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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
121

Nanoporous polymeric adsorbents for blood purification

Roche, Iain January 2009 (has links)
This thesis is concerned with applying engineering principles to the use of polymeric nanoporous adsorbents for use in blood purification to obtain original knowledge. Styrene divinylbenzene copolymer nanoporous adsorbents offer a potential means to remove middle molecular (MM) sized molecules when in direct contact with blood. (Continues...).
122

PILCs for trapping phosphorus in a heavy duty engine exhaust system : An experimental evaluation of the phosphorus sorption capability of different clay materials

Kvarned, Anders January 2016 (has links)
In order to fulfil the requirements in the EURO VI standard, regulating emissions from heavy duty vehicles, the exhaust aftertreatment system needs to maintain its efficiency for at least seven years or 700 000 km. In diesel applications the diesel oxidation catalyst (DOC) is located closest to the engine and is thus the most vulnerable to poisoning contaminants, such as phosphorus originating from fuel and oil additives, which deactivates the catalyst. An idea to reduce the impact from phosphorus impurities (recently patented by Scania CV) is to place a low-cost sacrificial substrate, consisting of one or more pillared clay mineral (PILC) with high affinity for phosphorus, upstream the aftertreatment system in order to protect and thus increase the lifetime of the catalytic components which contain platinum group metals. In this work one commercially available and four custom made PILCs, comprising of two conventional type PILCs and two of the type porous clay heterostructures (PCH), were evaluated. The PILCs were exposed to a phosphorus-containing gaseous mixture using a lab-scale experimental setup in order to determine their phosphorus sorption potential. The PILC materials exhibit potential to function as sacrificial substrates for phosphorus in the intended application. It was indicated to be a correlation between increasing iron content (wt%) and increasing phosphorus sorption capability. The most promising material was the custom made Al,Fe-pillared saponite, which was up to twice as effective in trapping phosphorus as the DOC. The commercial sample, the Al-pillared montmorillonite, was only about as efficient as the DOC.
123

Sorption behaviour of metal contaminants in clay minerals, soils and matrices : understanding the influence of organic matter, pH, ionic strength and mineralogy

Anjolaiya, Olanrewaju January 2015 (has links)
Many chemical and physical factors govern the mobility of metal contaminants in soils and clay systems; some of these chemical factors include mineralogical composition, cation exchange capacity, organic matter content, pH and the ionic strength of soil water. This makes understanding and therefore predicting the fate of metal contaminants in soils a complex undertaking. There were two broad objectives in this study. The first was to investigate binary and ternary sorption systems, with the aim to understand the effects that factors such as pH, ionic strength, organic matter and metal concentrations, have on sorption of simple clay minerals (bentonite and kaolinite) with metals (cadmium, caesium, nickel and strontium). The second was to investigate the retention of heavy metals and radionuclides by well characterised organic-rich and organic-poor clay soils, breaking them down to their individual components to help understand the effects of each component separately, the study also tested to see if the additivity principle holds for these heavy metals and radionuclides, the additivity principle presumes that the overall sorption behaviour of a complex mixture is a summation of the weighted individual sorption behaviours of its constituents. The study also determined the relationship between the natural organic matter (NOM) content and cation exchange capacity (CEC) of the soils and how these affect the mobility of the metals, while also considering the relative importance of the speciation of the metals. Two British clay soils (Mercia Mudstone and London Clay) and two Nigerian soils (an organic-rich Ikeja Loam and the other organic-poor Magodo Laterite) were characterised by X-ray diffraction (XRD) analysis. Batch techniques were employed for the sorption studies, and radiometric techniques, ICP-OES and ICP-MS were used to quantify metal distribution between phases. The sorption of dissolved organic matter to clay minerals is very dependent on pH; this dependence is greater with increasing concentration of organic matter. The formation of metal-humate complexes is dependent on the nature of the metal and pH. Caesium exhibits no discernible sorption to humic acid, cadmium sorption is enhanced by increasing alkalinity but this enhancement is slightly reduced in higher concentrations of humic acid, nickel sorption is mostly unaffected by pH except in higher concentrations of humic acid and enhanced only under very low concentrations of humic acid, while strontium sorption to humic acid is reduced with increasing alkalinity. The nature and preference of humic acid sorption for these metals are vital to understanding the role played by humic acid in the ternary sorption studies of metals, humic acid and clay minerals. Strongly acidic conditions dominate other factors affecting sorption such as ionic strength in sorption of metals to clay minerals. Caesium sorption to bentonite at pH 4 is poor and almost unaffected by ionic strength of the electrolyte solution; saturation of sorption sites is reached with low amounts of adsorbed caesium. Strontium also binds poorly to bentonite at pH 4, more so than caesium, but an ionic strength effect on sorption still exists and is discernible even under these conditions. Increasing alkalinity has the expected effect of increasing sorption capacity of bentonite for both metals. Bentonite has poor sorption properties, having low affinity for caesium and strontium, but has greater affinity for caesium than strontium. The presence of humic acid can enhance or suppresses sorption, this varies from metal to metal and from solid to solid, the degree of enhancement or suppression also depends on humic acid concentration. Kaolinite has better sorption properties than bentonie. Cadmium has greater sorption affinity for kaolinite in the absence of humic acid, but nickel sorption is more enhanced in the presence of humic acid. Although the presence of humic acid enhances cadmium and nickel sorption to kaolinite, low humic acid concentration provides the best conditions for maximum sorption of both metals. High concentrations of humic acid lead to colloid formation which block access of metals with larger hydration radii to sorption sites while also encouraging the formation of humic acid-metal complexes. As with bentonite, caesium and strontium are both poorly sorbed by kaolinite. Unlike with cadmium and nickel however, the enhancement of strontium sorption is supported by higher concentrations of humic acid, these confirm a greater preference for the formation of S-HA-Sr ternary and lower preference for the formation HA-Sr binary complexes. The presence of humic acid inhibits caesium binding, and retention but this reduces with increasing alkalinity, while the reverse is the case with strontium whose retention is very poor and improved in the presence of humic acid and increasing alkalinity. Both caesium and strontium are poorly sorbed and retained by kaolinite but their retention improves with increasing humic acid concentration and pH. Cadmium and nickel also exhibit poor retention to kaolinite but their retentions are more improved under alkaline conditions and higher humic acid concentrations, nickel more so than cadmium. Similar sorption affinities were exhibited by the British (London Clay and Mercia Mudstone) and Nigerian soils (Magodo Laterite and Ikeja Loam) for the metals studied, showing the significance of soil constituent contribution to sorption behaviour. Both British clay matrices have affinity for the metals in the order Cs >> Cd ≈ Ni >> Sr, London Clay has the greater sorption capacity for all the metals, the clay mineral content of Mercia Mudstone is almost entirely made up of Illite while London Clay contains a mixture of smectite, illite and kaolinite with smectite being the most prevalent clay mineral phase. These confirm that smectite-rich clay systems will exhibit better sorption and retention capacities for metal contaminants. Both Nigerian soils showed the same order of affinity for all the metals Cd >> Ni >> Cs >> Sr, cadmium s preferential sorption to kaolinite was observed in its greater sorption and retention by the Nigerian soils which are kaolinite-rich. This preferential sorption of cadmium by kaolinite is confirmed by the Standard Addition experiment where its contribution to cadmium sorption is clearly evident, a trend not replicated with nickel as the sorbing metal. The presence of organic matter in soils or clay systems improves their metal sorption capacity significantly, especially true for insoluble organic matter, however its significance is reduced as pH increases. The contribution of organic matter also depends on the sorption affinity of the metal for organic matter; metals such like strontium are more affected by organic matter presence. The overall sorption behaviour of complex systems such as soils is difficult to attribute to their individual constituents. The laterite soils can be considered a relatively simple soil system containing only four constituents in significant quantities, yet it is difficult to replicate its sorption behaviour using a replicate proportioned mixture of its constituent phases. The additively calculated sorption profiles for the synthetic laterite were different from those obtained experimentally, the reason for this is that the existence of significant particle size differences between the natural and synthetic soils give rise to differences in the availability of sorption sites which is evident from the different CEC values measured for both systems.
124

New Synthetic Strategies for Improved Gas separation by Nanoporous Organic Polymers

Altarawneh, Suha 01 January 2014 (has links)
Abstract NEW SYNTHETIC STRATEGIES FOR IMPROVED GAS SEPARATION BY NANOPOROUS ORGANIC POLYMERS Suha S. Altarawneh, Ph.D. The emission of carbon dioxide (CO2) from fossil fuel combustion is a major cause of climate change. Therefore, the efficient separation of CO2 from mixtures of gases such as flue gas and impure sources of CH4 (e.g. natural gas and landfill gas) is an essential step in meeting the ever increasing demands on natural gas and creating a cleaner environment. Carbon capture and storage technology (CCS) is one of the methods employed for gas separation using chemisorption and/or physisorption processes. Several materials such as porous polymers and amine solutions have been used as gas adsorbents. However, the amount of energy required for the adsorbent regeneration is one of the main concerns that needs to be addressed. In this regard, porous organic polymers (POPs) with defined porosity and preferential binding affinity for CO2 over N2 and CH4 are some of the most attractive materials that could fulfill the above requirement and are also applicable for use in gas storage and separation. Suitable POPs that can be used for gas storage applications need to have high porosity and mechanical stability under high pressure conditions (~100 bar). Alternatively, the most effective POPs in gas separation are those that have preferential binding affinity for CO2 over other gases present at low pressure settings. In all cases, the chemical nature of POPs and their textural properties are key parameters, however, the modest surface area of most POPs limits their efficiency. With the above considerations in mind, the aim of our research is to develop benzimidazole–linked polymers (BILPs) that have variable porosity levels and chemical functionality to enhance gas separation (CO2/CH4, CO2/N2). We have established new synthetic routes that utilize polycondensation reactions between aryl-aldehydes and aryl-o-diamine building units to construct new BILPs with improved gas separation properties. Our strategy targeted structural and textural modifications of BILPs. We used longer linkers (building units) to improve porosity; however, the flexible linkers offered only low porosity due to network interpenetration. To overcome this challenge, a more controlled network growth rate was assessed by adjusting imine-bond formation rates through different acid loading. The acid, HCl, was used to catalyze imine-bond formation. The new resulting acid-catalyzed BILPs have shown an improved porosity up to 92% compared to the non-catalyzed BILPs. We also used the “rational ligand design” approach to introduce new functionalities into BILPs (-OR) to alter the hydrophobic nature of their pores. In this regard, we have illustrated the applicability of this strategy to BILPs containing flexible aryl-o-diamine linkers. The bulky alkoxy groups were incorporated into the aryl-aldehyde building unit prior to polymerization. The resulting polymers have proven that the presence of the bulky pendant alkoxy-chains plays a significant role during the polymerization process which allows for increased control over network formation, and in turn, porosity. Sorption measurements, selectivity, and heats of adsorption data have confirmed the positive impact of the alkoxy-groups and shown that varying the pendant groups is a promising method for designing highly porous BILPs. In addition to pore functionalization with alkoxy-chains, we used pi-conjugated and N-rich building units to prepare new BILPs that have semiconducting properties in addition to their porous nature. This class of BILPs has shown that the extended-conjugated system improved BILPs electronic properties. The other studies performed in this research, involved the use of DFT theory to investigate CO2/BILPs interaction sites and binding affinities. The computational outcomes of DFT have shown that (C-H) bond of the aryl system is a possible site for CO2 interaction beside the free-N side and hydrogen bonding. All new polymers were characterized by spectral and analytical characterization methods and their sorption data were collected to evaluate their capability as candidates for gas separation applications.
125

Influence des fractions hydrophobique et hydrophilique de la matière organique dissoute sur la sorption de Cd, Cu et Pb dans l'horizon B de Podzol

Lafrenière, François January 2004 (has links)
Mémoire numérisé par la Direction des bibliothèques de l'Université de Montréal.
126

Comportamento ambiental do polietilenoglicol em solos brasileiros / Environmental behavior of polyethylene glycol in Brazilian soils

Castanho, Giuliane de Mello 28 September 2009 (has links)
Os polietilenoglicóis (PEGs) são polímeros sintéticos não iônicos, solúveis em água, que possuem diferentes propriedades físico-químicas devido ao efeito de sua cadeia longa, conferindo assim uma vasta disposição na aplicação industrial do PEG. Como exemplos de aplicação destacam-se o uso como lubrificante solúvel em água para moldes de borracha, fibras têxteis e operações de formação de metais, sendo também usado em tintas à base de água, revestimento de papéis, polimento, na indústria cerâmica, na confecção de fases estacionárias para cromatografia, entre inúmeras outras. O PEG também pode ser adicionado às dietas de ruminantes baseadas em foragem com alto teor de taninos, onde ele se insere como um agente complexante do tanino. Contudo, devido à ampla aplicação do PEG, mostra-se uma maior preocupação com seu uso e disposição no meio ambiente, uma vez que sua concentração, seja no solo ou água, possa ser grande. No entanto, pouco se sabe acerca do seu destino no ambiente, principalmente em condições tropicais, sendo que não foram encontrados na literatura estudos de monitoramento de águas subterrâneas e superficiais, e nem mesmo estudos de impacto ambiental. Neste contexto, este projeto se insere na busca sobre o destino do PEG-4000 no ambiente, buscando informações sobre sua mobilidade, degradação e sorção em solos, utilizando técnicas radiométricas (14C-PEG). Complementando o estudo do PEG, foi avaliado o transporte de pesticidas na presença do PEG, uma vez que ele possui uma alta solubilidade, podendo atuar como co-solvente, avaliando assim o papel do PEG na presença de contaminantes / Polyethylene glycols (PEGs) are non-ionic synthetic polymer, soluble in water, which have different physical and chemical properties because of its long chain, thereby providing a broad industrial application of PEG. Examples of application are the use as water-soluble lubricant for rubber molds, textile fibers and metallurgy, also used in water-based paints, paper coating, polishing, ceramic industry, in construction of stationary phases for chromatography, and numerous others. PEG can also be added to the diets of ruminants based on forage with a high content of tannins, where it comes as a complexing agent of tannin. However, due to the wide application of PEG, it is a greater concern about its use and disposal in the environment, since their concentration, either in soil or water, can be large. However, little is known about their fate in the environment, especially in tropical conditions, which were not found in the literature studies for monitoring underground and surface water, and even environmental impact studies. In this context, this project falls in the search on the fate of PEG-4000 in the environment, seeking information on their mobility, degradation and sorption in soils, using radiometric techniques (14C-PEG). Complementing the study of PEG, was evaluated the pesticides transport in the presence of PEG, since it has a high solubility and can act as co-solvent, thereby assessing the role of PEG in the presence of contaminants
127

Efeito da cinza de biomassa florestal na fertilidade e na sorção de imazetapir em solos ácidos / Effect of wood ash on soil fertility and on sorption behaviour of imazethapyr in acid soils

Nascimento, Bruna Botin 14 November 2013 (has links)
As indústrias de papel e celulose geram enormes quantidades de cinzas de caldeira todos os anos. A disposição final dessas cinzas em aterros costumava ser prática comum, porém a sua utilização em solos florestais e agrícolas merece consideração devido ao seu potencial de corrigir a acidez e de fertilizar os solos, minimizando assim a pressão sobre sua forma de descarte no ambiente. No entanto, o uso desse resíduo pode afetar diretamente a dinâmica de pesticidas no solo, além de adicionar metais pesados. Desta forma, o presente trabalho avaliou o efeito de três cinzas de biomassa florestal (C-1, C-11 e C-27) na fertilidade e na sorção do herbicida imazetapir em três solos com atributos físico-químicos distintos (RQd, LVd e LVAd). Além das três cinzas, calcário e o controle compuseram os tratamentos, os quais foram incubados por três meses. Posteriormente, estudos de sorção do herbicida imazetapir foram realizados nos diferentes tratamentos. As cinzas C-11 e C-27 aumentarem o valor do pH dos solos e os teores de macroelementos, mas reduziram os teores de microelementos catiônicos. A C-1 mostrou ser boa fonte de K para os solos. Nenhuma cinza mostrou-se limitante quanto ao teor de metais pesados. De forma geral, o imazetapir apresentou baixo potencial de sorção nos solos e seus respectivos tratamentos (Kd < 1,8 L kg-1). A C-11 e a C-27 reduziram enquanto que a C-1 aumentou o potencial de sorção do imazetapir nos solos, o que foi devido às alterações nos valores de pH do solo. A sorção foi ligeiramente maior no solo com maiores teores de argila e carbono orgânico (LVd), enquanto a dessorção foi maior no solo de teores intermediários (LVAd). Houve histerese em todos os solos, sugerindo irreversibilidade de parte do herbicida sorvido. / The pulp and paper industries generate huge amounts of wood ash every year. The ashes disposals in landfills used to be a common practice, but their use in agricultural and forest soils deserves special attention due to their potential to neutralize acidity and to fertilize soils, thus decreasing pressure about their environmental disposal. However, the use of this residue may directly impact the dynamic of pesticides as well as add heavy metals to the soils. Therefore, this study evaluated the effects of three wood ashes (C-1 , C-11, and C-27 ) in the fertility and sorption of imazethapyr in three soils (RQd, LVd, LVAd), with contrasting physical-chemical attributes. Besides the ashes, lime and control treatments were added, all of them incubated for three months. Afterwards, batch sorption isotherms for imazethapyr were performed for all treatments. The C-11 and C-27 enhanced soil-pH and macroelement contents, but decreased cationic microelement contents. The C-1 was a good source of K to the soils. There is little risk of contamination by heavy metals. Overall, imazethapyr sorption was low in all soils and their respective treatments (Kd < 1,8 L kg-1). The C-11 and the C-27 decreased whereas C-1 enhanced sorption of imazethapyr to the soils, most likely due to changes in soil-pH. Sorption was slightly higher in the soil with higher clay and organic carbon contents (LVd) whereas desorption was higher in the soil with intermediate values (LVAd). There was hysteresis, suggesting irreversibility during sorption/desorption processes.
128

Padronização da metodologia para análise de sorção de água e solubilidade de materiais resilientes temporários para  base de prótese / Standardization of methodology for water sorption and solubility analysis of temporary resilient denture liners

Maciel, Janaina Gomes 08 June 2016 (has links)
Não existem normas internacionais que determinem limites aceitáveis de sorção de água e solubilidade para os materiais resilientes temporários para base de prótese, além de haver divergências metodológicas nos estudos. Objetivou-se avaliar de forma padronizada essas propriedades físicas para materiais macios de curta duração ao longo de sua vida útil. Corpos de prova (50mm x 0,5mm/ ISO-10139-2) de 7 condicionadores teciduais (Coe-Comfort-CC, Softone-ST, Rite-Line-RL, Dura Conditioner-DC, Hydro-Cast-HC, DentusoftDS e Visco-gel-VG) e 2 reembasadores resilientes temporários (Trusoft-TS e Coe-Soft-CS) foram individualmente confeccionados e submetidos à dessorção até estabilização das massas. Então, foram imersos em água destilada a 37oC por 3, 5, 7 ou 14 dias (n=10) para depois serem pesados, dessecados e pesados novamente. Os dados foram obtidos em porcentagens de sorção/solubilidade e analisados estatisticamente por ANOVA 2 fatores e teste de Tukey HSD (&#x3B1;=0,05). Em todos os períodos, VG (12,06±0,93 a 16,62±0,87%) apresentou a maior sorção de água dentre os materiais testados, sendo as menores porcentagens observadas para CC (2,23±0,53 a 2,99±0,49%) (P<0,05). CC, CS e TS não apresentaram alteração significativa da sorção de água ao longo de 14 dias (P>0,05). Já os demais materiais exibiram um aumento significativo da sorção de água entre os períodos de 7 e 14 dias (P<0,05). Para a solubilidade, valores médios inferiores e estatisticamente semelhantes foram apresentados pelos materiais DC, HC, DS, TS, RT e CS (0,28±0,30 a 2,13±0,23%) (P>0,05). ST (4,09±1,60 a 8,80±1,15%) demonstrou maior solubilidade que CC (1,89±0,30 a 3,35±0,70%), mas os mais altos valores percentuais dentre os materiais testados foram observados para VG (20,30±4,26 a 23,59±20,24%) (P<0,05). CC, DC, DS, HC, RT, TS e CS não apresentaram alterações na solubilidade percentual média ao longo dos 14 dias de avaliação. Já os condicionadores teciduais VG e ST exibiram aumento dos valores médios apenas aos 14 dias de imersão em água. Conclui-se que, ao longo da vida útil média de um condicionador tecidual (7 dias), os materiais CC, DC, HC, DS, RL, CS e TS apresentaram comportamento in vitro satisfatório em relação à sorção de água e solubilidade. De acordo com os resultados obtidos, os materiais CC, TS e CS foram considerados os mais indicados dentre os testados para reembasamento de próteses em até 14 dias. / There are no international standards that determine acceptable limits of water sorption and solubility for the temporary resilient liners, besides the differences in the methodology of the studies. It was aimed to evaluate in a standardized manner these physical properties of short-term soft materials throughout their lifespan. Specimens (50mm x 0.5mm/ ISO-10139-2) of 7 tissue conditioners (Coe-Comfort-CC, Softone- ST, Rite-Line-RL, Dura Conditioner-DC, Hydrocast-HC, Dentusoft-DS and Visco-gel- VG) and 2 temporary resilient liner (Trusoft-TS e Coe-Soft-CS) were individually prepared and submitted to desorption until mass stabilization. Afterwards, they were immersed in distilled water at 37oC for 3, 5, 7, or 14 days (n=10) to then be weighed, dried and reweighed. The data were obtained in percentages of sorption/solubility and statistically analyzed by 2-way ANOVA and Tukeys test (&#x3B1;=0.05). In all periods, VG (12.06±0.93 to 16.62±0.87%) showed the highest water sorption among the tested materials, with the lowest percentages observed for CC (2.23±0.53 to 2.99±0.49%) (P<0.05). CC, CS and TS showed no significant changes in water sorption over 14 days (P>0.05). The other materials exhibited a significant increase in water sorption between the periods of 7 and 14 days (P<0.05). For the solubility, lower (and statistically similar to each other) values were presented by DC, HC, DS, TS, RT, and CS materials (0.28±0.30 to 2.13±0.23%) (P>0.05). ST (4.09±1.60 to 8.80±1.15%) showed higher solubility than CC (1.89±0.30 to 3.35± 0,70%), but the highest percentages among tested materials were observed for VG (20.30±4.26 to 23.59±20.24%) (P<0.05). CC, DC, DS, HC, RT, TS, and CS showed no changes in the mean percentage solubility throughout the 14-day trial. The tissue conditioners VG and ST exhibited increased average values only at 14 days of water immersion. It was concluded that, over the lifespan of a tissue conditioner (7 days), the materials CC, DC, HC, DS, RL, CS, and TS presented suitable in vitro performance with respect to water sorption and solubility. According to the results, the materials CC, TS, and CS were considered best suited among the tested materials for denture relining of up to 14 days.
129

Deactivation of PtH-ZSM-5 bifunctional catalysts by coke formation during benzene alkylation with ethane

Chua, Li Min January 2010 (has links)
The alkylation of benzene with ethane was studied at 370 oC over two Pt-containing ZSM-5 catalysts with SiO2/Al2O3 ratios of 30 and 80. While the benzene and ethane conversion decreased with time-on-stream for the PtH-ZSM-5(30) catalyst, the PtH-ZSM-5(80) catalyst demonstrated a stable performance. The deactivation of the PtH-ZSM-5(30) catalyst was found to be more significant, when compared to the PtH-ZSM-5(80) catalyst as a result of differences in the formation of coke. Results from gas sorption and x-ray diffraction experiments showed that coke is preferentially formed within the channel segments of the PtH-ZSM-5(30) catalyst as opposed to coke deposition on the outside surface of the PtH-ZSM-5(80) crystallites, subsequently blocking entrance to the zeolite channels. <br /> The location of the coke deposition was found to affect the product selectivity of the two PtH-ZSM-5 catalysts. The accessibility functions, derived from nitrogen and argon sorption data, suggested that, with prolonged time-on-stream, the coke molecules build up from the middle of the zeolite crystallites outwards towards the surface, as the reaction was carried out over the PtH-ZSM-5(30) catalyst. Partial blockage of the internal pore structure of the PtH-ZSM-5(30) catalyst decreased the diffusion length within the crystallites. In contrast to the typical effect of coking, where the selectivity of para- isomers would be enhanced with coke deposition, the effect of the reduction in the diffusion length of the PtH-ZSM-5(30) crystallites is consistent with the decreasing para-selectivity of the diethylbenzene (DEB) isomers with time-on-stream. <br /> n investigation of the causes of coke locations was conducted, and the results suggested that, the spatial distribution of Pt metal was responsible for the different locations of coke observed. Surface reactions initiated coking in the intercrystalline region of the PtH-ZSM-5(80) catalyst, as the Pt particles on the surface of the PtH-ZSM-5(80) crystallites increased the difficulty of access for reactants to the interior of the crystallites. Within the PtH-ZSM-5(30) catalyst, ethane dehydrogenation and benzene alkylation took place in the micropore network as a result of preferential intracrystalline deposition of Pt metal. Further conversions on the active sites within the PtH-ZSM-5(30) crystallites thus lead intracrystalline coking.
130

Aplicação do rejeito do beneficiamento do carvão de Moatize (Moçambique) como sólido sorvente na remoção de cromo (VI)

Barbosa, Dafne Lanfermann January 2017 (has links)
Uma das principais consequências dos processos de mineração e beneficiamento do carvão é a elevada produção de rejeitos. Esses materiais retornam às cavas de mineração ocasionando efeitos negativos ao meio ambiente, como a drenagem ácida de mina. Uma alternativa em potencial para esses rejeitos é aplica-los no tratamento de efluentes líquidos como sólidos sorventes. Dentre os principais poluentes aquosos destacam-se os metais pesados e, entre eles, o cromo hexavalente, devido aos seus efeitos carcinogênicos e mutagênicos, sendo altamente prejudicial aos organismos vivos. Neste contexto, o presente trabalho tem como objetivo utilizar o rejeito do beneficiamento do carvão de Moatize (Moçambique) como sólido sorvente para a remoção de cromo hexavalente de águas contaminadas. O sólido foi utilizado em duas granulometrias diferentes: no intervalo entre 0,7 e 1,5 mm (R1) e menor que 0,074 mm (R2). As amostras foram caracterizadas segundo sua massa específica, densidade aparente, área superficial (BET), volume de poros e diâmetro de poros (BJH), ponto de carga zero, composição química (FRX) e mineralógica (DRX). Ensaios experimentais foram realizados a fim de determinar as melhores condições de sorção, onde foram avaliados o efeito do pH, do tempo de residência e da concentração de sorvente As melhores condições encontradas para o sólido R1 foram: pH 2, 10 h de ensaio e concentração de sorvente de 8 g L-1, onde foi obtido 98,6% de remoção de Cr(VI). A maior remoção para o sólido R2 foi de 98,8%, obtida utilizando-se: pH 2, 50 min de ensaio e concentração de sorvente de 10 g L-1. Comparando com o limite previsto pela legislação brasileira CONAMA 430 para despejos industriais as concentrações finais de cromo hexavalente em solução ficaram abaixo do valor máximo estabelecido (0,1 mg L-1). A partir destas condições encontradas, foram construídas isotermas de equilíbrio e os modelos de Langmuir, Freundlich e Sips foram ajustados aos dados experimentais. Para o sólido R1, os modelos de Langmuir e Sips demostraram um bom ajuste, apresentando valores de R2 de 0,897 e 0,907 respectivamente. Já para o sólido R2, o modelo de Sips foi o que melhor representou os dados experimentais, com um R2 de 0,954. Os resultados encontrados indicam que o rejeito de carvão de Moatize pode ser utilizado para o tratamento de águas contaminadas com cromo hexavalente. / One of the main consequences of coal mining and beneficiation process is the large production of waste and by-products. These materials return to the mines generating significant negative impacts to the environment. One of the possible applications for the coal wastes is in the wastewater treatments, where it can be used as a sorbent. Amongst the main water pollutants, heavy metals stand out, especially hexavalent chromium, due to its carcinogenic and mutagenic effects, being highly prejudicial to the living organisms. In this context, the objective of this study is to use coal beneficiation waste from Moatize (Mozambique) as a sorbent to remove hexavalent chromium from aqueous solution. Coal waste was utilized in two different particle sizes: between 0.7 and 1.5 mm and smaller than 0.074 mm. These solids were characterized for their specific weight, bulk density, superficial area (BET), pore volume and diameter (BJH), point of zero charge, chemical composition (XRF) and mineral composition (XRD). Experiments were conducted to determinate the best sorption conditions, were the operating parameters investigated were: solution pH, contact time and sorbent concentration The best conditions for Cr(VI) sorption onto R1 were: pH 2, 10 h and 8 g L-1 of sorbent concentration, were 98.6% removal was obtained. Cr(VI) maximum removal onto R2 of 98.8% was achieved at pH 2, 50 min and 10 g L-1 of sorbent concentration. Comparing with the limit permitted by Brazilian legislation, CONAMA 430, for industrial wastewaters, the final Cr(VI) concentration in water were below the maximum established by law (0.1 mg L-1). From these results, equilibrium isotherms were build and the mathematical models of Langmuir, Freundlich and Sips were fitted to the experimental data. For the R1 sorbent, Langmuir and Sips models fitted better the experiments, with R2 values of 0.897 and 0.907, respectively. Sips model described better the experimental data when the R2 sorbent was used, with a R2 of 0.954. Results showed that Moatize’s coal waste can be utilized for hexavalent chromium wastewater treatment.

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