Growing environmental concerns, such as global warming, are giving rise to new regulations imposed by the International Maritime Organization (IMO) on sulfur content for marine fuels, thus, constraining refining processes. Oxidative desulfurization (ODS) is an appealing desulfurization method with some advantages over traditional processes like hydrodesulfurization (HDS), such as mild operating conditions and no-hydrogen consumption. ODS could be employed as a complementary or alternative process for HDS. During the oxidative desulfurization, the organo-sulfur compounds are oxidized to polar sulfones. Then, such sulfones are separated from the treated fuel oil using techniques such as liquid-liquid extraction. In the present work, the separation of oxidized sulfur-containing compounds of heavy fuel oil using ultrasound-assisted technology has been investigated and simulated in Aspen Plus. The oxidant selected was hydrogen peroxide, while the catalyst was acetic acid. The chosen solvent for the sulfone separation was acetonitrile. The primary goal of this work is to successfully emulate the operation performed by an oxidative desulfurization pilot plant-scale apparatus designed by Tecnoveritas®, which will later allow the analysis of the parameters on the overall sulfur removal efficiency.

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Volatile sulfur compounds are cause of concern because, when present in high concentrations, they constitute a danger for health because of their strong toxicity. Furthermore, for low concentrations, they are often a cause of complaint, because of their low odor threshold. In this context, the purpose of this Thesis is to evaluate a new technology for the abatement of sulfur-based malodorous compounds. The investigated technology consists in the use of ozone generating low-pressure UV mercury lamps, operating at room temperature. Hydrogen sulfide is often found in industrial processes, (e.g. WWTPs (Wastewater Treatment Plants), leather production, sewage treatment, garbage disposal, etc). Moreover, it presents both a very high toxicity a low odor threshold. Thus, due to its high representativeness of the case, hydrogen sulfide was chosen as reference compound for the purposes of this project. In order to evaluate a wide range of cases, several experiments using different residence times, humidity contents and inlet concentrations of the pollutant were conducted. The obtained results show that this technology generally presents discrete conversion efficiencies, although not suffcient to be used as freestanding process. For this reason, a pretreatment is revealed to be necessary. The best conversion efficiency was obtained for low flow rates and high moisture content. At the end of the project, as side-study, a possible pretreatment using an adsorbent bed constituted by granular ferric oxide was evaluated.

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.

Made available in DSpace on 2014-12-17T15:01:57Z (GMT). No. of bitstreams: 1 KahildeteRFD_TESE.pdf: 2018469 bytes, checksum: 2bf4c3c4dd7f5e60e73413d8e6ce2dd5 (MD5) Previous issue date: 2014-03-12 / The diesel combustion form sulfur oxides that can be discharged into the atmosphere as particulates and primary pollutants, SO2and SO3, causing great damage to the environment and to human health. These products can be transformed into acids in the combustion chamber, causing damage to the engines. The worldwide concern with a clean and healthy environment has led to more restrictive laws and regulations regulating the emission levels of pollutants in the air, establishing sulfur levels increasingly low on fuels. The conventional methods for sulfur removal from diesel are expensive and do not produce a zero-level sulfur fuel. This work aims to develop new methods of removing sulfur from commercial diesel using surfactants and microemulsion systems. Its main purpose is to create new technologies and add economic viability to the process. First, a preliminary study using as extracting agent a Winsor I microemulsion system with dodecyl ammonium chloride (DDACl) and nonyl phenol ethoxylated (RNX95) as surfactant was performed to choose the surfactant. The RNX95 was chosen to be used as surfactant in microemulsioned systems for adsorbent surface modification and as an extracting agent in liquid-liquid extraction. Vermiculite was evaluated as adsorbent. The microemulsion systems applied for vermiculite surface modification were composed by RNX95 (surfactant), n-butanol (cosurfactant), n-hexane (oil phase), and different aqueous phases, including: distilled water (aqueous phase),20ppm CaCl2solution, and 1500ppm CaCl2solution. Batch and column adsorption tests were carried out to estimate the ability of vermiculite to adsorb sulfur from diesel. It was used in the experiments a commercial diesel fuel with 1,233ppm initial sulfur concentration. The batch experiments were performed according to a factorial design (23). Two experimental sets were accomplished: the first one applying 1:2 vermiculite to diesel ratio and the second one using 1:5 vermiculite to diesel ratio. It was evaluated the effects of temperature (25?C and 60?C), concentration of CaCl2in the aqueous phase (20ppm and 1500ppm), and vermiculite granule size (65 and 100 mesh). The experimental response was the ability of vermiculite to adsorb sulfur. The best results for both 1:5 and 1:2 ratios were obtained using 60?C, 1500ppm CaCl2solution, and 65 mesh. The best adsorption capacities for 1:5 ratio and for 1:2 ratio were 4.24 mg sulfur/g adsorbent and 2.87 mg sulfur/g adsorbent, respectively. It was verified that the most significant factor was the concentration of the CaCl2 solution. Liquid-liquid extraction experiments were performed in two and six steps using the same surfactant to diesel ratio. It was obtained 46.8% sulfur removal in two-step experiment and 73.15% in six-step one. An alternative study, for comparison purposes, was made using bentonite and diatomite asadsorbents. The batch experiments were done using microemulsion systems with the same aqueous phases evaluated in vermiculite study and also 20ppm and 1500 ppm BaCl2 solutions. For bentonite, the best adsorption capacity was 7.53mg sulfur/g adsorbent with distilled water as aqueous phase of the microemulsion system and for diatomite the best result was 17.04 mg sulfur/g adsorbent using a 20ppm CaCl2solution. The accomplishment of this study allowed us to conclude that, among the alternatives tested, the adsorption process using adsorbents modified by microemulsion systems was considered the best process for sulfur removal from diesel fuel. The optimization and scale upof the process constitutes a viable alternative to achieve the needs of the market / Os ?xidos de enxofre formados pela combust?o do ?leo diesel podem ser descarregados para a atmosfera sob a forma de particulados e poluentes prim?rios como SO2 e SO 3, acarretando grandes preju?zos ao meio ambiente e ? sa?de humana e, ainda, podem se transformar em ?cidos na c?mara de combust?o, causando danos aos motores. A preocupa??o mundial com o meio ambiente saud?vel e despolu?do tem levado ? institui??o de normas e leis no sentido de reduzir os n?veis de emiss?o de poluentes no ar, estabelecendo teores de enxofre cada vez mais baixos nos combust?veis, de modo a seter produtos menos agressivos ao meio ambiente e ? sa?de p?blica. Os m?todos convencionais de remo??o de enxofre do diesel t?m custo elevado, al?m de n?o serem capazes de produzir combust?veis com n?vel zero de enxofre. Assim, este trabalho tem como objetivo desenvolver novos m?todos de remo??o de enxofre do diesel utilizando tensoativos e sistemas microemulsionados, procurando associar novas tecnologias e viabilidade econ?mica aos processos. Para escolha do tensoativo, foi feito um estudo de extra??o na regi?o de Winsor I, com cloreto de dodecilam?nio (DDACl) e nonil fenol etoxilado (RNX 95). A partir dos resultados foi escolhido o RNX 95, como constituinte dos sistemas microemulsionados utilizados na modifica??o dos adsorventes, para os processos de adsor??o e, como extratante, para extra??o l?quido-l?quido. Utilizou-se como adsorvente a vermiculita tratada com uma microemuls?o constitu?da por RNX 95 (tensoativo), n-butanol (cotensoativo), hexano (fase oleosa) e ?gua destilada, solu??o salina de CaCl220 ppm, solu??o salina de CaCl2 1500 ppm (fase aquosa), nos processos de adsor??o, em banho finito e em coluna, cuja fase fluida foi o ?leo diesel comercial (1233 ppm de enxofre). Na etapa de adsor??o em banho finito aplicaram-se duas abordagens estat?sticas pelo m?todo do planejamento fatorial completo (23), com tr?s vari?veis (temperatura, concentra??o da solu??o salina de CaCl2 e granulometria da vermiculita) em dois n?veis experimentais (superior e inferior), variando a raz?o vermiculita:diesel, sendo um planejamento fatorial para a raz?o igual a 1:2 e outro para raz?o igual a 1:5. A resposta experimental foi a capacidade da vermiculita em adsorver o enxofre. Os melhores resultados, tanto para a raz?overmiculita/diesel de 1:5 como para a raz?o 1:2, foram obtidos a uma temperatura de 60?C, concentra??o de CaCl 2 1500 ppm e granulometria da vermiculita 65 mesh, obtendo-se capacidades de adsor??o de 4,24 mg/g para a raz?o 1:5 e 2,87 mg/g, para a raz?o 1:2, indicando que a vari?vel mais significativa, em ambas as raz?es, foi a concentra??o da solu??o salina de CaCl2. Na extra??o l?quido-l?quido, realizada em duas e em seis etapas, utilizou-se a mesma propor??o de tensoativoe diesel e obtiveram-se percentuais de extra??o de 46,8% e 73,15%, respectivamente. Foi realizado tamb?m um estudo alternativo de modifica??o de outros adsorventes para fins de compara??o. Os ensaios foram feitos em banho finito com bentonita e diatomita, modificadas com microemuls?o. Os agentes modificadores foram os j? estudados neste trabalho acrescidos de solu??es salinas de BaCl220 ppm e 1500 ppm, como fases aquosas dos sistemas microemulsionados. Para a bentonita a melhor capacidade de adsor??o foi de 7,53 mg/g utilizando o sistema microemulsionado com ?gua destilada na fase aquosa e para a diatomita o melhor resultado ocorreu com a microemuls?o contendo solu??o salina de CaCl2 20ppm, obtendo-se uma capacidade de adsor??o de 17,04 mg/g. A realiza??o deste estudo permite concluir que, dentre as alternativas testadas, a adsor??o utilizando adsorventes impregnados por microemuls?es foi considerado o melhor processo de remo??o do enxofre do diesel e que a sua otimiza??o e scale upconstitui-se em uma alternativa vi?vel e de custo compat?vel comas necessidades do mercado