Due to the increasing usage of Sn in different electronics, such as solders and in touchscreens, together with Boliden Rönnskärs increased intake of electronic waste as a secondaryraw material, a Zn-containing product called Zn-clinker has increasing amounts of Sn. TheZn-clinker is shipped to Boliden Zn-smelter in Odda, where the Zn-clinker is mixed in withcalcine (roasted concentrate) and leached in several steps. Since Zn-clinker is a product froma halogen removal in a clinker-furnace, the feed material (Mixed Oxide), for this furnace, wasalso investigated since there are plans to replace clinkering with soda-washing in the future.Most of the Sn ends up in the leaching residue which then is deposited in the mountaincaverns close by the Boliden Odda smelter. Boliden is studying the possibility to recoverPb/Ag and Sn content from the leaching residue and create a valuable by-product. Bystudying how the leaching of Sn behaves, together with a characterization of the materials, thefollowing question should be answered: “During which sulphuric acid leaching conditions, ofZn-clinker and Mixed Oxide, is the leaching of Sn minimized?” The leaching results for Zn-clinker showed that 8-10% Sn will leach out, despite changingtemperature, redox potential, time and pH. A characterization of the material with SEM-EDSand XRD-analysis was also conducted to see if Sn could be identified in any phases in thematerials. The studies provided enough evidence that Zn2SnO4 could be concluded to be themain phase in the leaching residue for Zn-clinker, a form that would not leach underconditions presented in this project. However, 8-10% of the Sn will come together with Feand when Fe leach out, so does Sn. The leaching results for Mixed Oxide pointed towards that different phases from them foundin Zn-clinker was present. Sn losses varied between 10-20% but raised to 47% whentemperature was changed to 80 °C during leaching. The SEM-EDS analysis showed that theidentified Sn-phases contained more Sn than in Zn-clinker and together with the leachingresults, a conclusion that Sn would mainly be found as SnO2 or SnO in the Mixed Oxide, butthere is still uncertainty about the distributions of these forms. Unfortunately half of the As leached out during the soda-washing for Mixed Oxide, creating aleachate with Cl, F and As that need to be taken care of. This could be challenging andpresenting a costly side-project for the route different from the Zn-clinker route used today.Another observation was that PbCO3 formed during the soda-washing, a phase that willconsume more sulphuric acid during leaching.

Made available in DSpace on 2014-10-09T12:26:43Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:06:18Z (GMT). No. of bitstreams: 0 / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Made available in DSpace on 2014-10-09T12:51:44Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:08:36Z (GMT). No. of bitstreams: 0 / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP

Made available in DSpace on 2014-10-09T12:26:43Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:06:18Z (GMT). No. of bitstreams: 0 / A avaliação dos sistemas de fornecimento de energia para o futuro é da maior importância para se obter informações sobre o potencial de impacto ambiental dos vários estágios do ciclo de vida das tecnologias inovadoras, determinando as vantagens competitivas sobre as tecnologias convencionais e para o desenvolvimento de cenários futuros. Este trabalho apresenta e caracteriza os tipos de pilhas combustíveis de média e baixa temperatura mais pesquisadas e comercializadas nos últimos anos. Realiza-se também a apresentação da avaliação do impacto ambiental dos principais materiais utilizados nas pilhas a combustível, considerando as fases de fabricação, operação e disposição final após o término da vida útil. São apresentados vários dados de LCA (Life Cycle Assessment) efetuados para alguns tipos de pilhas. O trabalho efetuou uma contribuição ao estudo da avaliação de impacto ambiental das pilhas a combustível de média e baixa temperatura utilizando a metodologia Delphi. Foi construído um questionário e um banco de dados para formação do conjunto de respondentes que participaram da pesquisa. Eles receberam o questionário na primeira rodada e o responderam. Depois receberam novamente o questionário em conjunto com as respostas obtidas na primeira etapa, para nova rodada de respostas. Ao final o estudo verifica se ocorreu aumento de consenso e a influência dos respondentes mais qualificados sobre os menos qualificados. Os resultados mostraram que os respondentes acreditam numa redução do impacto ambiental das pilhas. O mais surpreendente é que os respondentes acreditam que os catalisadores do grupo PGM Podem ser substituídos. / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Made available in DSpace on 2014-10-09T12:51:44Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:08:36Z (GMT). No. of bitstreams: 0 / Investiga-se a influência de diferentes tratamentos sobre o sistema alumínio com cobertura de óxido de alumínio. A anodização do alumínio em meio de ácido sulfúrico e meio misto de sulfúrico e fosfórico foi empregada para alterar a resistência à corrosão, a espessura, o grau de cobertura e a microdureza do óxido anódico; e a eletrodeposição de ferro no interior óxido anódico em meio de sulfato com tratamento químico de selagem com cério, para alterar a sua condutividade elétrica e a sua resistência à corrosão. Para a eletrodeposição de ferro aplicou-se corrente contínua e pulsada e diversificou-se a composição do eletrólito de Fe(SO4)2(NH4)2.6H2O, com a adição dos ácidos bórico e ascórbico e para o tratamento de selagem, variou-se a concentração do CeCl3. A espectroscopia de energia dispersiva de raios X (EDS), a fluorescência de raios X (FRX) e a análise morfológica por microscopia eletrônica de varredura (MEV) permitiram verificar que, a corrente pulsada eleva o teor de ferro na camada anódica e a presença dos aditivos inibe a oxidação do ferro. As curvas cronopotenciométricas obtidas durante a eletrodeposição de ferro indicaram que a mistura dos ácidos bórico e ascórbico aumentaram a eficiência do processo de eletrodeposição. A espectroscopia de impedância eletroquímica (EIE), medidas de microdureza Vickers (H) e análise morfológica evidenciaram que o tratamento de selagem melhora a resistência à corrosão do filme óxido modificado com ferro. As medidas de impedância elétrica por duas pontas permitiram comprovar o aumento da condutividade elétrica do alumínio anodizado com ferro, mesmo após o tratamento com baixas concentrações de cério. Nanofios de ferro foram preparados utilizando os poros do óxido anódico como matriz. / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP

Non-oxidative acid leaching of pyrrhotite from Kevitsa’s Ni-concentrate and methods to recover by-products, have been investigated. Selective dissolution of pyrrhotite (Fe1-xS, 0<x<0.25) can enrich the content of the valuable metals, such as Ni and Co, in the final concentrate and will reduce the amount of Fe and S sent to the smelters. The pyrometallurgical smelting of leached concentrate will thus give less formation of smelter by-products in form of slag and SO2. The leaching was studied through an experimental design plan with parameter settings of  38.8% to 57.8% H2SO4 and temperatures from 60 to 100°C. The best results were obtained in experiments carried out at the lower experimental range. Leaching at 60°C with an initial acid concentration of 38.8% H2SO4 was found sufficient to selectively dissolve most of the pyrrhotite; leaving an enriched solid residue. A QEMSCAN analysis of the solid residue confirmed that most of the pyrrhotite had been dissolved and showed that pentlandite was still the main Ni-mineral. Chemical assays showed that more than 95% of the Ni, Co, and Cu remained in the final residue.    The utilized leaching process generates by-products, in the form of large quantities of Fe2+ in solution and gaseous H2S. To recover Fe2+, crystallization of iron(ii) sulfate (FeSO4∙nH2O) from leach solution through cooling have been studied. The crystallized crystals were further dehydrated into the monohydrate (FeSO4∙H2O) through a strong sulfuric acid treatment (80%H2SO4). XRD analysis confirmed that FeSO4∙H2O was the main phase in the final crystals, and a chemical analysis showed a Fe content of about 30%, 1.5% Mg, 0.4% Ca, and 0.2% Ni.    The possibility to leach the concentrate by circulating the acidic solution from the crystallization stage has been tested. The recirculation of the solution showed no negative effects, as the recoveries of elements and chemical assays of the final solid residue were found to be similar to the obtained assay when the concentrate was leached in a fresh solution. / Icke-oxidativ syralakning av magnetkis från Kevitsas Ni-koncentrat har studerats samt metoder för tillvaratagande av biprodukter. Genom en selektiv upplösning av magnetkis (Fe1-xS, 0<x<0.25) kan värdefulla metaller som Ni och Co anrikas i det slutliga koncentratet. Samtidigt som mängden Fe och S som skickas till smältverken minskar, vilket också innebär att mindre biprodukter i form av slagg och SO2 erhålls vid den pyrometallurgiska smältningen av Ni-koncentratet. En experimentell design plan genomfördes för att studera lakningen där syrakoncentrationen varierades från 38.8% till 57.8%H2SO4 och temperatur från 60 till 100°C. Bäst resultat erhölls vid de lägre parameterinställningarna. Lakning vid 60°C med en initial syrakoncentration på 38.8%H2SO4 visade sig vara tillräcklig för att selektivt lösa upp merparten av all magnetkis och lämna kvar en anrikad produkt. Via QUEMSCAN bekräftades att merparten av all magnetkis hade löst upp sig och att huvudsakligt Ni-mineral fortfarande var pentlandit. Kemiska analyser visade att mer än 95% av Ni, Co och Cu stannade kvar i fasta godset.    Den tillämpade lakningsmetoden genererar biprodukter i form av stora mängder Fe2+ i lösning och H2S i gasform. För att tillvarata Fe2+ har kristallisering av laklösning som järn(ii) sulfat (FeSO4∙nH2O) studerats genom kylning. De kristalliserade kristallerna avvattnades till monohydrat, FeSO∙1H2O, genom avvattning i stark svavelsyra (80%H2SO4). XRD bekräftade FeSO∙1H2O som huvudfas i slutliga kristallerna och kemisk analys visade på ca 30%Fe med huvudsakliga orenheter i form av 1.5% Mg, 0.4%Ca och 0.2% Ni.    Möjligheten till att laka i återcirkulerad lösning efter kristallisering har undersökts. Lakning i återcirkulerad lösning visade inga negativa effekter då liknande halter och utbyten erhölls till det fasta godset.

Im Oktober 1875 erschien Clemens Winklers Schlüsselpublikation zum Schwefelsäure-Kontaktverfahren. Der Freiberger Chemiker lieferte nicht nur die wesentlichen Grundlagen des Prozesses, sondern initiierte eine Entwicklung, die der chemischen Industrie ein modernes Produktionsverfahren für eine wichtige Grundchemikalie in die Hand gab und damit ihre Entwicklung entscheidend beförderte. Neben Winklers Leistungen werden auch die bisher wenig gewürdigten Anstrengungen der Freiberger Hüttenwerke herausgestellt, denen es nach einigen Umwegen 1879 gelungen war, die erste wirklich funktionsfähige Kontaktanlage in Betrieb zu nehmen.

A modified two-element membrane pressure vessel assembly has been used to monitor process operational changes in a full-scale reverse osmosis (RO) water treatment plant (WTP). This study evaluated the effectiveness of the assembly as an on-line monitoring device intended to detect scale formation conditions when connected to an operating RO process train. This study was implemented to support the requirements of a larger University of Central Florida (UCF) research project ongoing at the city of Sarasota’s Public Works and Utilities (City) water treatment facilities located in Sarasota, Florida. During the time-frame of this study, the City was in the process of eliminating their sulfuric acid feed from the pretreatment system of their existing 4.5 million gallon per day (MGD) RO membrane process. The City was motivated to eliminate its dependence on sulfuric acid to reduce operating costs as well as reduce operation health and safety risks associated with the use of the acid as a pretreatment chemical. Because the City was concerned with secondary process impacts associated with acid elimination, additional measures were desired in order to protect the full-scale process. This thesis reports on the design, fabrication and installation of a third-stage two membrane element pressure vessel “canary” sentinel monitoring device (Canary), its effectiveness as an online scaling monitor during full-scale acid elimination, and presents the results of the study. The Canary sentinel device was controlled using the normalized specific flux of the two membrane elements fed by a portion of the second stage concentrate of one of the City’s full-scale RO process skids. Although the Canary demonstrated the ability to detect changes in an RO process operation, scaling did not occur under the conditions evaluated in this study. An autopsy of one iv of the Canary elements revealed that no scaling had occurred during the acid elimination process. Therefore, the Canary was found to be useful in its function as a sentinel, even though no scaling was detected by the device after acid elimination at the City’s full-scale plant had been accomplished.

Red muds are non-recyclable wastes formed after bauxite processing, occupy significant areas and are environmentally hazardous. At the same time, red mud contains a large number of valuable components - rare earth metals, iron and titanium. The thesis analyzes the existing technologies for processing red mud and the effectiveness of existing methods for extracting valuable components from red mud. The aim of the study was to study the leaching of red mud in sulfuric acid in order to extract iron into a solution and concentrate titanium in an insoluble residue. As a result of the work, optimal leaching conditions were established, ensuring removal of iron from red mud by 80% and concentrating up to 70% of titanium in an insoluble residue. / Красные шламы представляют собой неутилизируемые отходы, образующиеся после переработки бокситов, занимают значительные площади и являются экологически опасными. В тоже время в красном шламе содержится большое количество ценных компонентов - редкоземельные металлы, железо и титан. В диссертации проанализированы существующие технологии переработки красного шлама и эффективность существующих методов извлечения ценных компонентов из красных шламов. Целью работы являлось исследование выщелачивания красного шлама в серной кислоте с целью извлечения железа в раствор и концентрирования титана в нерастворимом остатке. В результате проведенной работы были установлены оптимальные условия выщелачивания, обеспечивающие извлечение из красного шлама железа на 80% и коцентрирование до 70 % титана в нерастворимом остатке.

Cellulose nanocrystals (CNCs) are frequently prepared by sulfuric acid hydrolysis of a purified cellulose starting material. CNC yields, however, are generally low, often below 20%. This study employs response surface methodology to optimize the hydrolysis conditions for maximum CNC yield. Two experimental designs were tested and compared: the central composite design (CCD) and the Box–Behnken design (BBD). The three factors for the experimental design were acid concentration, hydrolysis temperature, and hydrolysis time. The responses quantified were CNC yield, sulfate group density, ζ-potential, z-average diameter, and Peak 1 value. The CCD proved suboptimal for this purpose because of the extreme reaction conditions at some of its corners, specifically (1,1,1) and (–1,–1, –1). Both models predicted maximum CNC yields in excess of 65% at similar sulfuric acid concentrations (~59 wt %) and hydrolysis temperatures (~65 °C). With the BBD, the hydrolysis temperature for maximum yield lay slightly outside the design space. All three factors were statistically significant for CNC yield with the CCD, whereas with the BBD, the hydrolysis time in the range 60–150 min was statistically insignificant. With both designs, the sulfate group density was a linear function of the acid concentration and hydrolysis temperature and maximal at the highest acid concentration and hydrolysis temperature of the design space. Both designs showed the hydrolysis time to be statistically insignificant for the ζ-potential of CNCs and yielded potentially data-overfitting regression models. With the BBD, the acid concentration significantly affected both the z-average diameter and Peak 1 value of CNCs. However, whereas the z-average diameter was more strongly affected by the hydrolysis temperature than the hydrolysis time, the Peak 1 value was more strongly affected by the hydrolysis time. The CCD did not yield a valid regression model for the Peak 1 data and a potentially data-overfitting model for the z-average diameter data. A future optimization study should use the BBD but slightly higher hydrolysis temperatures and shorter hydrolysis times than used with the BBD in this study (45–65 °C and 60–150 min, respectively). / Master of Science