustion process is further reduced during last dilution stage. Finally, basic rules for design optimization of the combustor are drafted. These are based on conventional one-dimensional fluid and thermodynamic relations and on the CHEMKIN simulations.

A numerical analysis of homogeneous natural gas/diesel/air mixture, that could be formed when small amounts of diesel pilot are used in a diesel dual fuel engine or when using natural gas/diesel dual fuel homogeneous charge compression ignition combustion, was studied to provide insight on future experimental investigations to be conducted by the institution. Use was made of Curran’s normal-heptane mechanism in CHEMKIN to deduce its effects on lean fuel/air mixtures with respect to ignition timing and carbon monoxide (CO) and oxides of nitrogen (NOx) emissions. For the cases considered, increase in the amount of n-heptane addition resulted in advanced ignition closer to TDC thereby increasing peak cylinder pressure and gross IMEP. Increase in the amount of n-heptane addition also resulted in early decomposition of the fuel consequently advancing the production of OH radicals that oxidised the CO. For the same fuel/air mixture strength, increase in the amount of n-heptane addition increased NOx production due to increased peak temperature, residence time and availability of O2. When using leaner mixtures and small amounts of n-heptane to promote/advance ignition, however, peak cylinder temperatures were reduced and hence comparatively reducing engine-out NOx emissions.