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Strength of Nano-Cemented Paste Backfill Cured in Iso- and Non-Isothermal ConditionsBenkirane, Othmane 20 January 2023 (has links)
One hundred billion tons of mine solid waste are estimated to be produced worldwide each year. In Canada, the mining and oil industries produce the most solid and semi-solid waste in the country, with more than a billion tons each year. In the earlier days of mining, the initial practices that were used to contain these waste materials consisted of surface storage, river dumping or just simple abandonment, while the more recent practices include dam impoundment and underground waste fill. These methods however can potentially cause environmental hazards and geotechnical problems. Against this context and as a result of stricter environmental regulations, cemented paste backfilling has been developed as a solution. This relatively new technology uses the produced waste tailings to backfill the mine stopes, greatly reducing their environmental impact while offering proper structural support in an efficient manner. However, the cost of cemented paste backfill (CPB) is greatly impacted by the binder content which can constitute up to 75% of its total cost. Additionally, the binder is usually mostly composed of ordinary Portland cement, and its production is highly energy-intensive and generates a large volume of carbon dioxide (CO₂). Indeed, it is estimated that the cement industry accounts for approximately 7% of the global anthropogenic CO₂ emissions, which is expected to increase on an annual basis. All of these factors have compelled the mining industry to seek alternatives for cement to enhance CPB strength, in hopes of reducing its carbon footprint.
Against this context, this study investigates the effect of the addition of nanoparticles, namely nano silica (SiO₂) and nano-calcium carbonate (CaCO₃), on the strength development of CPB cured at a constant room temperature and in non-isothermal conditions. Nanoparticles have been studied and used as chemical admixtures in different cementitious materials with promising results; non-isothermal curing conditions better reflect the in-situ thermal curing conditions of CPB. Thus, numerous different laboratory tests and analyses, including uniaxial compressive strength (UCS), scanning electron microscopy (SEM) and mercury intrusion porosimetry (MIP) tests, thermogravimetric/derivative thermogravimetric (TG/DTG) analyses and electrical conductivity monitoring, have been conducted on CPB samples with or without nanoparticles, and cured at room temperatures or under non-isothermal conditions. The non-isothermal conditions replicate the development of temperature in two different sizes of CPB structures in the field. The results show that CPB that contains nanoparticles show a higher UCS over the entire period of curing in all of the tested conditions. The mechanical performance is further enhanced when tested under higher temperatures in non-isothermal temperature profiles. Most of the strength increase takes place at the early ages (3 days) of the testing. The reason for the improvement in the mechanical strength is linked to accelerated binder hydration and the nucleating and filler effects of the nano-material, which is corroborated by results obtained through microstructural analyses and EC monitoring. The use of natural gold tailings affects the mechanical performance of CPB and the accelerating effect of the nanoparticles due to sulphate attacks. Overall, these promising findings can help to contribute to reducing the carbon footprint of mining activities, and improve the efficiency and cost-effectiveness of mine backfilling processes.
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[pt] CARACTERIZAÇÃO QUÍMICA E MECÂNICA DO FILME DE DEPOSIÇÃO FORMADO DURANTE O PROCESSO CORROSIVO DO AISI 1080 EM AMBIENTE CONFINADO CONTENDO CO2 / [en] CHEMICAL AND MECHANICAL CHARACTERIZATION OF THE DEPOSITION FILM FORMED DURING THE CORROSIVE PROCESS OF AISI 1080 IN A CONFINED ENVIRONMENT CONTAINING CO2ANA CAROLINA ARAUJO ANDRADE 30 May 2023 (has links)
[pt] Durante a exploração e produção de petróleo, dificuldades operacionais precisam ser superadas
na injeção de CO2 para aumento da produção. Na presença de água, o CO2 reage e forma o
H2CO3, que pode vir a corroer o aço carbono presente nos dutos flexíveis. Diversos fatores
influenciam no processo corrosivo, entre eles a pressão parcial de CO2, a temperatura, pH do
meio e a relação volume de solução/área metálica exposta (V/A). Desta forma, o objetivo deste
trabalho foi avaliar a composição e propriedades mecânicas dos produtos de corrosão
depositados sobre a superfície do aço carbono 1080 imersos em água do mar sintética, a
temperatura de 40 graus C, durante 15 e 121 dias. Para avaliar a influência da pressão parcial de
CO2, os ensaios foram realizados a 1, 10 e 20 bar de CO2, já para avaliar a influência da relação
V/A, os ensaios foram realizados a 1 mL.cm-2
e 20 mL.cm-2
. As taxas de corrosão foram
determinadas utilizando o método gravimétrico, as caracterizações dos produtos de corrosão
foram realizadas por Microscopia Óptica (MO), Microscopia Eletrônica de Varredura (MEV),
Espectroscopia de Energia Dispersiva (EDS) e Dispersão de Raios X (DRX). Adicionalmente,
foi utilizada a Nanoindentação para determinar as propriedades mecânicas do filme formado.
A partir da MO, foi identificado a formação de dois filmes em quase todas as condições
estudadas. Ao avaliar a influência da pressão, não foram observadas variações significativas na
taxa de corrosão. Já os resultados obtidos para avaliar o efeito da relação V/A, foi possível
concluir que o ambiente confinado reduz significativamente a taxa de corrosão. Ao avaliar as
propriedades mecânicas dos filmes, foi possível observar que em todos os casos, a dureza e o
módulo de elasticidade são menores no filme interno quando comparados ao filme externo. Isso
pode estar relacionado a formação de uma camada externa mais compacta, constituída
predominantes por pequenos grãos de FeCO3, conforme os resultados obtidos através do MEV
e DRX / [en] During oil exploration and production, operational difficulties need to be overcome in CO2
injection to increase production. In the presence of water, CO2 reacts and forms H2CO3, which
can corrode the carbon steel present in flexible pipes. Several factors influence the corrosive
process, including the partial pressure of CO2, the temperature, pH of the medium and the
volume of solution/exposed metallic area (V/A) ratio. Thus, the objective of this work was to
evaluate the composition and mechanical properties of the corrosion products deposited on the
surface of carbon steel 1080 immersed in synthetic sea water, at a temperature of 40 C degrees, for 15
and 121 days. To evaluate the influence of the partial pressure of CO2, the tests were carried
out at 1, 10 and 20 bar of CO2, and to evaluate the influence of the V/A ratio, the tests were
carried out at 1 mL.cm-2
and 20 mL. cm-2
. Corrosion rates were determined using the
gravimetric method, characterizations of corrosion products were performed by Optical
Microscopy (OM), Scanning Electron Microscopy (SEM), Energy Dispersive Spectroscopy
(EDS) and X-Ray Scattering (XRD). Additionally, Nanoindentation was used to determine the
mechanical properties of the formed film. From the OM, the formation of two films was
identified in almost all conditions studied. When evaluating the influence of pressure, no
significant variations in the corrosion rate were observed. As for the results obtained to evaluate
the effect of the V/A ratio, it was possible to conclude that the confined environment
significantly reduces the corrosion rate. When evaluating the mechanical properties of the films,
it was possible to observe that in all cases, the hardness and the elastic modulus are lower in the
inner film when compared to the outer film. This may be related to the formation of a more
compact outer layer, consisting predominantly of small FeCO3 grains, according to the results
obtained through SEM and XRD.
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Mesocrystalline materials and the involvement of oriented attachment - a reviewBahrig, L., Hickey, Stephen G., Eychmüller, A. January 2014 (has links)
No / The latest advances in mesocrystal formation and non-classical crystallization of pre-synthesised nanoparticles have been reviewed with the focus on providing a fuller description of a number of complex systems and their properties and applications through examination of the crystallisation mechanisms at work. Two main crystallization principles have been identified; classical crystallization and particle based aggregation modes of non-classical pathways. To understand the non-classical pathways classical crystallization and its basics are introduced before non-classical pathways, such as oriented attachment and mesocrystal formation, are examined. In particular, the various destabilization mechanisms as applied to the pre-synthesized building blocks in order to form mesocrystalline materials as well as the interparticular influences providing the driving forces are analyzed and compared to the mechanisms at work within classical crystallization. Furthermore, the new properties of the mesocrystalline materials that derive from the collective properties of the nanoparticular building units, and their applications potential are presented. It is shown that this new class of materials has the potential to impact in a number of important areas such as sensor applications, energy conversion, photonic crystals as well as for energy storage, optoelectronics and heterogeneous catalysis or photocatalysis.
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Raman spectroscopy as a non-destructive screening technique for studying white substances from archaeological and forensic burial contextsSchotsmans, Eline M.J., Wilson, Andrew S., Brettell, Rhea C., Munshi, Tasnim, Edwards, Howell G.M. January 2014 (has links)
No / Raman spectroscopy was evaluated as a non-destructive analytical tool for the characterisation of white substances in burials. In addition, Fourier transform Raman spectroscopy was used to assess the conversion of hydrated lime into calcium carbonate. Fourteen samples of white substances from archaeological and forensic sites were analysed and characterised. The results show that not all white residues in burials are lime. Lime can easily be mistaken for other building materials (gypsum), for minerals (brushite) or degraded metal (cerussite). This study highlights the need for chemical analysis of white residues when encountered in burials. Analytical information derived from Raman spectra of white substances can further assist in the interpretation of the taphonomic processes of burials and their funerary context. Copyright (c) 2014 John Wiley & Sons, Ltd.
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Development of Innovative Carbon Mineralization Technologies to form Tailored Carbonates for Carbon-Negative Built EnvironmentWilliams, Jonah Martin January 2024 (has links)
Human activities since the beginning of the industrial revolution have led to vast amounts of CO₂ being emitted into the atmosphere (May 2023, 424 ppm; NOAA), which is principally responsible for anthropogenic climate change; the effects of which are expected to be globally devastating. In order to combat the unbalanced carbon cycle and reduce the effects of climate change, it is widely accepted that the adoption and use of carbon capture utilization and storage (CCUS) technologies will be necessary to limit warming to 2.0 degrees C (IPCC 2022). Among the industrial sectors to decarbonize, the built environment will be notably challenging, principally due to the challenges associated with reducing the carbon impact of structural materials, such as cement and steel. These construction industries currently account for roughly 8% of global emissions, with projections that this number will increase with a growing global population and more rapid urbanization, especially in developing areas.
The abysmal state of U.S. infrastructure decay (ASCE 2021 Grade: C-minus) is also concerning as the replacement of concrete, cement, steel, and asphalt will require and release numerous amounts of carbon; however, this also presents a unique opportunity to deploy CCUS technologies to capture and utilize carbon in the creation of next-generation built-environment materials. These materials include fillers, pozzolans, supplementary cementitious materials (SCMs), and geopolymers such as carbonates, amorphous silica/silicates, bio-chars, and structural allotropes of carbon, like crystalline carbon nanotubes (CNTs) or graphene. The production of these carbon neutral or even carbon-negative materials can be achieved through advanced ex-situ carbon mineralization reaction pathways and novel biomass-to-carbonate conversion technologies, such as alkaline thermal treatment (ATT). In the former, alkaline waste, such as landfilled concrete rich in Ca, can be processed to produce calcium carbonates. This captures atmospheric CO2 and also creates new filler materials which can be incorporated into construction materials. The latter reaction pathway, ATT, takes waste biomass and alkaline wastes as feedstocks and directly converts them into H2 gas and carbonates in a single reaction pathway conducted at moderate conditions (1 atm, 300 degrees C). Although advantageous, both of these synthesis pathways contain unique challenges related to kinetic barriers, conversion issues, mass transfer limitations, and the degree of carbon capture and utilization which can be achieved. Thus, the objective of this study is directed towards overcoming these limitations and coupling these two relatively understudied and novel reaction pathways as a tandem method for carbon sequestration and the creation of new building materials and clean energy.
First, the hydrometallurgical processing of waste concrete in a two-step aqueous dissolution and carbonation reactor system is explored. This system is developed and designed to process hydrated waste cement paste, which has extremely high Ca and Si contents. The kinetics of the dissolution process are detailed and the properties of the unreacted residue is examined, revealing a high surface area, amorphous Si-rich material which was shown to be an excellent clinker replacement in new cement mixtures. The dissolution kinetics were fit to a diffusion controlled reactive model, and methods to further increase the elemental extraction of Ca, Al, Fe, and Si, such as internal abrasive media, was also studied. The Ca-rich mother liquor was then carbonated at various conditions using CO₂ gas and the properties, uses, and potential CO₂ capture metrics of these Si-rich residues and calcium carbonates was detailed.
In an effort to explore alternative carbon mineralization processes, the use of novel leaching agents, such as regenerable ammoniacal salts was also studied. Typical dissolution and carbonation processes require copious amounts of commodity chemicals, such as acid and base; however, cycling of ammonia/ammonium, similar to the chemistries of the Solvay process, is a promising alternative. The use of ammonium chloride and ammonium bisulfate was studied in the context of material extraction from waste cement paste and subsequent carbonate formation. The process was assessed from a carbon circularity standpoint, revealing significant cost and emissions reductions when compared to conventional carbon mineralization for the treatment of alkaline waste. Additionally, the profiling of carboxylic acid ligands, such as formate, glutamate, acetate, and citrate, to further enhance kinetics during leaching were studied. These agents were found to significantly enhance both of these parameters, resulting in almost 100% of Ca material extraction in a single pass with a sodium citrate ligand.
Producing the metastable forms of anhydrous calcium carbonate, such as vaterite and aragonite, was heavily examined in the context of new built-environment building blocks as alternatives to conventional limestone. The production and use of these polymorphs has not been well studied or documented; yet, both vaterite and aragonite are expected to have niche market uses in a carbon-constrained world. The favorable conditions to synthesize vaterite was explored, revealing that a high carbonate to calcium molar ratio is necessary to stabilize this polymorph at ambient reaction conditions. Surface active salt species, such as NH₄+ and sulfate, also had a profound effect on vaterite morphology and stability. Aragonite was successfully stabilized at high carbonation reaction temperatures (~70 degrees C); however, the use of alternative crystallization systems, such as a semi-continuous system vs. traditional batch process was able to produce higher purity aragonite at lower temperatures (40-50 degrees C). The use of crystal seeding also showed remarkable templating abilities and allowed for aragonite production at room temperature (25 degrees C). Both polymorphs were shown to be exceptional fillers for cement through isothermal calorimetry, with aragonite also showing high yield stress development via rheometric testing adding to its potential use in advanced 3-D printed cements, plastics, and papers.
The alkaline thermal treatment of waste biomass derived from coastal marine sources was studied to convert biomass into carbonate materials in a carbon-negative manner, while producing H₂ as a valuable product. Various reaction conditions were profiled, including temperature, steam load, hydroxide utilized, and biomass source. A strong correlation was found between carbon conversion/H₂ yield and the basicity of the hydroxide salt, which matched well with thermodynamic calculations performed. These findings were utilized to inform more advanced and refined ATT reaction pathways, coupled with the use of novel regeneration schemes. One potential reactant regeneration pathway is through the use of molten salt electrolysis, in which carbonates are electrosplit into solid carbon (e.g., CNTs) and O₂. Eutectic regenerable alkaline hydroxide mixtures of Li, Na, and K were studied in their ability to convert biomass into electrochemically active carbonate salts mixtures. Interestingly, the content of LiOH in the salt greatly poisoned the biomass conversion potential; however, lithium is the most electroactive carbonate salt for downstream electrolysis. Finally, the electrolytic processing of these biomass-derived carbonate salts was shown to yield high amounts of CNTs, a valuable allotrope of carbon and significant strength enhancer of cementitious materials.
Lastly, a brief discussion of the combination of these two reactive pathways in the context of producing low-carbon or even carbon-negative next-generation built environment building materials is performed with respect to a circular material economy and scalability. From the results of these studies, recommendations are made for future research advancements to continue to accelerate CCUS activities and reaction pathways in the realm of the most difficult-to-decarbonize industries, such as the built environment.
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Étude de la réactivité et de l'hydratation des particules obtenus par carbonatation de saumures alcalines / Study of reactivity and hydration of particles obtained by carbonation of alkaline brinesGrandjean, Mathilde 04 April 2013 (has links)
Cette thèse porte sur l'étude de la caractérisation et le traitement de saumures alcalines. La carbonatation directe de saumures résiduaires (SR), par introduction d'une partie du CO2 issu de fumées industrielles, est réalisée dans un souhait de réduction des émissions de CO2 et en vue d'une valorisation potentielle des produits obtenus. Cette recherche se concentre sur l'étude des composés carbonatés, l'objectif général est d'établir le lien entre la réactivité des carbonates et leur valorisation (ici, désulfuration de fumées acides). Les SR sont complexes, l'étude de leur composition chimique et minéralogique a été réalisée en partie par spectroscopie Raman afin de mettre en évidence les interactions OH-Cl dans les échantillons humides. Les différents hydroxydes sont consommés au cours de la carbonatation pour précipiter des carbonates de calcium (calcite, aragonite). La composition chimique détermine les réactions de carbonatation alors que les paramètres physiques influencent la vitesse des réactions ainsi que la morphologie et la pureté des carbonates. L'évolution des phases au cours de la carbonatation des SR a été suivie par spectroscopie et un premier modèle statistique de prédiction des concentrations en carbonates a été développé. La deuxième partie de ce travail porte sur la caractérisation des carbonates obtenus et des paramètres, tel que l'hydratation, pouvant influencer leur valorisation. L'importance de l'hydratation dans la réactivité des produits DECALCO a été observée de l'échelle microscopique au pilote semi-industriel. Les essais de désulfuration de fumées acides ont été menés avec des taux de conversion du SO2 atteignant 65 à 70 % / This study is a contribution to the characterization and the treatment of alkaline industrial wastes. The direct carbonation of residual brines (RB) by CO2 bubbling results in a gas emission reduction and a potentially valorization of resulting products. This research was focused on carbonate products. The main objective is to link reactivity and valorization (here, desulfurization of industrial fumes). The RB are complex, their chemical and mineralogical composition was studied in particular by Raman spectroscopy to monitor OH-Cl interaction in humid samples. The different hydroxides phases are consumed during carbonation to precipitate calcium carbonates (calcite and aragonite). The chemical composition of RB determines the main part of the reaction of carbonation whereas physical parameters influence the reaction kinetics, the by-products morphology and purity. The feasibility of on-line monitoring of the phases evolution during carbonation using spectroscopy has been validated and a first statistical model for the prediction of carbonate concentration has been developed. The second part of this works concerns the characterization of precipitated carbonates and some parameters as hydration which can influence their valorization. The importance of hydration on the carbonates reactivity was observed in microscopy and at pilot scale. Desulfurization tests of industrial fumes in semi-humid way provided a conversion rate of SO2 ranging between 65 and 70%
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Remoção de bário de efluente aquoso industrial por precipitação mediante dessupersaturação, adição de sulfato em excesso e abrandamento: estudo dos mecanismos dos aspectos tecnológicos e da ecoeficiência dos processos. / Barium removal from aqueous industrial effluent by desupersaturation, excess sulfate addition and softening: study of mechanisms of technological aspects and ecoefficiency of processes.Ronquim, Flávia Marini 08 April 2019 (has links)
Em um cenário global de indisponibilidade hídrica, até regiões sem histórico de escassez de recursos hídricos vêm sendo impactadas pela ausência de chuvas e circunstâncias de adversidade climática. Com perspectivas cada vez menos favoráveis quanto ao abastecimento hídrico, têm-se difundido progressivamente, no Brasil e no mundo, alternativas de tratamento de efluentes aquosos industriais visando seu reúso na própria indústria, diminuindo a necessidade de captação de água em corpos hídricos. Os processos de separação com membrana (PSM\'s) têm tido destaque, sobretudo para reúso em caldeiras e torres de resfriamento. Em um PSM, no entanto, os íons removidos da corrente de alimentação durante o processo de dessalinização concentram-se no compartimento de rejeito das membranas (concentrado). Consequentemente, os sais de baixa solubilidade comumente ultrapassam sua saturação e excedem seus limites metaestáveis, passando a oferecer risco de deposição sobre as membranas. As deposições salinas, chamadas incrustações (ou scaling) prejudicam o processo de dessalinização: reduzem a taxa de recuperação de água, aumentam o consumo energético e danificam membranas e tubulações. Uma vez que o sulfato de bário (BaSO4) é um dos sais com maior potencial incrustante em efluentes industriais, e cujas incrustações apresentam maiores resistências às práticas convencionais de limpeza, estudou-se métodos preventivos de incrustação de BaSO4 por remoção de íons bário de fase líquida a montante de um PSM. A depleção de bário de solução foi analisada mediante: (i) precipitação de BaSO4 por meio de dessupersaturação (com adição de sementes) e efeito do íon comum (excesso de sulfato) e (ii) precipitação de CaCO3 por abrandamento com incorporação do íon Ba2+ no precipitado. Desenvolveu-se, inicialmente, um estudo conceitual da precipitação de BaSO4 por modelagem termodinâmica, aplicada ao tratamento de um efluente padrão de refinaria de petróleo supersaturado em BaSO4. As simulações termodinâmicas apontam que o pre-tratamento de efluentes por dessupersaturação, com opção de adicionar sulfato (via adição externa ou reciclo) são promissores para aumentar o rendimento de PSM\'s. Em estudos experimentais com efluente sintético de refinaria de petróleo, foi obtida a cinética de precipitação do BaSO4 para o ajuste de um modelo de precipitação de BaSO4. Observou-se que o tempo de indução do BaSO4 foi reduzido à medida que se aumentou o excesso de sulfato (em relação ao bário presente) ou à medida que se adicionou sementes de BaSO4. Após um período curto de precipitação (alguns minutos), a solução permanecia supersaturada por longos períodos (horas), com razões de supersaturação residuais dentro da faixa de 1,1 a 3,0. Esses valores foram associados com uma dependência de quarta ordem da taxa de crescimento do cristal com a taxa de supersaturação. Verificou-se que a carga de sementes de BaSO4 é diretamente proporcional à depleção de supersaturação, que sementes heterogêneas (CaCO3, CaSO4.2H2O) são ineficazes para a precipitação do BaSO4 e que os íons cálcio inibem a precipitação de BaSO4. A precipitação de CaCO3 (em mix de vaterita e calcita) por abrandamento em efluente sintético foi eficaz para remover bário da solução. O mecanismo que controla o processo foi identificado como sendo a substituição isomórfica do íon cálcio pelo íon bário no retículo cristalino do carbonato de cálcio. Consequentemente, a remoção de bário da solução é favorecida quando se aumenta a quantidade de carbonato de cálcio precipitado e quando o coeficiente de distribuição aparente em vateita e calcita (DBa, que indica a quantidade de bário incorporada ao sólido) é elevado. Valores altos de pH e de concentração de cálcio elevam a precipitação de CaCO3 e, portanto, maximizam a remoção de bário. O coeficiente de distribuição aparente do bário mostra-se independente do pH inicial (na faixa de 9,5 a 11,7) e aumenta com a concentração de cálcio. Ele também aumenta com a quantidade de sementes de calcita, o que pode ser consequência de uma maior incorporação de bário em camadas que crescem sobre substratos puros de CaCO3 ou ainda, pode ser devido à manifestação de mecanismos de adsortivos com o aumento de lugares ativos disponíveis para incorporação de bário. Em experimentos com efluente real, ao contrário do observado com soluções sintéticas, a remoção de bário por dessupersaturação foi realizada com eficiência mesmo em presença do íon cálcio, devido provavelmente a sua complexação com aditivos orgânicos. Em precipitação de calcita, fatores que aumentam a supersaturação inicial, como adição de carbonato e aumento do pH, elevaram a precipitação de CaCO3, o que maximizou a remoção de bário. Tais fatores, no entanto, reduziram valores de DBa em calcita, possivelmente devido à diminuição na sorção de íons que estimulam a incorporação do bário. Dosagens de sulfato (insuficientes para precipitar BaSO4) reduziram a quantidade de calcita precipitada, diminuindo a remoção de bário e, inesperadamente, elevando DBa em calcita. Por fim uma análise de ecoeficiência foi feita em um estudo de reúso de água com zero de descarte líquido em refinaria de petróleo aplicando as técnicas de precipitação estudadas. A implantação de etapas de precipitação e de unidades maiores de osmose inversa (OI) acarretaram em reduções no consumo de energia no tratamento térmico do concentrado da OI, diminuindo proporcionalmente a emissão de gases de efeito estufa, consumo de água e degradação ecotoxicológica de água doce. Além disso, verificou-se redução de capital de investimento (dada à aquisição de equipamentos de evaporação menores) e redução nos custos energéticos operacionais. / In a global scenario of water unavailability, even regions with no records of water scarcity have been impacted by the absence of rainfall and climatic adversity. With increasingly unfavorable perspectives on water supply, alternatives to water treatment for industrial reuse have been progressively diffused in Brazil and around the world, reducing the need for water withdraw in water bodies. The membrane separation processes (PSM) have been emphasized in the tertiary treatment of industrial effluents, providing improvement in water quality for reuse in boilers or cooling towers. In a PSM, however, the salts removed from the feed stream during the desalination process are concentrated in the brine stream (concentrate). At this stage, the low solubility salts commonly exceed their saturation in the system, and surpasses their metastable limits, offering risk of deposition on the membranes. Salt deposits, called scaling, jeopardize the desalination process: they reduce the rate of water recovery, increase energy consumption and damage membranes and pipes. Since BaSO4 is one of the salts with the greatest scaling potential in the industry, and which the fouling presents the greatest resistance to conventional cleaning practices, preventive methods of BaSO4 scaling were studied by removal of barium ions from the liquid phase upstream a PSM. The barium depletion from solution was analyzed during the processes of: (i) precipitation of BaSO4 by means of desupersaturation (with addition of seeds) and common ion effect (excess of sulfate) and (ii) chemical precipitation of CaCO3 (softening) with incorporation of the Ba2+ ion in the precipitated crystal. A conceptual study of the BaSO4 precipitation was first developed by thermodynamic modeling, applied to the treatment of a standard oil refinery effluent supersaturated in BaSO4. The thermodynamic simulations show that effluents pretreatment by desupersaturation, with the option of adding sulfate (via external addition or recycle), are promising to increase the yield of PSM\'s. In experimental studies with synthetic oil refinery effluent, BaSO4 precipitation kinetics were obtained in order to adjust a BaSO4 precipitation model. The BaSO4 induction time was reduced as the excess sulfate (relative to the barium present) was increased and/or as BaSO4 seeds were added. After a short period of precipitation (a few minutes), the solution remained supersaturated for long periods (hours), with residual supersaturation ratios within the range of 1.1 to 3.0. These values were associated with a fourth order dependence of the crystal growth rate with the supersaturation rate. It was found that BaSO4 seed loading is directly proportional to the supersaturation depletion, heterogeneous seeds (CaCO3, CaSO4.2H2O) are ineffective for BaSO4 precipitation and that calcium ions inhibit BaSO4 precipitation. The precipitation of CaCO3 (as a mix of vaterite and calcite) by softening in synthetic effluent was effective to remove barium from solution. Isomorphic substitution of calcium by barium ion in the crystalline lattice of calcium carbonate was identified as the controlling mechanism of sorption process. Consequently, removal of barium from the solution is favored when the amount of precipitated calcium carbonate is increased and when the apparent distribution coefficient (DBa, which indicates the amount of barium incorporated into the solid) is raised. High values of pH and calcium concentration raise the precipitation of CaCO3 and, therefore, maximize the barium removal. The apparent barium distribution coefficient is independent of the initial pH (in the range of 9.5 to 11.7) and increases with calcium concentration. It also increases with the amount of calcite seeds, which may be consequence of higher barium incorporation in growing layers on CaCO3 pure substrates, or may be due to manifestation of adsorption mechanisms by the increase on available active places for barium incorporation. In experiments with real effluent, unlikely the synthetic solutions, the removal of barium by desupersaturation was performed efficiently even in the presence of calcium ion, probably due to its complexation with organic additives. In calcite precipitation, factors that increase initial supersaturation, such as carbonate addition and pH increase, elevates CaCO3 precipitation, which maximized the barium removal. These factors, however, reduced DBa in calcite, possibly due to a decrease on sorption process of ions which may stimulate barium incorporation. Sulphate dosages (insoluble to precipitate BaSO4) reduced the amount of precipitated calcite, decreasing barium removal and unespectly reducing the DBa in calcite. Finally, an eco-efficiency analysis was carried out in a water reuse study with zero liquid discharge in an oil refinery, applying the precipitation techniques studied. The implementation of precipitation stages and larger units of OI resulted in reductions in energy consumption in the thermal treatment of OI concentrate, reducing proportionally the emission of greenhouse gases, water consumption and ecotoxicological degradation of fresh water. In addition, there was reduction of investment costs (given the purchase of smaller evaporation equipment) and reduction in the operational energy costs.
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Avaliação da viabilidade de cistos de Giardia spp. e oocistos de Cryptosporidium parvum em água filtrada obtida após tratamento convencional com flotação e ozonização / Viability assessment of Giardia spp. cysts and Cryptosporidium parvum oocysts in filtered water obtained after conventional treatment with flotation and ozonationBoni, Dayane Mendes 09 September 2016 (has links)
Esta pesquisa avaliou o uso de ozônio para inativar cistos de Giardia spp. e oocistos de Cryptosporidium parvum presentes na água filtrada obtida após a utilização da tecnologia de ciclo completo com flotação (coagulação, floculação, flotação e filtração) em escala de bancada, empregando o cloreto de polialumínio – PAC – como coagulante. O método de floculação em carbonato de cálcio – FCCa, sem e com a etapa de separação imunomagnética – IMS – foi utilizado na quantificação dos protozoários. A recuperação nos ensaios de qualidade utilizando o kit Easyseed® de Giardia spp. foi de 8,4% ± 97,4% sem IMS e com IMS, com duas dissociações, o valor foi de 7,4% ± 39,7% e, com três dissociações, a recuperação alcançou 9,6% ± 34,7%, portanto, somente o ensaio com IMS e duas dissociações, não atendeu os padrões do Método 1623.1. A recuperação de Cryptosporidium parvum, obteve valor de 3,4% ± 100% em ensaio sem IMS e com IMS, o valor obtido foi de 1,0% ± 70,0% com duas dissociações e 1,8% ± 44,4% com três dissociações e nos três métodos apresentados, não houve conformidade com os critérios do Método 1623.1. Na etapa de desinfecção com ozônio, os ensaios realizados na Etapa 1, que se utilizou 5 mgO3L-1 e tempo de contato de 1 min sem IMS, as maiores inativações atingidas foram de 2,52 e 2,22 log para cistos de Giardia spp. e oocistos de Cryptosporidium parvum, respectivamente. Com o tempo de contato de 5 min, as maiores inativações foram de 2,52 e 2,92 log de cistos de Giardia spp. e oocistos de Cryptosporidium parvum, respectivamente. Na Etapa 2, com IMS, utilizando a mesma dosagem e tempo de contato de 1 min, obteve-se 2,27 e 0,21 log de inativação para cistos e oocistos, respectivamente. Comparando-se com o tempo de contato de 5 min, foram obtidos 2,9 e 2,3 log de inativação para cistos e oocistos, respectivamente. Na avaliação de custo, o método de FCCa sem IMS demonstrou ser o mais econômico em relação ao procedimento com IMS. A influência da inclusão da terceira dissociação ácida no método com IMS também foi analisada e este procedimento não resultou em diferenças estatísticas significativas nos resultados. / This research evaluated the use of ozone to inactivate Giardia spp. cysts and Cryptosporidium parvum oocysts present in the filtered water obtained after the use of the complete cycle of flotation technology (coagulation, flocculation, flotation and filtration) on a bench scale employing polyaluminium chloride - PAC as coagulant. The calcium carbonate flocculation method - FCCa, without and with immunomagnetic separation step - IMS has been used in the quantification of protozoa. The recovery in quality test using the kit Easyseed® for Giardia spp. was 8.4% ± 97.4% non-IMS and IMS with two dissociations, the value was 7.4% ±39.7% and with three dissociations, the recovery reached 9.6% ± 34,7%, so only the test with IMS and two dissociations, did not meet the standards of method 1623.1. Recovery of Cryptosporidium parvum obtained value of 3.4% ± 100% in non-IMS and IMS testing, the value obtained was 1.0% ± 70.0% with two dissociations and 1.8% ± 44.4% with three dissociations and the three methods presented, there was non-compliance with the criteria of Method 1623.1. In step disinfection with ozone, tests performed in Step 1 was used 5 mgO3L-1 and contact time of 1 min without IMS, the major inactivation achieved were 2.52 and 2.22 log for Giardia spp. cysts and Cryptosporidium parvum oocysts, respectively. With 5 minutes of contact time, the greater inactivation were 2.52 and 2.92 log for Giardia spp. cysts and Cryptosporidium parvum oocysts, respectively. In Step 2, with IMS, using the same dose and 1 min contact time, there was obtained 2.27 and 0.21 log inactivation for cysts and oocysts, respectively. Compared with the 5 min of contact time, were obtained 2.9 and 2.3 log inactivation for cysts and oocysts, respectively. In evaluating cost, the FCCa method without IMS proved to be the most economical in relation to the procedure with IMS. The influence of inclusion of the third acid dissociation method in IMS was also analyzed and this procedure did not result in statistically significant differences in the results.
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CALAGEM SUPERFICIAL COM CALCÁRIO CALCÍTICO E DOLOMÍTICO DE DIFERENTES GRANOLUMETRIAS EM SISTEMA PLANTIO DIRETO / Surface application of calcitic and dolomitic lime with different particle sizes under a no-till systemRodrighero, Maik Barbosa 21 December 2012 (has links)
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Previous issue date: 2012-12-21 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / To control soil acidity in no-till systems, lime is broadcast on the surface without incorporation. In order to test the hypothesis that the source and particle size of the corrective influence the soil reaction and crop response to lime on the surface in no-till system, two experiments were conducted in Tibagi (PR), one in clayey Oxisol and another in sandy Litholic Neosol. A randomized complete block design was used in a
factorial 2 × 2 × 4 with three replications, in each experiment. The treatments consisted of four rates of lime on the surface, estimated to raise the base saturation of the topsoil (0-20 cm), at 50, 70 and 90%; two sources of lime were used, calcitic and dolomitic,and two ranges of lime material effective calcium carbonate equivalent (ECCE), range
B (ECCE 60-75%) and range D (ECCE > 90%). In both experiments, the lime was applied on the soil surface in August 2010. During the spring-summer season in 2010-
11 and 2011-12, corn and soybean were grown on the clayey soil, and soybean and corn on the sandy soil, respectively. After 12 months of liming, soil chemical analyses were
performed in samples taken at the 0-5, 5-10, 10-20, 20-40, and 40-60 cm depths. Leaf samples of corn and soybean were taken during crop flowering, in the second year of cultivation, for foliar diagnosis. Grain yields of corn and soybean, in both experiments,were evaluated in two years, after the physiological maturity, and grain moisture was corrected to 130 g kg-1. Surface application of lime in both soils, after 12 months, promoted amelioration of soil acidity mainly in the 0-5 cm layer and, to a lesser extent in the 5-10 cm, regardless of the source and range of lime ECCE. Calcitic lime showed
a stronger reaction than dolomitic lime in the soil surface layers. The extraction with cation exchange resin overestimated the exchangeable Ca and Mg content in relation to the 0.1 mol L-1 KCl solution when coarser grain size lime was applied on the surface. Surface liming increased the Ca-leaf content, especially with the use of calcitic lime,
and Mg-leaf content mainly with the use of dolomitic limestone, and reduced Mn and Zn contents in the leaves, regardless of the source of lime, in the corn and soybean
crops. Grain yields of corn and soybean in clayey Oxisol and corn in sandy Litholic Neosol were increased with the lime rates, but were not affected by sources and ECCE ranges of material lime. Surface application of lime in soils under no-till was proved of fundamental importance to maximize crop grain yield, regardless of the lime source being calcitic or dolomitic, or the ECCE range, B or D of the material lime. / No sistema plantio direto, a correção da acidez é feita por meio da aplicação de calcário na superfície sem incorporação. Com a hipótese de que a fonte e a granulometria dos
corretivos interferem na reação do solo e na resposta das culturas à calagem superficial em plantio direto, foram realizados dois experimentos em Tibagi (PR), sendo um em
Latossolo Vermelho argiloso e outro em Neossolo Litólico arenoso, no período de 2010 a 2012. O delineamento empregado, em cada experimento, foi o de blocos completos ao acaso, em esquema fatorial 2 × 2 × 4, com três repetições. Os tratamentos foram constituídos de quatro doses de calcário na superfície, estimadas para elevar a saturação por bases do solo (0–20 cm), a 50, 70 e 90%; duas fontes de calcário, calcítico e dolomítico; e duas faixas de poder relativo de neutralização total (PRNT), faixa B (PRNT de 60 a 75%) e faixa D (PRNT > 90%). Nos dois experimentos, o calcário foi aplicado a lanço sobre a superfície do solo em agosto de 2010. Realizaram-se dois cultivos em 2010–11 e 2011–12, com milho e soja no solo argiloso, e soja e milho no
solo arenoso. Após 12 meses da aplicação, análises químicas de solo foram realizadas em amostras coletadas nas camadas de 0–5, 5–10, 10–20, 20–40 e 40–60 cm de profundidade. Amostras de folhas de milho e soja foram coletadas por ocasião do florescimento das culturas, no segundo ano de cultivo, para fins de diagnose foliar. A produtividade de grãos de milho e soja, nos dois experimentos, foi avaliada, nos dois
anos, após a maturação fisiológica, corrigindo-se a umidade dos grãos para 130 g kg-1 de água. A aplicação superficial de calcário nos dois solos, após 12 meses, promoveu correção da acidez principalmente na camada de 0-5 cm e, em menor grau, na de 5-10 cm, independentemente da fonte e da faixa de PRNT dos corretivos. O calcário calcítico apresentou maior reação do que o calcário dolomítico nas camadas superficiais do solo. A extração com a resina de troca catiônica superestimou os teores de Ca e Mg trocáveis em relação à solução de KCl 1 mol L-1 quando houve aplicação superficial de calcário com granulometria mais grossa. A calagem superficial aumentou as concentrações de Ca-foliar, principalmente com a utilização de calcário calcítico, e de Mg-foliar,especialmente com o uso de calcário dolomítico, e reduziu os teores foliares de Mn e Zn, independentemente da fonte de calcário, nas culturas de milho e soja. As
produtividades de milho e soja, no Latossolo argiloso, e de milho, no Neossolo arenoso,foram aumentadas com as doses de calcário, mas não foram influenciadas pelas fontes e
faixas de PRNT dos corretivos. A calagem superficial em solos sob plantio direto se mostrou de fundamental importância para maximizar a produtividade de grãos das culturas, independentemente da fonte de calcário, calcítico ou dolomítico, e da faixa, B ou D, de PRNT dos corretivos.
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Unsicherheitsbilanzen in der quantitativen FT-IR-SpektroskopieYozgatli, Hakan Peter 22 May 2002 (has links)
Die Unsicherheit analytischer Ergebnisse lässt Rückschlüsse auf die Zuverlässigkeit der angewandten Analyseverfahren zu. Entsprechend den Qualitätsanforderungen an akkreditierte Prüf- und Kalibrierlaboratorien (siehe u.a. Norm ISO/IEC 17025) ist daher die Angabe der Messunsicherheit erforderlich. Zur Ermittlung der Messunsicherheit typischer FT-IR-spektroskopischer Analysen von Feststoffen und Flüssigkeiten wurde eine systematische Untersuchung des Einflusses zahlreicher FT-, proben- und gerätespezifischer Parameter auf den Messwert durchgeführt. Die Überprüfung der Ordinatenrichtigkeit bei FT-IR-spektroskopischen Messungen an Gläsern erfolgte mit Hilfe eines Transmissionsstandards des National Physical Laboratory (NPL), der aus einem Schott NG11 Neutralglasfilter besteht, und bei Messungen an Flüssigkeiten durch Vergleich der nach einem Absolutverfahren bestimmten Extinktionskoeffizienten des Dichlormethans mit von der IUPAC publizierten Standardwerten. Nach Optimierung der Messbedingungen stimmen die Transmissionswerte des NPL-Standards und die Extinktionskoeffizienten des Dichlormethans mit den entsprechenden Standardwerten überein. Die für die Bestimmung dieser Messgrößen aufgestellten Unsicherheitsbilanzen gestatten die quantitative Abschätzung des Einflusses einzelner Parameter auf die Gesamtunsicherheit. Bei Anwendung der KBr-Presstechnik für die quantitative Analyse von unlöslichen Feststoffen haben die Partikelgröße des Analyten und die Homogenität der Presslinge einen dominierenden Einfluss auf die Qualität der Spektren. Um die Unsicherheit zu minimieren, die auf dem Einfluss der Partikelgröße beruht, muss es ein Ziel der Probenvorbereitung sein, dass die Partikeldurchmesser der Kalibriersubstanz und des Analyten einen Wert von ca. 2 µm nicht überschreiten und möglichst gleich groß sind. Bei Untersuchungen mit Calciumcarbonat-Proben unterschiedlicher Partikeldurchmesser hat sich die Halbwertsbreite der auszuwertenden Bande, die mit der Partikelgröße korreliert, als ein geeignetes Maß für die Beurteilung erwiesen, wie gut letztere Bedingung erfüllt ist. Eine inhomogene Verteilung der absorbierenden Partikel im Pressling kann durch Durchstrahlen der gesamten Oberfläche des Presslings oder durch Mitteln der an verschiedenen Positionen des Presslings gemessenen Spektren berücksichtigt werden. Diese Arbeiten zeigen, dass die Anwendung der KBr-Presstechnik bei sorgfältiger Probenvorbereitung und Einhaltung optimaler Messbedingungen im Rahmen der Messunsicherheit zu richtigen Ergebnissen führt. / The uncertainty of analytical results allows to assess the reliability of the applied analytical methods. According to quality requirements for accredited laboratories (see e.g. ISO/IEC 17025) it is necessary to report the uncertainty of measurement. In order to evaluate the uncertainty of typical quantitative FT-IR spectroscopic analysis of solids and liquids a detailed study of the influence of numerous FT-, sample- and instrument-specific parameters on the measurand was performed. The trueness of FT-IR spectroscopic measurements on glasses was tested with a transmittance standard of the National Physical Laboratory (NPL) that consists of a Schott NG11 neutral density filter. The trueness of FT-IR spectroscopic measurements on liquids was checked by the comparison of the molar absorptivities of dichloromethane determined by transmission measurements with the standard values published by IUPAC. After optimisation of the measurement conditions the transmittance values of the NPL standard and the molar absorptivities of dichloromethane are in accordance with the corresponding standard values. The uncertainty budgets evaluated for these measurends makes it possible to assess the contribution of a single parameter on the combined uncertainty. By using the KBr pressed pellet technique for the quantitative analysis of insoluble solids the particle size of the analyte and the homogeneity of the pellets are the major contributions to the quality of spectra. In order to minimize the uncertainty due to the particle size a purpose of the sample preparation must be to reduce the particle sizes of the calibration sample and the analyte to a maximum size of 2 µm and both particle sizes should agree. A detailed study with calcium carbonate samples with different mean particle sizes has shown that the half-width of the analysed band depends on the particle size and is suitable to test how far the last mentioned condition is fulfilled. In order to minimize the uncertainty due to an inhomogeneous distribution of the absorbing particles in the pellets the infrared beam must pass through the whole surface area of a pellet or the mean value of the spectra measured at different positions on the surface area has to be evaluated. This work proves that the use of the pressed pellet technique can lead to correct results within the limits of the uncertainty if the sample preparation is carried out carefully and optimal measurement conditions are kept.
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