Um sistema de tratamento constituído de um reator anaeróbio de mistura completa e um reator anaeróbio compartimentado (ABR) foi operado durante 140 dias para estudar os efeitos do pré-tratamento das águas residuárias de uma indústria química, por carvão ativado em pó (CAP), e suas implicações nos processos de nitrificação e desnitrificação. Utilizou-se, no pré-tratamento do resíduo, duas concentrações de carvão ativado em pó. Para aplicação de 10 mg/l de CAP a remoção de DQO foi de 60% e a de NTK foi de 50%. Nesta fase, os processos de remoção de nitrogênio foram plenamente viabilizados. Para 5 mg/l de CAP a remoção de DQO foi de 44% e a remoção de NTK 46%, neste período se observou inibição por metais pesados e acúmulo de nitrito no sistema. / A treatment system composed of both an aerobic complete-mix reactor and a anaerobic baftled reactor (ABR) was operated for 140 days to study the effects of the treatment of wastewater chemical industry by powdered activate carbon (PAC) and its implications in nitrification - denitrification processes. In the residue preliminary treatment, two concentrations of PAC were used. For the application of 10 mg/l of CAP the removal of COD was 60% and the removal of TKN was 50%. In this phase, the processes of nitrogen removal were possible to be completely carried out. For 5 mg/l of CAP, the removal of COD was 44% and the removal of TKN 46%. In this period, the inhibition by heavy metaIs and nitrite accumulation in the system was observed.

O crescimento desordenado das cidades, a utilização de áreas para plantio próximas aos mananciais e o lançamento de águas residuárias domésticas e industriais sem tratamento são consideradas as principais fontes de poluição dos corpos d´água. Tal poluição contribui para o enriquecimento dos corpos hídricos em relação aos nutrientes. Isto, combinado com fatores climáticos proporciona condições para a ocorrência de florações de algas que podem apresentar espécies potencialmente tóxicas. Desta forma, aumenta a preocupação com desenvolvimento de técnicas de tratamento que forneçam água de qualidade garantindo a saúde da população consumidora. Nesta pesquisa, foram preparadas águas de estudo com diferentes concentrações de microcistina, com as quais foram testados alguns processos de tratamento, em escala de bancada, que consistiram na pré-cloração, adsorção em carvão ativado em pó, coagulação/floculação, flotação por ar dissolvido e centrifugação. O fluxograma de tratamento com aplicação de carvão ativado logo após a mistura rápida foi o que apresentou melhores resultados em termos de cor aparente, turbidez e concentração residual de microcistina. Foi avaliada a influência da concentração de microcistina nos tratamentos simulados. Constatou-se que para 104,92 µg/L de microcistina a aplicação de 3,0 mg\'CL IND.2\'/L (10 segundos antes da mistura rápida) e 30 mg/L de CAP (logo após a mistura rápida) não foram capazes de reduzir a concentração de microcistina para menos de 1 µg/L, conforme o limite estabelecido pela Portaria 518/04 do Ministério da Saúde. Assim, optou-se pela estimativa da dosagem mínima de carvão ativado em pó (CAP) em função da concentração inicial de microcistina das três águas preparadas. O residual de microcistina em cada água preparada, após a aplicação da dosagem estimada de CAP, foi: Água de Estudo 1 = 0,80 µg/L, Água de Estudo 2 = 0,82 µg/L e Água de Estudo 3 = 0,23 µg/L. / The disordered growth of cities, the use of planting areas near the water sources and the launch of domestic and industrial wastewater without treatment are the main sources of water bodies\' pollution. Such pollution contributes to increase the nutrient loading in the water bodies. In association with climatic factors, this enrichment of nutrient provides suitable conditions for the bloom of potentially toxic algae. Thus, increases the concern over to develop treatment techniques that provide water quality able to ensure the health of the consumer population. In this research, waters were prepared with different concentrations of microcystin and some treatments were tested in bench scale. These tests consisted in prechlorination, adsorption on powdered activated carbon, coagulation/flocculation, dissolved air flotation and centrifugation. The diagram of treatment with activated carbon application after the rapid mix showed better results of apparent color, turbidity and residual concentration of microcystin. The influence of the concentration of microcystin in the simulated treatments was evaluated. It was found that for 104.92 µg/L of microcystin the application of 3.0 mg\'CL IND.2\'/L (10 seconds before rapid mix) and 30 mg/L of PAC (after a quick mixture) were not able to reduce the concentration of microcystin to less than 1 µg/L, as the limit established by Order 518/04 of the Health Ministry. Thus, it was decided to estimate the minimum dosage of powdered activated carbon (PAC) according to the initial concentration of microcystin found in the three prepared waters. The residual concentration of microcystin in each water, after the estimated dosage application of PAC was: Water 1 = 0.80 µg/L; Water 2 = 0.82 µg/L; Water 3 = 0, 23 µg/L.

Abstract Water contamination is a global problem and the growing utilization of limited water resources creates a need for efficient purification methods. Industrial effluents are polluting the natural waters, e.g. uncontrolled mining activities in developing countries have created numerous environmental hazards and different types of pollutants. This study focuses on novel adsorbents and photocatalytic materials in order to reach the aim of more efficient and affordable water treatment. This thesis aimed at making active, efficient, and viable adsorbents out of waste materials, as well as using photocatalysis in water treatment for organic pollutants originating from different types of industries. Local Peruvian agro-waste was used as a precursor for activated carbon that was used in adsorption studies for single (As(V) and methylene blue, MB), and multicomponent mixtures (As(V)/Pb/Cd), and real polluted river water. An industrial intermediate product, hydrous TiO2, was used for As(III)/As(V) removal. Photocatalytic materials included a commercial photoactive TiO2 (P25), and tailor-made TiO2 based nanofibers (NF) decorated with Pt/Pd. The results show that the agro-waste based activated carbons show high potential as adsorbents (e.g. ~100% As(V) removal in 2 h). With the multicomponent solution there is evidently competition for the adsorption sites; Pb was removed most efficiently. The specific surface area and pore size distribution play an important role in MB adsorption, as with As(V) the ash content is the most influential parameter. The industrial intermediate product has a high adsorption capacity towards both As(III) and As(V) (over 96% removals in 4 h), and is promising for use in natural and wastewater treatment due to its adsorption properties, availability, low cost, and non-toxicity. Photocatalysis was found to be an efficient removal method for the pollutants tested, also in the diluted industrial wastewater matrix, e.g. diuron was removed 99% in 1 h. The NFs are promising for the efficient photocatalytic degradation of organic effluents in aqueous streams such as wastewaters originating from e.g. biofuel production or fine chemicals and pharmaceutical industry. This study provides new and valuable knowledge for the purification of waters, especially when aiming at developing inexpensive water treatment materials and methods for different applications. / Tiivistelmä Puhtaan veden puute on maailman laajuinen ongelma, ja raskasmetallien ja orgaanisten haitta-aineiden päätymistä ympäristöön ja luonnonvesiin voidaan vähentää hyvällä ja tehokkaalla teollisuuden jätevesien käsittelyllä. Uusia ja tehokkaita, ympäristön kannalta suotuisia ja kestäviä vedenpuhdistustekniikoita tarvitaan erityisesti kehitysmaissa, joissa esim. kontrolloimaton kaivostoiminta aiheuttaa ympäristö- ja terveyshaittoja. Työn kokeellisessa osassa valmistettiin perulaisesta maatalousjätteistä aktiivihiiltä kemiallisella aktivoinnilla, ja seurattiin niiden kykyä adsorboida haitta-aineita (As(V), Pb, Cd, metyleenisini) yksi- ja monikomponenttiliuoksista ja saastuneesta luonnonvedestä (Puyango-Tumbesjoki, Peru). Lisäksi tutkittiin teollisuuden välituotteen (TiO2) aktiivisuutta arseenin, As(III) ja As(V), adsorptiossa. Viimeisessä osiossa tutkittiin valokatalyysiä orgaanisten haitta-aineiden poistossa vesiliuoksista sekä kaupallisella TiO2 P25 -katalyytillä että kokeellisilla Pd/Pt-dopatuilla TiO2 -nanokuiduilla. Tulokset osoittavat, että paikallisesta raaka-aineesta valmistetut aktiivihiilet ovat hyvin potentiaalisia vedenpuhdistusmateriaaleja saavuttaen jopa 100% As(V) poistuman (2h). Adsorboitavien ionien välillä on nähtävissä kilpailua monikomponettiadsorptiossa; lyijyn havaittiin poistuvan tehokkaimmin tutkituissa olosuhteissa. Adsorbentin ominaispinta-ala ja huokoskokojakauma ovat tärkeitä tekijöitä metyleenisinin adsorptiossa, kun taas tuhkapitoisuudella on arseenin adsorptioon suurempi vaikutus. Teollisuuden TiO2-välituotteella havaittiin olevan korkea adsorptiokapasiteetti sekä As(III)- että As(V)-spesieksiä kohtaan saavuttaen yli 96% poistumat (4h). Se on lupaava materiaali edelleen kehitettäväksi ja käytettäväksi esimerkiksi luonnonvesien ja jätevesien puhdistuksessa johtuen sen hyvistä adsorptio-ominaisuuksista, saatavuudesta, edullisuudesta ja myrkyttömyydestä. Valokatalyysin havaittiin olevan toimiva menetelmä orgaanisten molekyylien hajottamiseen, myös laimeasta teollisuuden jätevesimatriisista, esim. diuroni poistui 99% tunnissa. Nanokuitujen tapauksessa aktiivinen metalli vaikutti merkittävämmin reaktion tehokkuuteen kuin ominaispinta-ala. Tämä työ tarjoaa uutta ja tärkeää tietoa vesien puhdistukseen kun tavoitteena on löytää tehokas ja edullinen menetelmä erityyppisiin sovelluksiin.

Abstract Gasification is an energy conversion method for the utilisation of biomass for obtaining energy (heat and power). In the gasification process carbon residue is formed as a waste. For improving the cost-effectiveness of the gasification process the utilisation of this waste is important and the present legislation also creates requirements for the utilisation of waste material. Activated carbon is typically used for purification of water, for example, wastewaters as well as gaseous emissions. Consequently, commercial activated carbon is fairly expensive and its preparation is energy consuming. However, this inhibits sometimes its widespread use in wastewater treatment and therefore there is a need to develop cost-effective adsorbents from alternative biomass-based low-cost raw materials to remove harmful substances from aqueous solutions. The first aim of this thesis was to determine physical and chemical properties of carbon residues from wood gasification, and fly ashes from burning processes were used as reference samples. The properties are essential to known when evaluating the potential utilisation applications for unknown carbon residue samples. Properties of carbon residue indicate that it would be suitable adsorbent due to the high carbon content but its activation or modification is needed. The second aim was to modify this industrial carbonaceous by-product by physical and chemical activation and chemical modification methods to maximise the adsorption capacity of material. Based on our results, adsorption properties can be enhanced by using zinc chloride as a chemical activating agent, carbon dioxide as a physical activating agent and ferric chloride in the chemical modification and adsorbents with specific surface areas 285, 590 and 52 m2 g-1 were produced, respectively. The third aim was to test produced adsorbents to anions removal. Chemically activated carbon residue removes phosphate well and physically activated carbon residue removes phosphates and nitrates. Chemically modified carbon residue was observed to be suitable sorbent for sulphate removal. Optimal initial pH and concentration were determined and effect of time was studied and kinetic calculations and isotherm analysis was done for studied adsorbents. / Tiivistelmä Kaasutus on tehokas tapa hyödyntää biomassaa sähkön- ja lämmöntuotannossa. Kaasutuksessa muodostuu jätteenä hiilijäännöstä, jonka hyödyntäminen on tärkeää kaasutusprosessin kustannustehokkuuden parantamiseksi. Myös nykyinen lainsäädäntö asettaa vaatimuksia jätemateriaalien hyödyntämiselle. Aktiivihiiltä on tyypillisesti käytetty mm. jäteveden sekä kaasujen puhdistukseen. Aktiivihiili on kuitenkin kallista ja sen valmistaminen on energiaa kuluttava prosessi, mikä rajoittaa sen käyttöä. Tämän vuoksi tarvitaan uutta tietoa myös kustannustehokkaampien adsorbenttien valmistamiseen soveltuvista vaihtoehtoisista biomassapohjaisista raaka-aineista. Tutkimuksen tavoitteena oli aluksi määrittää puun kaasutuksessa muodostuneen hiilijäännöksen fysikaalisia ja kemiallisia ominaisuuksia, joiden tunteminen on tärkeää arvioitaessa soveltuvia hyödyntämiskohteita kyseiselle tuntemattomalle jätemateriaalille. Referenssinäytteinä käytettiin polttolaitoksilla muodostunutta lentotuhkaa. Hiilijäännöksen ominaisuuksien perusteella se voisi olla soveltuva adsorbentti, mutta aktivointi tai modifiointi on välttämätöntä hiilijäännöksen adsorptiokapasiteetin parantamiseksi. Työn toinen tavoite oli parantaa hiilijäännöksen adsorptio-ominaisuuksia fysikaalisesti ja kemiallisesti aktivoimalla tai kemiallisesti modifioimalla. Tulosten perusteella adsorptio-ominaisuuksia voidaan parantaa parhaiten käyttämällä sinkkikloridia kemiallisessa aktivoinnissa, hiilidioksidia fysikaalisessa aktivoinnissa ja rautakloridia kemiallisessa modifioinnissa, jolloin valmistettujen adsorbenttien ominaispinta-alat olivat 285, 590 ja 52 m2 g-1. Työn kolmas tavoite oli tutkia valmistettujen adsorbenttien adsorptiokykyä anionien poistossa laboratoriomittakaavassa. Kemiallisesti aktivoitu hiilijäännös poistaa tehokkaasti fosfaattia, fysikaalisesti aktivoitu fosfaattia ja nitraattia ja kemiallisesti modifioitu hiilijäännös on hyvä sorbentti sulfaatinpoistossa. Adsorptiokokeissa määritettiin optimaalinen alku pH ja alkukonsentraatio ja lisäksi tutkittiin ajan vaikutusta adsorptioon. Tulosten perusteella tehtiin kinetiikkamallinnusta sekä isotermianalyysi.

Ce manuscrit s’intéresse à une filière globale et durable de dépollution des eaux souterraines. Le polluant cible, le tétrachloroéthylène, est un composé organique volatil. La première étape de cette filière est la séparation du contaminant de l’eau. Elle a été réalisée par adsorption sur charbons actifs dans une colonne en lit fixe. Les résultats obtenus en laboratoire sur les capacités et les cinétiques d’adsorption ont permis de montrer l’efficacité de ce procédé. Un modèle issu de ces expériences a représenté correctement des conditions opératoires variées correspondant à celles utilisées dans l’industrie. Ce modèle a été validé par un pilote préindustriel installé sur site et fonctionnant en conditions réelles. La gestion des charbons actifs chargés en polluant a été étudiée. La régénération thermique a été privilégiée. Cette opération présente l’intérêt de rétablir les capacités d’adsorption des carbones activés et de récupérer les polluants en phase liquide. Bien que préférable à la production d’adsorbants, elle pourrait encore être plus durable et compétitive économiquement en effectuant le traitement thermique par voie solaire. Il a été montré que le taux de régénération est le même pour les régénérations solaire et classique. Il est donc possible, dans le cas du tétrachloroéthylène, de remplacer une source d’énergie fossile par le soleil. La solution de distillat obtenue lors de la régénération peut être minéralisée par photocatalyse hétérogène. Cette opération a été réalisée en laboratoire avec une lampe reproduisant le spectre solaire. La faisabilité de la photocatalyse solaire sur le résidu issu de cette filière de dépollution a ainsi été montrée. / This manuscript focuses on a comprehensive and durable treatment of polluted groundwater. The target contaminant, tetrachlorethylene, is a volatile organic compound. The first step in the treatment is the separation of contaminants. It was carried out by adsorption on activated carbons in a fixed bed column. The results obtained in the laboratory on the adsorption capacity and kinetics have shown the efficiency of this process. A mathematic model represented properly the various operating conditions corresponding to those used in the industry. This model has been validated by a pre-industrial pilot installed onsite and operating in real conditions. Management of spent activated carbons was studied. The thermal regeneration was chosen because it has the interest to restore the adsorption capacity of adsorbents and to collect the pollutants in a liquid phase. Although preferable to the production of activated carbons, it could still be economically more competitive and more sustainable by performing the heat treatment by solar means. It has been shown that the regeneration rate is the same for the solar and classical regenerations. It is therefore possible, in the case of tetrachlorethylene, to replace a fossil energy source by the sun.The distillate solution obtained during the regeneration can be mineralized by heterogeneous photocatalysis. This operation was carried out in the laboratory with a lamp reproducing the solar spectrum. The feasibility of solar photocatalysis on the final residue of the water treatment has been shown.

Le premier chapitre de ce manuscrit est dédié aux traitements primaires et biologiques conventionnels. Les abattements de nombreux polluants prioritaires et émergents ont été déterminés pour la décantation, la décantation physico-chimique lamellaire, les boues activées faible charge et la biofiltration. Les composés hydrophobes et les métaux, les composés organiques volatils et les molécules biodégradables sont plutôt bien éliminés par ces filières. La normalisation des abattements à celui de l'azote a permis de démontrer que la filière décantation physico-chimique lamellaire + biofiltration a une efficacité comparable à la filière décantation + boues activées, bien que plus compacte et opérant avec un temps de séjour hydraulique plus faible. En complément, l'analyse dans trois effluents de STEP du SIAAP de 55 résidus pharmaceutiques et hormones (PPHs), et de 6 autres polluants émergents, a permis de caractériser finement la contamination de ces rejets par ces composés, et de montrer la forte fréquence de détection à des concentrations supérieures à 100 ng/L de 14 composés. Dans le second chapitre, les campagnes menées ont permis de fournir des données sur cinq types de boues, dont les boues brutes, centrifugées, digérées, séchées et les cakes de boues, et sur quatre procédés de traitement des boues communément utilisés en France (centrifugation, digestion anaérobie, séchage thermique et cuisson + filtration presse). De nombreux composés ont été détectés dans ces boues et ce à des niveaux de concentrations variant du µg/kg MS (matière sèche) au g/kg MS. Certains polluants, comme les LAS, métaux ou PCBs, ne sont pas du tout éliminés au cours des traitements des boues, entrainant une augmentation de leur teneur, alors que d'autres, tels que les alkylphénols ou les PPHs, sont abattus partiellement par digestion et séchage thermique. La digestion anaérobie est le procédé qui permet la meilleure élimination de ces composés. La présence de plusieurs composés dans les centrats et condensats indique qu'un transfert a lieu et que la biodégradation et la volatilisation ne sont pas les seuls mécanismes d'élimination. Le dernier chapitre décrit les performances d'un pilote de traitement tertiaire, fonctionnant avec du charbon actif en poudre (CAP) ou en micro-grain (CAµG), à l'échelle industrielle, au cours de 32 campagnes de mesure. Les résultats ont montré que la plupart des PPHs, alkylphénols, édulcorants, pesticides et parabènes pouvaient être abattus efficacement (> 80%) par du charbon actif en lit fluidisé, à des doses limitées de charbon (10-20 g/m3). La dose de charbon influence fortement les performances, que ce soit avec du CAP ou du CAµG. Le CAµG permet d'obtenir des abattements en PPHs comparables au CAP à une même dose (10 ou 20 gCAµG/m3), même si certains composés sont légèrement mieux abattus (5-15%) avec le CAP, probablement par l'action du FeCl3. Cependant, le CAµG a plusieurs avantages opérationnels par rapport au CAP. En particulier, le CAµG est réactivable, facile à utiliser, il fonctionne à des temps de séjour élevés favorisant le développement d'une activité biologique et sans ajout de coagulant/flocculant pour maintenir le lit de charbon. Par ailleurs, ce type de procédé permet l'affinage du traitement des paramètres globaux de qualité des eaux, notamment le CAµG qui retient les MES et élimine totalement les nitrites. La corrélation entre performances du procédé et abattement de l'absorbance UV à 254 nm a été établie, indiquant que ce paramètre pourrait être utilisé comme indicateur de performance. La mise en place d'expériences complémentaires en laboratoire a permis de mieux appréhender le processus de sorption sur le CAP. Le lien étroit entre surface spécifique, densité apparente du CAP et abattement des PPHs a été démontré, ainsi que l'importance de la dose de CAP et du temps de contact. L'impact positif du FeCl3, et l'influence négative de la quantité et de la qualité de la matière organique ont été observés / The first chapter is dedicated to the conventional primary and biological treatments. Hence, removals of a wide range of priority and emerging micropollutants were assessed for primary settling, physico-chemical lamellar settling, low load activated sludge process and biofiltration. Hydrophobic compounds and metals, as well as volatile organic compounds and biodegradable pollutants are rather well eliminated by these treatments. Moreover, considering removals normalized with nitrogen removals, the physico-chemical lamellar settling + biofiltration wastewater treatment plant (WWTP) is as efficient as the primary settling + low load activated sludge WWTP, despite its lower hydraulic retention time and its higher compactness. As a complement, the analysis in 3 WWTP effluents from SIAAP of 55 pharmaceuticals and hormones (PPHs) and 6 other emerging pollutants allowed characterizing the contamination of these discharges, and highlighting the high occurrence of 14 compounds at concentrations above 100 ng/L. In the second chapter, the contamination by micropollutants of different types of Parisian sewage sludges was assessed, as well as their fate during sludge treatments. Various compounds, such as alkylphenols, linear alkylbenzene sulfonates (LAS), metals, organotins, phthalates, polybromodiphenylethers (PBDEs), perfluorinated acids (PFAs), polychlorobiphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs) and PPHs, were quantified in raw, centrifuged, digested, thermally dried sludges and sludge cakes (cooking + press-filtering). Some of them (LAS, metals, PCBs) are not eliminated or less than dry matter by sludge treatments resulting in a content increase, while others (alkylphenols, organotins, PBDEs, PPHs, PFAs) are more removed than dry matter by anaerobic digestion and thermal drying. Overall, anaerobic digestion is the most efficient sludge process. Finally, the detection of several pollutants in the centrifuged and condensed waters from centrifugation and thermal drying indicates that a transfer is occurring and that biodegradation and volatilization are not the only mechanism to be involved in micropollutant removal from sludge. The last chapter aimed at investigating the performance of a large scale pilot operating with powdered (PAC) or micro-grain activated carbon (µGAC), during 32 campaigns. Results showed that most of PPHs, alkylphenols, artificial sweeteners, parabens and pesticides are efficiently removed (> 80%) by activated carbon in fluidized bed at moderate doses (10-20 g/m3). Furthermore, the activated carbon dose has a great influence on performances, whether with PAC or µGAC. Then, µGAC has several operational advantages (reactivability, ease of operation, high solid retention time, no need for coagulant/flocculant addition to handle the fluidized bed) over the PAC together with similar performances at a similar fresh µGAC dose (20 gµGAC/m3 ≈ 20 gPAC/m3). In addition this type of process allows an improvement of the conventional wastewater quality parameters, especially µGAC which retains total suspended solids and eliminates totally nitrites. Finally, a correlation between micropollutant and UV-254 removals has been confirmed, suggesting that this parameter could be used as a performances indicator. The complementary laboratory scale experiments performed within this chapter allowed understanding better the PAC adsorption mechanism in wastewater. The correlation between the specific surface, the bulk density of the PAC and PPHs removal has been displayed, as well as the importance of the fresh PAC dose and the contact time. Moreover, the positive effect of FeCl3 and negative influence of the quantity and quality of organic matter on micropollutant adsorption have been observed

Philosophiae Doctor - PhD / Aqueous ion-intercalation batteries (AIB’s) have the potential to provide both high power for hybrid-electric transport, and low cost bulk energy storage for electric grid supply. However, a major setback to AIB development is the instability of suitable ionintercalation anode material in aqueous electrolyte. To counter this problem, the use of activated carbon (AC) (a supercapacitor anode) paired against the low cost ionintercalation cathode spinel LiMn2O4 (LMO) provides a stable alternative. This thesis comprises two novel areas of investigation concerning: (1) the development of the AC/LMO cell for high power applications, and (2) the introduction of PbSO4 as a high capacity alternative anode material paired against LMO for low cost bulk energy storage. The study on AC/LMO explores the electrode combination’s practical specific energy and power capability at high P/E (power to energy ratio) of 50:1 suitable for hybrid electric vehicle batteries. To study the relationship between electrode material loading density, active material performance, and current collector mass contribution, a specially designed cell was constructed for galvanic cycling of different thicknesses of electrode. Between a loading density range of 25 – 100 mg, ~50 mg of total active material between two 1 cm2 current collectors produced the highest 50:1 P/E ratio values of 4 Wh/kg and 200 W/kg, constituting a 4-fold reduction of the active material values of thin films at 50:1 P/E. The cycling potentials of the individual electrodes revealed that doublings of electrode film loading density increased the LMO electrode’s polarization and voltage drop to similar levels as doublings in applied current density. However, by increasing the charging voltage from 1.8 V to 2.2 V, 6 Wh/kg and 300 W/kg was obtainable with minimal loss of energy efficiency. Finally a large-format cell of a calculated 3 Ah capacity at 50:1 P/E was constructed and tested. The cell produced ~60% of the anticipated capacity due to a suspected high level of resistance in the electrode contact points. The overall conclusion to the study was that AC/LMO holds promise for high power applications, and that future use of higher rate capability forms of LMO offers a promising avenue for further research. v The second part of this thesis presents the development of a novel cell chemistry, PbSO4/LMO, that has yet to be reported elsewhere in existing literature. The cell uses aqueous pH 7, 1 M, Li2SO4 electrolyte, and forms an electrode coupling where the PbSO4 anode charge/discharge is analogous to that in Pb-acid batteries. The average discharge voltage of the cell was 1.4 V and formed a flat charge/discharge plateau. The use of a low cost carbon coating method to encapsulate PbSO4 microparticles had a marked improvement on cell performance, and compared to uncoated PbSO4 improved both rate capability and specific capacity of the material. The active materials of the carbon-coated PbSO4/LMO cell produced a specific energy 51.1 Wh/kg, which, if a 65% yield is possible for a practical cell format, equals 38.4 Wh/kg, which is 15 Wh/kg higher than AC/LMO bulk storage cells at 23 Wh/kg, but lower than Pb-acid batteries at ~25-50 Wh/kg. Interestingly, the specific capacity of PbSO4 was 76 mAh/g compared to 100 mAh/g in Pb-acid cells. The predicted cost of the cell, providing a 65% value of the active material specific energy for a practical cell can be realized, is on par with Pb-acid battery technology and, importantly, uses 2.3 × less Pb/kWh. The cycling stability achieved thus far is promising, but will require testing over comparable cycle life periods to commercial batteries, which could be anywhere between 5 – 15 years.

Depuis une quinzaine d’années, les matériaux poreux de type Metal Organic Frameworks (MOFs) offrent de nouvelles perspectives dans le cadre du stockage d’hydrogène par adsorption. Ces matériaux possèdent une structure et un réseau de pores particulièrement bien adaptés à l’adsorption des gaz. Ainsi, le téréphtalate de Chrome (III) (MIL-101(Cr)), composé chimiquement très stable, possède une grande capacité de stockage de l’hydrogène, du dioxyde de carbone et du méthane. Afin de renforcer sa capacité de stockage d’hydrogène, un dopage au charbon actif (AC) du matériau a été envisagé. Les synthèses des matériaux dopés et non-dopés ont été réalisées et, pour cela, différents agents minéralisants (acide fluorhydrique, acide acétique et acétate de sodium) ont été testés. Les matériaux synthétisés furent caractérisés par diffraction des rayons X (DRX), par microscopie électronique à balayage (MEB), par analyses thermogravimétriques (ATG) et par adsorption d’azote à 77K. Les capacités de stockage d’hydrogène de ces matériaux à 77 K et 100 bar ont été évaluées par mesures des isothermes d’adsorption d’hydrogène, réalisées par méthodes volumétrique et gravimétrique. Les résultats obtenus par ces deux méthodes sont en parfait accord et le matériau composite affiche une capacité d’adsorption de 13.5 wt%, qui est supérieure à celle du matériau non dopé (8.2 wt% dans les même conditions expérimentales). Les cinétiques d’adsorption ont été mesurées à 77 K par méthode volumétrique. Les résultats obtenus ont été comparés au modèle de la force motrice linéaire, Linear Driving Force (LDF). Un modèle de diffusion dépendant de la température a été développé afin de tenir compte des variations de températures qui se produisent durant le processus d’adsorption. / Since the last 15 years, the porous solids such as Metal-Organic Frameworks (MOFs) have opened new perspectives for the development of adsorbents for hydrogen storage. The structure and the pore networks of these materials are especially adapted to the adsorption of gases. The chromium (III) terephthalate-based MIL-101(Cr) is a very stable material which exhibits good adsorption uptakes for hydrogen (H2), carbon dioxide (CO2) and methane (CH4).In this study, syntheses were carried out by different ways and several mineralizing agents such as hydrofluoric acid (HF), acetic acid (CH3COOH) and sodium acetate (CH3COONa) have been tested. Moreover, Activated Carbon (AC) has been introduced in the framework to create an AC incorporated composite material with an enhanced specific surface area. Conventional techniques such as powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), thermogravimetric analysis (TGA) and nitrogen (N2) adsorption isotherms at 77 K were used for materials characterizations.In the aim to evaluate hydrogen storage capacities of these materials, hydrogen adsorption isotherms were measured at 77 K via both volumetric and gravimetric methods, and the obtained results are in good agreement. A hydrogen uptake value of 13.5 wt% has been measured at 77 K and 100 bar for the composite material which shows a great improvement of hydrogen capacity compared to the pristine MIL-101(Cr) (8.2 wt%).Finally, hydrogen adsorption kinetics has been measured at 77 K using volumetric method. The obtained results were compared to the Linear Driving Force (LDF) and a temperature dependent diffusion model was also considered to take into account the temperature variations which occur during the adsorption process.

El presente trabajo tiene como objetivo satisfacer una demanda generada en el mercado del negocio más grande del país: la minería. El presente proyecto generará bienestar económico para una parte de la población ya que generará trabajo y desarrollo económico. El documento presenta todo el sustento social, económico, operativo y tecnológico del proyecto. El producto generado es un producto poco común en el mercado pero tiene aplicaciones muy beneficiosas para el procesamiento de diferentes minerales. La propuesta plantea el diseño de una planta de producción de carbón activo en base a cáscara de café. El procesamiento de minerales con el producto presentado agrega valor al producto mineral final, generando una ventaja competitiva en el mercado minero, por lo que consideramos que el producto tendrá una gran acogida y podría motivar a muchos negocios mineros a darle diferentes ventajas competitivas a diferentes minerales. / The present work has the purpose of satisfying a demand generated in the biggest business on the country: mining. The present project will generate economic wellness for a part of the population because it will generate work and economic development. This document presents the economic, social, operative and technological support for the project. The product generated is poorly known on the market but has beneficial applications on minerals processing. The project proposal presents the design of an coffee shell based activated carbon production plant. The minerals processing with the presented product adds value on the final mineral product, generating a competitive advantage in the mining market, that is why we consider that the product will have a big reception and could motivate different mining businesses to add different competitive advantages to their minerals. / Trabajo de investigación

Made available in DSpace on 2017-06-01T18:20:38Z (GMT). No. of bitstreams: 1 dissertacao_paula_macedo.pdf: 713310 bytes, checksum: 941c18a8ca32e16587bf1e5a6169267d (MD5) Previous issue date: 2012-12-10 / The coconut fibers (Cocos nucifera) when intended in landfills under anaerobic conditions, cause the emission of methane, one of the most important greenhouse gas. In this work, is proposed the use of coconut fiber mixed in different ratios with alternative waste in order to mitigate the impacts caused by waste, enabling the production of new products. As an alternative, it was proposed to do the relationship coconut / residue equal to 100/0, 75/25 50/50 25/75 and 0/100 by collecting the waste orange, banana, and cashew acerola (pulp and peel) in the appropriate places. For immediate analysis were determined the ash content (600 ° C) and humidity (105 ° C)ASTM D-1762/64, the levels of volatile material (ash in a muffle furnace at 950 ° C) and fixed carbon, ASTM D-1762/64, and calorific power, according to ABNT-NBR 8633/84, the various treatments. The data were submitted to statistical analyzes where it was possible to draw graphs that demonstrate the relationship among the measurements performed, indicating the mixture of coconut fiber with cherry and banana the most promising. / As fibras-de-coco (Cocos nucifera) quando destinadas em aterros sob condições anaeróbias, provocam a emissão de metano, um dos mais importantes gases de efeito estufa. Neste trabalho, são propostos usos das fibras-de-coco misturadas em diferentes relações com resíduos alternativos, com o objetivo de mitigar os impactos provocados pelos resíduos, possibilitando a produção de carvão ativado. Como alternativa, fez-se a proposição de se utilizar a relação coco/resíduo igual a 100/0, 75/25, 50/50, 25/75 e 0/100, coletando-se os resíduos de laranja, banana, caju e acerola (bagaço e cascas) nos locais apropriados. Para análise imediata foram determinados os teores de cinzas (a 600 ºC) e umidade (a 105 ºC) segundo a norma ASTM D-1762/64, os teores de material volátil (a cinza em mufla a 950 ºC) e de carbono fixo, segundo a norma ASTM D-1762/64, e o poder calorífico, segundo a norma ABNT-NBR 8633/84, dos diversos tratamentos. Os dados obtidos foram submetidos à análise estatística onde foi possível elaborar gráficos que demonstrassem a relação entre as determinações realizadas, indicando a mistura da fibra-de-coco com acerola e com banana a mais promissora.