The desulfurizing powers of aplite, aplite-soda ash mixtures, and aplite-dehydrated lime combinations when added to a ladle of cast iron were tested. Ladle conditions were simulated by melting cast iron in a crucible and introducing the reagent mixtures into the molten metal by means of a cast iron cup and steel rod. It was found that in every case the desulfurizlng power was appreciably below that of soda ash and did not warrant testing the mixture to determine its effect upon the corrosion of ladle refractory linings. / Master of Science

Parmi les biocarburants de deuxième génération, la chaîne "biomass to liquid" vise à convertir les résidus agricoles en carburant. Cette voie suppose une première étape de gazéification de la biomasse en un gaz de synthèse, mélange de CO et de H2. Ce gaz doit ensuite être désulfuré, afin de ne pas endommager le catalyseur Fischer-Tropsch, à l'aide d'oxydes métalliques tel que l'oxyde de zinc, qui se sulfure selon la réaction suivante : ZnO(s) + H2S(g) → ZnS(s) + H2O(g) a l'heure actuelle, aucune étude ne décrit les mécanismes de la réaction. le but de ce travail a donc été d'identifier les différentes étapes du mécanisme de sulfuration puis d'établir une loi de vitesse de réaction. L'étude cinétique a été réalisée par thermogravimétrie. La formation de cavités au cœur des particules sulfurées a été observée par MEB et MET, mettant en évidence une croissance externe de la phase de ZnS. Un mécanisme de sulfuration en huit étapes élémentaires a été proposé avec diffusion des atomes de zinc et d'oxygène de l'interface interne ZnO/ZnS vers la surface externe du ZnS formé. Le régime limitant de la réaction a été déterminé via l'étude de l'influence des pressions partielles de H2S et de H2O sur la vitesse de réaction. Un régime mixte sur la base de deux étapes élémentaires a été envisagé : une réaction d'interface externe avec désorption des molécules d'eau et la diffusion des atomes d'oxygène. la formation de cavités à l'interface interne ZnO/ZnS entraînant une diminution de la surface de contact entre les phases ZnO et ZnS a été mise en évidence, phénomène probablement à l'origine du ralentissement de la réaction observé sur les courbes cinétiques. / Among the second generation biofuels processes, the "biomass to liquid" process aims at turning agricultural wastes into fuels. This process comprises a first step of feed gasification into a synthesis gas, composed of CO and H2. Sulfur compounds such as H2S are also present in the synthesis gas and must be removed, in order to prevent Fischer-Tropsch catalyst poisoning. deep desulfurization is achieved with metal oxides such as zinc oxide, which reacts with H2S according to the reaction: ZnO(s) + H2S(g) → ZnS(s) + H2O(g) nevertheless to our knowledge, most of the studies found in the literature do not describe accurately the mechanism involved at a crystal scale. The aim of this work was to determine the elementary steps of the ZnO sulfidation reaction, and in fine to establish a kinetic rate model in agreement with the proposed mechanism. The sulfidation reaction has been studied through thermogravimetric experiments. SEM and TEM characterizations of sulfided ZnO have revealed the presence of voids inside particles, that is evidence an external growth of ZnS phase. A sulfidation mechanism with eight elementary steps has been proposed, based on zinc and oxygen diffusion through the ZnS layer from the internal ZnO/ZnS interface to the ZnS surface. The rate determining step of the reaction was determined from the study of the influence of H2S and H2O partial pressures on the reaction rate. A "mixed kinetics" based on two elementary steps was considered: external interface reaction with H2O desorption and oxygen diffusion. Cavities formation at the internal ZnO/ZnS interface leading to a decreasing contact zone between ZnO and ZnS phases might be responsible for the reaction rate blocking observed on the kinetic curves.

Master of Science / Department of Biological and Agricultural Engineering / Stacy L. Hutchinson / Coal-fired generation accounts for 45% of the United States electricity and generates harmful emissions, such as sulfur dioxide. With the implementation of Flue Gas Desulfurization (FGD) systems, sulfur dioxide is removed as an air pollutant and becomes a water pollutant. Basic physical/chemical wastewater treatment can be used to treat FGD wastewater, but increased regulations of effluent water quality have created a need for better, more economical wastewater treatment systems, such as constructed wetlands. At Jeffrey Energy Center, north of St. Mary’s, KS, a pilot-scale constructed wetland treatment system (CWTS) was implemented to treat FGD wastewater before releasing the effluent into the Kansas River. The objectives of this study were to 1.) determine if a portable water quality meter could be used to assess water quality and track pollutant concentrations, 2.) develop a water balance of the CTWS, 3.) generate a water use coefficient for the CWTS, and 4.) create a mass balance on the pollutants of concern. Water quality measurements were taken with a HORIBA U-50 Series Multi Water Quality Checker and compared to analytical water tests provided by Continental Analytic Services, Inc. (CAS) (Salina, KS). The water balance was created by comparing inflows and outflows of data determined through flow meters and a Vantage Pro2™ weather station. Information from the on-site weather station was also used to compute the system water use coefficient. Water sampling was conducted from date to date at 10 locations within the CWTS. In general, there was little to no relationship between the HORIBA water quality measurements and the analytical water tests. Therefore, it was recommended that JEC continue to send water samples on a regular basis to an analytical testing laboratory to assess the CWTS function and track pollutants of concern. Because the water balance was conducted during system initiation, there was a great deal of fluctuation due to problems with the pumping system, issues with the upstream FGD treatment system, extreme weather events, and immature vegetation. This fluctuation resulted in the system having a non-steady state operation, which weakened the ability to calculate a system water use coefficient. However, during periods of strong system function, the water use coefficient was similar to previous studies with maximum water use being approximately equal to the reference evapotranspiration. The results of the mass balance indicated high removals mercury, selenium, and fluoride, but low removals of boron, manganese, chloride, and sulfate were exported from the CWTS.

O mercado atual exige das indústrias siderúrgicas aços de melhor qualidade produzidos por meio de processos que causem menor impacto ao meio ambiente. Dessa forma, este trabalho teve como objetivo reciclar o resíduo de mármore gerado na indústria de rochas ornamentais, que possui em sua composição óxido de cálcio (CaO) e óxido de magnésio (MgO). O CaO é suficiente para substituir a cal nas escórias e o MgO contribui para a diminuição do desgaste dos refratários, através do emprego do resíduo no processo produtivo do aço. Além disso, foi realizada a substituição da fluorita por óxido de boro como fluxante na composição de misturas dessulfurantes. O resíduo de mármore foi caracterizado utilizando as seguintes técnicas: análise química via EDXFR, análise granulométrica via espalhamento de luz, área de superfície específica pelo método BET, difração de raios-X, microscopia eletrônica de varredura (MEV) e análise de micro-regiões por EDS. Visando verificar a eficiência na dessulfuração, foram formuladas misturas sintéticas utilizando a cal convencional ou resíduo de mármore, e a fluorita ou o óxido de boro. As misturas foram formuladas com o auxílio dos programas de termodinâmica computacional, Thermo-Calc e FactSage. Estas misturas foram adicionadas no aço fundido a temperatura de 1600°C sob atmosfera de argônio e agitadas por meio de um rotor de alumina. Amostras de metal foram retiradas para verificar a variação do teor de enxofre durante o experimento. O resíduo de mármore caracterizado, apresentou em sua composição 40% de CaO e 14% de MgO, na forma dos carbonatos CaCO3 e MgCO3. Obteve uma perda de massa de 42,1%, na forma de CO2 a temperatura de 780°C. Os experimentos mostraram que, as misturas testadas apresentaram, na maioria dos casos, eficiência de dessulfuração acima de 60%. / The present market requires from steel industry better quality of steel that was produced by processes that cause less impact to the environment. Thus, this study aims to recycle the marble waste generated from the industry of ornamental rocks, which has in its composition calcium oxide (CaO) and magnesium oxide (MgO). Using this waste in the steel production process, the amount of CaO is enough to replace the lime in the slag whereas the MgO contributes to reduce the wear of the refractory material. Furthermore, it was part of this study to test the replacement of the fluorite by boron oxide as desulfurizing flux into the composition of mixtures. The marble waste was characterized using the following techniques: chemical analysis (EDXFR), particle size analysis with a light scattering method, specific surface area by BET method, Xrays diffraction (XRD), scanning electron microscopy (SEM), analysis of micro-regions by energy dispersive spectroscopy (EDS) and thermogravimetry analysis (TG) with mass spectrometer coupled (MS). In order to verify the efficiency of desulfurization, mixtures were formulated using conventional lime or marble waste, and fluorite or boron oxide. The blends were prepared using the computational thermodynamics programs, Thermo-Calc and FactSage. These mixtures were added into the molten steel under an argon atmosphere and the metallic bath stirred by a rotor of alumina at the temperature of 1600ºC. Metal Samples were removed periodically in order to verify the variation of sulfur content during the experiments. The characterization of marble waste showed in its composition the amount of 40% CaO and 14% MgO in a CaCO3 and MgCO3 carbonates forms. It was also observed a mass loss of 42.1%, in the form of CO2 at a temperature of 780 ° C. The experiments showed that the tested mixtures desulfurization efficiency was above 60%, in most cases.

Combined treatment technologies for the removal of waste carbon, nitrogen, and/or sulfur under anoxic/anaerobic conditions have recently received considerable attention. It has been reported that nitrate and/or reduced N-oxides, such as nitrite (NO2-), nitric oxide (NO), and nitrous oxide (N2O), which are products of denitrification, suppress methanogenesis. Research was conducted to investigate the effect of N-oxides and sulfide on mixed, mesophilic (35oC) methanogenic cultures, along with the effect of the type of electron donor on the kinetics and pathway of nitrate reduction. Among all N-oxides tested, NO exerted the most and nitrate exerted the least inhibitory effect on the fermentative/methanogenic consortia. Long-term exposure of a methanogenic culture to nitrate resulted in an increase of N-oxide reduction and a decrease of methane production rates. Sulfide addition to sulfide-free enriched cultures resulted in inhibition of NO2-, NO, and N2O reduction causing accumulation of these intermediates, which in turn inhibited methanogenesis and fermentation. In nitrate-amended, sulfide-acclimated cultures, nitrate reduction occurred via dissimilatory nitrate reduction to ammonia (DNRA); thus, accumulation of N-oxides was avoided and inhibition of methanogenesis was prevented. The nitrate reduction rates in cultures fed with different electron donors followed the descending order: H2/CO2 > acetate > glucose > dextrin/peptone > propionate. Denitrification was observed in the propionate-, acetate-, and H2/CO2-fed cultures regardless of the COD/N value. Both denitrification and DNRA were observed in the dextrin/peptone- and glucose-fed cultures and the predominance of either of the two pathways was a function of the COD/N value. Nitrate reduction processes were incorporated into the IWA Anaerobic Digestion Model No. 1 (ADM1) in order to account for the effect of nitrate reduction processes on fermentation and methanogenesis. The extended ADM1 described the experimental results very well. Model simulations showed that process interactions during nitrate reduction within an overall methanogenic system cannot be explained based on only stoichiometry and kinetics, especially for batch systems and/or continuous-flow systems with periodic, shock nitrate loads. The results of this research are useful in predicting the fate of carbon-, nitrogen-, and sulfur-bearing waste material, as well as in understanding microbial process interactions, in both natural and engineered anoxic/anaerobic systems.

The reduction of sulphur in transportation fuel has gained significant importance as the regulatory agencies worldwide react to air quality concerns and the impact of sulphur oxides on the environment. The overall objective of this research was to identify, develop and characterize, based on underlying scientific principles, sorbents that are effective in removal of refractory sulphur compounds from fuel through the process of selective adsorption. It was determined that impregnation of powdered activated carbon with a transition metal (TM) significantly boosted the adsorption performance of the activated carbon. It is hypothesized that the impregnation resulted in the formation of new adsorptive sites that strongly interacted with the lone pairs of electrons on sulphur and nitrogen while having minor impact on the existing oxygen functional groups on the surface of the activated carbon. The percent loading of the TM was determined through wet adsorption study. The best performing sorbent was shown to have maximum adsorption capacities of approximately 1.77 and 0.76 mmol-S/g-sorbent for DBT and 4,6 DMDBT, respectively, with approximately 100% regenerability through solvent wash and thermal treatment. On average, the PTM impregnation showed approximately 137% increase in adsorption capacity of the activated carbon. The sorbent also has good adsorption capacities for organo-nitrogen compounds (i.e., quinoline and carbazole) and a low selectivity towards aromatics, which is desired in adsorptive desulphurization. The surface morphology of the activated carbon, the oxygen functional groups on the surface of the activated carbon, as well as strong (chemisorption) interaction between the TM???s partly vacant and far reaching ???d??? orbital and lone pair electrons on sulphur and nitrogen are considered to be the main contributing factors to the observed enhancement. It was established in this study that the adsorption isotherms of the impregnated activated carbons best fit Sips isotherm equation, which is a combination of the Langmuir and Freundlich equations. This finding fits well with our initial hypothesis regarding the introduction of new adsorptive sites as a result of TM impregnation and that the sites did not fit well with Langmuir???s monolayer and uniform adsorption mechanism. A kinetic study of the sulphur adsorption using a flow reactor showed a good fit with pseudo second order kinetic model, indicative of an adsorption that is highly dependent on the concentration of available sites on the surface of the sorbent. On average, as expected, the TM impregnated ACC exhibited a higher initial rate of adsorption. The adsorption onto TM sites tends to be more exothermic than adsorption (mainly physisorption) on activated carbon. Therefore, more thermodynamically favoured chemisorption is expected to occur more rapidly than physisorption. It was determined that on average, the initial adsorption rate does not change significantly with temperature while the sulphur adsorption capacity decreases with increase in temperature. It is postulated that the increase in temperature increases surface diffusivity but impedes diffusion flux. The impediment of the diffusion flux will result in reduction in adsorbed quantity. It was also shown that the intra-particle diffusion exists in the adsorption of DBT on TM impregnated activated carbon, however, it is not likely that the overall adsorption is controlled or noticeable impacted by it. As the temperature of the reactor increases the Weber-Morris intra-particle diffusion plot moves away from the origin, and thus intra-particle diffusion becomes less of a controlling mechanism. This further confirms the fact that the boundary layer (i.e., surface diffusion) and potentially adsorptive interactions at the surface are the dominating mechanisms in the sulphur adsorption onto TM impregnated activated carbon. It was determined that the distribution of TM species on the surface of the activated carbon is relatively inhomogeneous, with some areas showing well dispersed TM species while other areas showing large clusters. Different impregnation method that can improve dispersion on the surface may significantly enhance adsorption performance of the sorbent. Furthermore, in this study impregnation of activated carbon using several other transition metals were examined. It was determined that other less expensive transition metals can also improve the adsorption performance of the activated carbon. Further study on less expensive options for impregnating the activated carbon may be beneficial.

ABSTRACT REMOVAL OF HYDROGEN SULFIDE BY REGENERABLE METAL OXIDE SORBENTS Karayilan, Dilek M.S., Department of Chemical Engineering Supervisor : Prof. Dr. Timur Dogu Co-Supervisor: Prof. Dr. G&uuml / lSen Dogu June 2004, 166 pages High-temperature desulfurization of coal-derived fuel gases is an essential process in advanced power generation technologies. It may be accomplished by using metal oxide sorbents. Among the sorbents investigated CuO sorbent has received considerable attention. However, CuO in uncombined form is readily reduced to copper by the H2 and CO contained in fuel gases which lowers the desulfurization efficiency. To improve the performance of CuO-based sorbents, they have been combined with other metal oxides, forming metal oxide sorbents. Sulfidation experiments were carried out at 627 oC using a gas mixture composed of 1 % H2S and 10 % H2 in helium. Sorbent regeneration was carried out in the same reactor on sulfided samples at 700 oC using 6 % O2 in N2. Total flow rate of gas mixture was kept at 100 ml/min in most of the experiments. In this study, Cu-Mn-O, Cu-Mn-V-O and Cu-V-O sorbents were developed by using complexation method. Performance of prepared sorbents were investigated in a fixed-bed quartz microreactor over six sulfidation/regeneration cycles. During six cycles, sulfur retention capacity of Cu-Mn-O decreased slightly from 0.152 to 0.128 (g S)/(g of Sorbent) while some decrease from 0.110 to 0.054 (g S)/(g of Sorbent) was observed with Cu-Mn-V-O. Cu-V-O showed a very good performance in the first sulfidation and excessive thermal sintering in the first regeneration prevented further testing. Sulfur retention capacity of Cu-V-O was calculated as 0.123 (g S)/(g of Sorbent) at the end of the first sulfidation. In addition, SO2 formation in sulfidation experiments was observed only with Cu-V-O sorbent.

O mercado atual exige das indústrias siderúrgicas aços de melhor qualidade produzidos por meio de processos que causem menor impacto ao meio ambiente. Dessa forma, este trabalho teve como objetivo reciclar o resíduo de mármore gerado na indústria de rochas ornamentais, que possui em sua composição óxido de cálcio (CaO) e óxido de magnésio (MgO). O CaO é suficiente para substituir a cal nas escórias e o MgO contribui para a diminuição do desgaste dos refratários, através do emprego do resíduo no processo produtivo do aço. Além disso, foi realizada a substituição da fluorita por óxido de boro como fluxante na composição de misturas dessulfurantes. O resíduo de mármore foi caracterizado utilizando as seguintes técnicas: análise química via EDXFR, análise granulométrica via espalhamento de luz, área de superfície específica pelo método BET, difração de raios-X, microscopia eletrônica de varredura (MEV) e análise de micro-regiões por EDS. Visando verificar a eficiência na dessulfuração, foram formuladas misturas sintéticas utilizando a cal convencional ou resíduo de mármore, e a fluorita ou o óxido de boro. As misturas foram formuladas com o auxílio dos programas de termodinâmica computacional, Thermo-Calc e FactSage. Estas misturas foram adicionadas no aço fundido a temperatura de 1600°C sob atmosfera de argônio e agitadas por meio de um rotor de alumina. Amostras de metal foram retiradas para verificar a variação do teor de enxofre durante o experimento. O resíduo de mármore caracterizado, apresentou em sua composição 40% de CaO e 14% de MgO, na forma dos carbonatos CaCO3 e MgCO3. Obteve uma perda de massa de 42,1%, na forma de CO2 a temperatura de 780°C. Os experimentos mostraram que, as misturas testadas apresentaram, na maioria dos casos, eficiência de dessulfuração acima de 60%. / The present market requires from steel industry better quality of steel that was produced by processes that cause less impact to the environment. Thus, this study aims to recycle the marble waste generated from the industry of ornamental rocks, which has in its composition calcium oxide (CaO) and magnesium oxide (MgO). Using this waste in the steel production process, the amount of CaO is enough to replace the lime in the slag whereas the MgO contributes to reduce the wear of the refractory material. Furthermore, it was part of this study to test the replacement of the fluorite by boron oxide as desulfurizing flux into the composition of mixtures. The marble waste was characterized using the following techniques: chemical analysis (EDXFR), particle size analysis with a light scattering method, specific surface area by BET method, Xrays diffraction (XRD), scanning electron microscopy (SEM), analysis of micro-regions by energy dispersive spectroscopy (EDS) and thermogravimetry analysis (TG) with mass spectrometer coupled (MS). In order to verify the efficiency of desulfurization, mixtures were formulated using conventional lime or marble waste, and fluorite or boron oxide. The blends were prepared using the computational thermodynamics programs, Thermo-Calc and FactSage. These mixtures were added into the molten steel under an argon atmosphere and the metallic bath stirred by a rotor of alumina at the temperature of 1600ºC. Metal Samples were removed periodically in order to verify the variation of sulfur content during the experiments. The characterization of marble waste showed in its composition the amount of 40% CaO and 14% MgO in a CaCO3 and MgCO3 carbonates forms. It was also observed a mass loss of 42.1%, in the form of CO2 at a temperature of 780 ° C. The experiments showed that the tested mixtures desulfurization efficiency was above 60%, in most cases.

Submitted by Marco Antonio Oliveira da Silva (maosilva@ipen.br) on 2017-10-27T12:15:25Z No. of bitstreams: 0 / Made available in DSpace on 2017-10-27T12:15:25Z (GMT). No. of bitstreams: 0 / A síntese de zeólitas a partir de cinzas leves e pesadas de carvão mineral foi realizada por tratamento hidrotérmico alcalino, as quais foram nomeadas ZCL e ZCP, respectivamente. As zeólitas organomodificadas ZML e ZMP foram obtidas a partir da modificação superficial de ZCL e ZCP, respectivamente, utilizando o surfactante catiônico brometo de hexadeciltrimetilamônio. A partir das soluções remanescentes geradas na síntese de ZCL e ZCP foi possível sintetizar duas novas zeólitas. As características físicoquímicas dos nanomateriais zeolíticos sintetizados, bem como de suas respectivas matérias primas, tais como: capacidade de troca catiônica, massa específica, área específica, composição química, mineralógica e morfológica, entre outras, foram determinadas. Os adsorventes ZML e ZMP foram utilizados na remoção dos corantes Azul Direto 71 (DB71) e Rodamina B (RB) de soluções aquosas em sistema de batelada. Desta forma, quatro sistemas DB71/ZML, RB/ZML, DB71/ZMP e RB/ZMP foram investigados. Os modelos de pseudoprimeira ordem e pseudo-segunda ordem foram aplicados aos dados experimentais para o estudo da cinética de adsorção. O modelo de pseudosegunda ordem foi o que melhor descreveu o processo de adsorção de todos os sistemas corante/zeólita organomodificada. O equilíbrio da adsorção foi analisado a partir de quatro modelos de isoterma, sendo eles: Langmuir, Freundlich, Temkin e Dubinin-Radushkevich (D-R). Os resultados mostram que os modelos de Freundlich e Langmuir melhor descreveram os dados experimentais dos sistemas DB71/ZML e DB71/ZMP, respectivamente. Para os sistemas com RB, o modelo de D-R foi o que melhor se ajustou para ambos adsorventes ZML e ZMP. O planejamento fatorial 24 foi aplicado para a análise dos seguintes fatores que influenciam o processo de adsorção: concentração inicial do corante (Co), pH, dose de adsorvente (M) e temperatura (T). De acordo com as condições estudadas concluiu-se, com o intervalo de confiança igual a 95%, que para o sistema DB71/ZML, os fatores e suas interações que mais influenciam foram C0, M, pH, pH*M, pH*C0, M*C0, pH*M*C0, nessa ordem. No sistema DB71/ZMP, a ordem de influência foi: M, C0, pH, pH*M, pH*C0, M*C0, pH*M*C0. Para os sistemas RB/ZML e RB/ZMP, os resultados foram: M, C0, M*C0, pH, pH*M e M, C0, M*C0, respectivamente. O equilíbrio de adsorção foi atingido em cerca de 40 min para todas as amostras. As porcentagens de remoção do DB71 estavam na faixa de 50 80% e 20 50% para ZML e ZMP, respectivamente. A faixa de porcentagens de remoção do RB variou entre 60 80% e 30 50% para ZML e ZMP, respectivamente. / Dissertação (Mestrado em Tecnologia Nuclear) / IPEN/D / Instituto de Pesquisas Energéticas e Nucleares - IPEN-CNEN/SP

This diploma thesis deals with the control calculation of fluid biomass boilers with circulating fluidized bed. The introduction briefly introduced fluidized bed boilers and explained what biomass is. Furthermore there is a stoichiometric calculation of combustion. The calculation of the losses and the efficiency of the boiler is following. Desulphurization is calculated briefly. The main part is devoted to the design and calculation of individual heat exchanging surfaces: superheater P1, superheaters 2 and 3, the wall superheater, the return chamber, hanging tubes, economizer and air heater. At the end is calculated total tolerance boiler. Work is completed with a diagram of temperature of working media and combustion.