La Nouvelle-Calédonie détient d’importantes réserves de nickel latéritique et est devenue, en 2017, le cinquième producteur mondial de Ni. Ces dépôts sont habituellement considérés comme résultant d’altération latéritique intense de la péridotite, qui constitue la principale source de nickel. Ainsi, le principal modèle conceptuel de la formation des minerais de nickel latéritique en Nouvelle-Calédonie est un modèle per descensum où la plupart des éléments (Mg, Ni et Si) ont été lessivés depuis la surface, en particulier lors du développement du sol latéritique. Le nickel est ensuite reprécipité, soit dans la goethite de la latérite fine, soit au niveau de la saprolite, sous forme de goethite et de silicates Mg-Ni, dont des talc-like ou kérolite. Les observations minéralogiques et structurales récentes ainsi que les données minières ont cependant mis en évidence de nombreux types d’hétérogénéités dans les concentrations, et la distribution des porteurs de Ni. Comprendre les facteurs la mobilité de cet élément, ses mécanismes de piégeage ainsi que les paramètres chimiques et hydrodynamiques à l’origine de ce piégeage, est essentiel afin de prévoir la distribution du nickel dans les profils latéritiques en Nouvelle-Calédonie, et constitue l’objectif de cette thèse. Ce travail est basé sur le développement (i) d’un modèle 1D s’intéressant en particulier au comportement géochimique du nickel lors de l’altération de l’ophiolite, sa comparaison avec les observations in situ et une compréhension détaillée de la mobilité des éléments traces pendant le processus, et (ii) d’un modèle 2D hydro-géochimique couplé avec l’hydrodynamique complexe des profils latéritiques, améliorant ainsi la connaissance du contrôle structural sur la redistribution et la minéralisation du nickel. Tandis que les simulations 1D permettent de mieux comprendre les aspects chimiques contrôlant les processus de rétention du nickel au sein d’un profil, le modèle 2D se révèle être un outil puissant pour la compréhension de la formation des dépôts locaux les plus riches en nickel. Les résultats du modèle 2D montrent une remobilisation du nickel depuis les horizons supérieurs puis sa reprécipitation sous forme de silicates dans la saprolite. Le nickel remobilisé provient principalement de la zone saprolitique à cause de la dissolution des silicates de nickel formés précédemment ainsi que de l’olivine résiduelle de cette zone. Ce modèle a également révélé que l’horizon latéritique (et en particulier les oxy- hydroxydes de nickel) avait un faible impact dans la remobilisation du nickel. L’infiltration latérale de l’eau contenant le nickel dissout issu des formations surincombantes est à l’origine de la formation des zones les plus riches dans les parties inférieures du profil. Cette redistribution est entièrement contrôlée par l’hydrodynamique locale, la topographie ainsi que l’orientation et la position des fractures. Les modèles présentés permettent d’expliquer les processus de formation des minerais de nickel latéritique saprolitique, améliorant ainsi la compréhension des paramètres contrôlant la mobilité des éléments traces dans un environnement ultramafique. Ceci donne une nouvelle clé de distribution du nickel dans les profils actuels, qui peut devenir un outil pour la prospection minière, et la recherche de nouvelles ressources exploitables / New Caledonia hosts significant lateritic nickel reserves, and presently became the fifth largest Ni producer in the world. These deposits are generally thought to be closely as- sociated with the intense chemical and mechanical weathering of peridotite bedrock that is a principal source of nickel. Thus, the main ore genesis model for Ni ores in New Caledonia is based on a single per descensum model where most elements (Mg, Ni, and Si) are leached from the surface, particularly, during lateritic soil development. Nickel is then concentrated either in the fine-grained laterite where goethite is the main Ni bearer, the so-called ’lateritic ore’, or below the laterites, in the saprolite level, where nickel occurs as goethite and several types of Mg-Ni silicates, in particular kerolite. Recent mineralogical and structural observations together with mining data have revealed a lot of different types of heterogeneities associated with the distribution and mineralogy of Ni bearing minerals. Therefore, in depth investigations of Ni mobility, its retardation processes along with its governing chemical and hydrodynamic parameters are of big importance for understanding and subsequent prediction of Ni distribution in profiles of New Caledonia. Such an investigation is an objective of the present work. The concept is based on the development of i) a powerful 1D model with particular emphasis on Ni geochemical behavior during ophiolite weathering, its comparison with in situ observations, and detailed understanding of trace elements mobility, and ii) 2D hydro-geochemical model coupled with complex hydrodynamics, that would additionally provide new insight into the structural control on Ni redistribution and mineralization. While the 1D simulations provide a remarkable result for understanding the chemical features that drive Ni retention processes in a profile, 2D model appears to be a powerful tool for understanding how local Ni-enrichments may form. The results of this model show the reactivation of Ni from upper horizons and its concentration in neo-formed silicates in bottom of the saprolite. The reactivated Ni comes mostly from the saprolite horizon due to the redissolution of previously formed Ni-bearing silicates and still persisting in this olivine zone. Modeling has revealed minor contribution of the laterite horizon (Ni-oxi-hydroxides) into the Ni remobilization. The lateral infiltration of water with remobilized Ni from areas such as topographic highs to downstream slope areas leads to the formation of richest deposits in this lower part of profile. The manner of redistribution is fully governed by the topographic slopes, orientation and position of the fractures. Presented models appear to be of importance in attempt of explanation of Ni mineralization processes, revealing the main keys to understanding the control of trace elements mobility in ultramafic environment. The latter gives new insights into the Ni distribution in present day profiles and, therefore, may greatly help in mineral prospecting and forecasting the distribution of future resources

Arsenic (As) contaminated groundwater has been a major concern due to the negative impacts to exposed people. This research was conducted to assess and compare the removal efficiency of As from groundwater by laterite, sand, and ash. The experiment was carried out in 14 days in a household scale in Son Dong commune, Hoai Duc district, Ha Noi. Groundwater was pumped directly from a well and flowed through 20 cm (diameter) x 80 cm (length) columns. The initial As concentration in groundwater was 526 μg/L decreasing to an average of 189, 192 and 154 μg/L after being filtrated using sand, ash, and laterite, respectively. Average removal efficiency of sand, ash and laterite during the experiment was 63.3, 63.9, and 70.5%, respectively. Laterite had higher As removal efficiency may be due to higher content of goethite and kaolinite in this sorbent which resulted in better adsorption of As. The concentrations of As in the outflow water were higher than the allowable limit set by the national technical regulation on drinking water quality (QCVN 01:2009/BYT). Therefore, it requires higher volume of sorbents or additional treatment technologies for removal of As from groundwater. / Ô nhiễm asen (As) trong nước ngầm hiện nay là một vấn đề cấp bách đối với xã hội bởi những rủi ro tiềm ẩn với sức khoẻ con người. Nghiên cứu được thực hiện nhằm đánh giá và so sánh khả năng hấp phụ As trong nước ngầm của đá ong, cát và tro. Thí nghiệm được tiến hành trong vòng 14 ngày đặt tại một hộ gia đình có nguồn nước ngầm bị ô nhiễm As thuộc xã Sơn Đồng, huyện Hoài Đức, Hà Nội. Nước ngầm được bơm từ giếng và chảy qua các cột đựng vật liệu có đường kính và chiều dài lần lượt là 20 cm và 80 cm. Nồng độ As ban đầu là 526 μg/L đã giảm xuống còn 189, 192 và 154 μg/L sau khi lọc bằng cát, tro và đá ong. Hiệu suất xử lý As trung bình của cát, tro và đá ong lần lượt là 63,3, 63,9 và 70,5 μg/L. Đá ong xử lý As tốt hơn có thể do hàm lượng goethit và kaolinit cao hơn trong vật liệu hấp phụ này dẫn đến khả năng hấp phụ As tốt hơn. Tuy nhiên hàm lượng As trong nước đầu ra vẫn chưa đạt quy chuẩn cho nước uống (QCVN 01:2009/BYT). Do đó, cần tăng thêm lượng vật liệu hoặc kết hợp với các phương pháp khác để xử lý As hiệu quả hơn.

This study was carried out to evaluate the sorption capacity of Pb, As, Cd, Zn, and Mn by laterite from Tam Duong District (Vinh Phuc Province) and Thach That District (Hanoi City). Laterite samples were exposed to different initial concentrations of heavy metals in solutions (2.5, 5.0, 10, 20, and 50 mg/l) at pH = 5.5 during 24 hours. The results demonstrated that sorption capacity of heavy metals was in the following order: Pb> As> Cd> Zn>Mn. The highest sorption capacity of Pb, As, Cd, Zn, and Mn of laterite from Tam Duong was 1553, 756, 397, 281, and 143 mg/kg, respectively and the highest removal efficiency was 94, 76, 70, 56 and 37%. The results indicated that laterite from Tam Duong District showed lower sorption capacity than that from Thach That District. The disparity sorption capacity of Pb, As, Cd, Zn, Mn between laterite from Thach That and Tam Duong was 10.3–11.6, 11.9–17.9, 11.5–13.7, 9.5–17.6, and 11.1–14.3%, respectively. Laterites from Tam Duong and Thach That are a promising environmental material which can be used in the removal of heavy metals from wastewater. / Nghiên cứu này được thực hiện nhằm đánh giá khả năng hấp phụ Pb, As, Cd, Zn, và Mn bởi laterit đá ong khu vực huyện Tam Dương (Vĩnh Phúc) và huyện Thạch Thất (Hà Nội). Mẫu đá ong được tiến hành thí nghiệm trong các dung dịch có hàm lượng kim loại nặng ban đầu khác nhau (2,5; 5,0; 10; 20 và 50 mg/l) tại pH=5,5 trong 24 giờ. Kết quả nghiên cứu cho thấy mức độ hấp phụ kim loại nặng bởi laterit đá ong lần lượt là Pb> As> Cd> Zn>Mn. Dung lượng hấp phụ Pb, As, Cd, Zn và Mn cao nhất của laterit Tam Dương lần lượt là 1553, 756, 397, 281 và 143 mg/kg và hiệu suất hấp phụ cao nhất lần lượt là 94, 76, 70, 56 và 37%. Dung lượng hấp phụ kim loại nặng của laterit huyện Tam Dương thấp hơn khu vực huyện Thạch Thất. Sự chênh lệch về dung lượng hấp phụ Pb, As, Cd, Zn và Mn giữa laterit Thạch Thất và laterit Tam Dương lần lượt là 10,3–11,6; 11,9–17,9; 11,5– 13,7; 9,5–17,6 và 11,1–14,3%. Kết quả nghiên cứu bước đầu cho thấy đá ong khu vực huyện Tam Dương và Thạch Thất là vật liệu hấp phụ tiềm năng phục vụ ứng dụng trong xử lý nước thải bị nhiễm kim loại nặng.

A fundamental theoretical and experimental study on calcium sulphate scale formation in hydrometallurgical solutions containing various minerals was conducted. A new database for the Mixed Solvent Electrolyte (MSE) model of the OLI Systems® software was developed through fitting of existing literature data such as mean activity, heat capacity and solubility data in simple binary and ternary systems. Moreover, a number of experiments were conducted to investigate the chemistry of calcium sulphate hydrates in laterite pressure acid leach (PAL) solutions, containing Al2(SO4)3, MgSO4, NiSO4, H2SO4, and NaCl at 25–250ºC. The database developed, utilized by the MSE model, was shown to accurately predict the solubilities of all calcium sulphate hydrates (and hence, predict scaling potential) in various multicomponent hydrometallurgical solutions including neutralized zinc sulphate leach solutions, nickel sulphate–chloride solutions of the Voisey’s Bay plant, and laterite PAL solutions over a wide temperature range (25–250°C). The stability regions of CaSO4 hydrates (gypsum, hemihydrate and anhydrite) depend on solution conditions, i.e., temperature, pH and concentration of ions present. The transformation between CaSO4 hydrates is one of the common causes of scale formation. A systematic study was carried out to investigate the effect of various parameters including temperature, acidity, seeding, and presence of sulphate/chloride salts on the transformation kinetics. Based on the results obtained, a mechanism for the gypsum–anhydrite transformation below 100°C was proposed. A number of solutions for mitigating calcium sulphate scaling problems throughout the processing circuits were recommended: (1) operating autoclaves under slightly more acidic conditions (~0.3–0.5 M acid); (2) mixing recycled process solutions with seawater; and (3) mixing the recycling stream with carbonate compounds to reject calcium as calcium carbonate. Furthermore, aging process solutions, saturated with gypsum, with anhydrite seeds at moderate temperatures (~80°C) would decrease the calcium content, provided that the solution is slightly acidic.

A fundamental theoretical and experimental study on calcium sulphate scale formation in hydrometallurgical solutions containing various minerals was conducted. A new database for the Mixed Solvent Electrolyte (MSE) model of the OLI Systems® software was developed through fitting of existing literature data such as mean activity, heat capacity and solubility data in simple binary and ternary systems. Moreover, a number of experiments were conducted to investigate the chemistry of calcium sulphate hydrates in laterite pressure acid leach (PAL) solutions, containing Al2(SO4)3, MgSO4, NiSO4, H2SO4, and NaCl at 25–250ºC. The database developed, utilized by the MSE model, was shown to accurately predict the solubilities of all calcium sulphate hydrates (and hence, predict scaling potential) in various multicomponent hydrometallurgical solutions including neutralized zinc sulphate leach solutions, nickel sulphate–chloride solutions of the Voisey’s Bay plant, and laterite PAL solutions over a wide temperature range (25–250°C). The stability regions of CaSO4 hydrates (gypsum, hemihydrate and anhydrite) depend on solution conditions, i.e., temperature, pH and concentration of ions present. The transformation between CaSO4 hydrates is one of the common causes of scale formation. A systematic study was carried out to investigate the effect of various parameters including temperature, acidity, seeding, and presence of sulphate/chloride salts on the transformation kinetics. Based on the results obtained, a mechanism for the gypsum–anhydrite transformation below 100°C was proposed. A number of solutions for mitigating calcium sulphate scaling problems throughout the processing circuits were recommended: (1) operating autoclaves under slightly more acidic conditions (~0.3–0.5 M acid); (2) mixing recycled process solutions with seawater; and (3) mixing the recycling stream with carbonate compounds to reject calcium as calcium carbonate. Furthermore, aging process solutions, saturated with gypsum, with anhydrite seeds at moderate temperatures (~80°C) would decrease the calcium content, provided that the solution is slightly acidic.

Les travaux présentés dans ce mémoire sont principalement consacrés à l’étude des processus d’adsorption des ions phosphate par des matériaux naturels de Côte d’Ivoire : le schiste ardoisier; le grès et la latérite. L’objectif final est une application de ces matériaux comme massifs filtrants de marais artificiels pour la déphosphatation des ERU (Eaux Résiduaires Urbaines (ERU)). Dans un premier temps, la réactivité des ions phosphate a été abordée vis-à-vis du schiste en réacteurs « batch » et colonne. L’influence de différents paramètres physicochimiques a été caractérisée. La capacité d’adsorption diminue avec la dose de schiste qui augmente. Elle dépend du pH et diminue lorsque celui-ci augmente dans la gamme 2-11 puis ré-augmente au-delà. Une corrélation entre concentration aqueuse en ions calcium, magnésium, aluminium et fer issus de la dissolution du schiste et concentration en ions phosphate en solution a été établie. Une cinétique de pseudo-second ordre a été mise en évidence et les isothermes ont été décrites à partir du modèle de Langmuir. Les expériences réalisées en réacteur colonne, pour une concentration initiale en ions phosphate de 25 mg L-1 et à un débit de 0,23 ml min-1 présentent une percée à V/Vp = 17 correspondant à une capacité de sorption de 0,2 mg g-1en accord avec les expériences en réacteur « batch ». Un réacteur micro-pilote de type marais artificiel à écoulement vertical saturé garni de schiste ardoisier a été développé et les performances vis-à-vis des ions phosphates, de l’azote, des MES (Matières En Suspension) et de la matière organique ont été évaluées. L’influence de la granulométrie du massif filtrant et de la densité de culture du panicum maximum sur la performance de ce micro-pilote a été établie. Le filtre de schiste de granulométrie la plus fine présente une performance épuratoire légèrement supérieure. Le débit d’infiltration dans les filtres diminue après traitement de l’ERU et le taux de colmatage est moins élevé pour les filtres plantés. La densité de culture la plus élevée conduit à une performance épuratoire légèrement plus favorable. La capacité d’adsorption des ions phosphates liée aux plantes seules est faible, confirmant l’importance du choix du massif filtrant. La réactivité des ions phosphate a été finalement étudiée vis-à-vis du grès et de la latérite en réacteurs « batch » et colonne. Le statut du fer, en substitution dans des argiles pour le schiste et sous forme d’hématite et goethite dans la latérite et le grès influence la réactivité du matériau. L’ordre d’efficacité des adsorbants a été établi comme suit : latérite ≥ grès ≥ schiste. Ces trois matériaux offrent des perspectives intéressantes en tant que massifs filtrants de marais à flux vertical saturé / This thesis is devoted to the study of phosphate ions adsorption processes by natural minerals of Ivory Coast, i.e. shale, sandstone and laterite mainly. Phosphate sorption by shale was first investigated in batch and column experiments. Batch experiments allowed the assessment of the influence of initial phosphate concentration, sorbent dosage, contact time, and pH on phosphate removal. The phosphate removal efficiency increased with increasing shale dosage while phosphate uptake decreased. Phosphate uptake strongly depended on pH, decreasing first with increasing pH in the range of 2-11 and then increasing at the highest pH value of 12. A correlation between aqueous Ca, Mg, Al, and Fe concentrations and phosphate uptake was observed. The kinetics was well described using the pseudo-second order model and isotherms with Langmuir sorption model. Column experiments with a flow rate of 1 ml min-1 and 25 mg L-1 initial phosphate concentration showed a breakthrough point at V/Vp of ~17 corresponding to a phosphate uptake of 0.2 mg g-1 in agreement with batch experiments. The performance of shale was evaluated as filter material in (Vertical Flow Constructed Wetland) VFCW in removal of phosphate ions, nitrogen, suspended solids, and organic compounds, using municipal wastewater. The influence of both shale granulometry and plants density was evaluated. The shale with the finest particle size offers a slightly higher efficiency. The flow rate decreased after wastewater treatment and the fooling is less pronounced for planted VFCW. The filter with the highest plant density offers only slightly higher efficiency towards phosphate and nitrate removal. The phosphate sorption capacity of the plants is negligible confirming the importance in the choice of the filter medium. Finally, phosphate removal by shale was compared to sandstone and laterite in both batch and column experiments. The different chemical compositions of the materials influence strongly the reactivity towards phosphate ions. It is supposed that the status of iron in the material, i.e. in substitution in clays in shale and occurring as hematite and goethite in laterite and sandstone, explained the differences of reactivity. Both batch and column experiments revealed that phosphate uptake decreased in the following ranking order laterite > sandstone > shale. These three materials appear as promising filter materials in VFCW

Orientador: Francisco Sergio Bernardes Ladeira / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Geociencias / Made available in DSpace on 2018-08-09T09:17:40Z (GMT). No. of bitstreams: 1 Leonardi_FernandaAparecida_M.pdf: 23677977 bytes, checksum: 4c5706f5e614cdc53595822a8c7cceb9 (MD5) Previous issue date: 2007 / Resumo: Muitos trabalhos no âmbito da geomorfologia buscaram associar níveis altimétricos às superfícies de erosão. Partindo-se da teoria de Davis, de topos concordantes ou topos de mesma altitude (uma abordagem clássica baseada em pontos de maior altitude), realiza-se a associação destas superfícies com a ocorrência de perfis bauxíticos, identificando-se assim as antigas superfícies ou paleosuperfícies. Portanto, este trabalho tem como objetivo principal correlacionar as superfícies geomórficas com os perfis de alteração, no caso, os Perfis Lateríticos-Bauxíticos, utilizando-se destes como marcos estratigráficos. A partir do trabalho de campo, no Planalto de Poços de Caldas encontrou-se três tipos de Perfis Bauxíticos: de Serra, de Campo e Retrabalhados. Os Perfis de Serra são mais espessos que os Perfis de Campo, com maior teor de alumínio e menor teor de sílica, indicando que provavelmente se formaram no topo, onde a drenagem permitiu uma maior lixiviação e concentração de alumínio. O que diferencia um Perfil de Serra do de Campo é uma camada de argila existente entre a rocha e a bauxita. Esta camada de argila não possui estruturas da rocha e é bastante homogênea, enquanto, em todo o depósito encontram-se volumes com estrutura concêntrica e sistemas de fraturas preservados do material de origem. Os Perfis Bauxíticos Retrabalhados possuem sua origem nos Perfis de Serra, pois nestes materiais a concentração de alumínio é elevada e a de sílica é baixa. Ao correlacionar os Perfis Bauxíticos, com as prováveis superfícies geomórficas, segundo a altimetria, percebe-se que não há uma ordem, os perfis estão distribuídos aleatoriamente nas bordas e no interior da área, em diferentes patamares do relevo, onde especialmente observa-se a ocorrência de Perfis Bauxíticos de Serra posicionados em altimetrias de Perfis de Campo e Perfis Retrabalhados posicionados sobre Perfis de Serra, acima dos 1.400 metros. O controle estrutural observado em campo, na literatura e nas cartas topográficas nos mostra zonas de falhas comuns, podendo-se associar esta descontinuidade do perfil bauxítico com essas movimentações. Uma das evidências mais claras são os padrões de drenagem que são preferencialmente controlados pelos alinhamentos estruturais que seccionam o embasamento. Muitas movimentações, provavelmente, ocorreram anteriormente à formação dos perfis bauxíticos, entretanto ocorreu uma reativação das falhas, pois se verificou que as falhas cortam os materiais associados aos Perfis de Serra, Perfis de Campo e em alguns casos, afetam os níveis de Perfis Retrabalhados, indicando que a atividade tectônica não se restringiu apenas em moldar o quadro (junto com o clima) dos processos erosivos que afetaram os perfis in situ, mas avançou para além dos eventos de formação dos materiais lateríticos depositados / Abstract: Many works in the geomorphology scope have tried to associate the elevation levels with the erosion surfaces. Starting from Davis' accordance tops or similar elevation theory (a classical aproach based in points of higher elevation) it is proposed the association of these surfaces with the occurrence of Bauxite Profiles, identifying the old surfaces or paleosurfaces. Therefore, this work has the main objective of correlating the geomorphic surfaces with the alteration profiles, in this case the Bauxite Laterite Profiles, applying these as statigraphic marks. Through the field work in Poços de Caldas Plateau were found three types of Bauxite Profile: Rim, Plateau and Reworked Profiles. The Rim Profiles are thicker than the Plateau Profiles, with bigger amount of aluminium and smaller of silica, indicating that they probably were formed in top, where the drainage allowed a bigger leaching and concentration of aluminium. The aspect that distinguishes a Rim from a Plateau Profile is a clay layer between the rock and the bauxite. This clay layer does not have rock structures and it is rather homogeneous, while, in the whole deposit were found contents with concentrical structure and fractures systems preserved from the material of origin. The Reworked Bauxite Profiles have their origin in Rim Profiles, because in these materials the concentration of aluminium is high and silica is low. Correlating the Bauxite Profiles with the probable geomorphical surfaces, following the altitude, it is not noticed any order, the profiles are distributed at random in the borders and in the inner area, in different levels of relief, where it is specially observed the occurrence of Bauxite Rim Profiles located in elevations of Plateau Profiles, and Reworked Profiles located over Rim Profiles, above 1,400 meters. The structural control observed in field, in literature and in the topographic maps shows zones of common faults, and 0it can associate this discontinuity of the Bauxite Profile with these movements. One of the clearest evidences are the drainage patterns, which are mainly controlled by basement structural alignments. Probably many movements have taken place before the formation of the Bauxite Profiles, however, a reactivation of the faults has ocurred, therefore it was verified that the faults cut the materials associated with Rim Profiles, Plateau Profiles and, specially in some instances, affect the levels of Reworked Profiles, indicating that the tectonic activity did not restrict only in molding the chart (with the climate) of the erosive processes which have affected the profiles ¿in situ¿, but it has advanced farther on the events of formation of the deposited laterite materials / Mestrado / Análise Ambiental e Dinâmica Territorial / Mestre em Geografia

This article presents nano composite TiO2.Fe2O3/laterite materials, which were successfully prepared by hydrometallurgical method. The materials were modified using urea as the nitrogen source. The particles size of the materials is from 20-30 nanometers. The obtained materials can not only absorb arsenic compounds but also enhance the ability of converting As (III) or As (V) into Aso, which is removed from solution. Arsenic removal efficiency of these materials is high. Using sunlight in a hydraulic retention time, about 180 minutes, the arsenic value at the inflow was about 10 mg/L but the outflow was negligible. Covering TiO2.Fe2O3 nano on laterite have brought high economical efficiency, on one hand, it saved material and on the other hand, it can be continuously operated without the centrifugal separation of the nano material. / Bài báo này giới thiệu về phương pháp điều chế vật liệu nano TiO2.Fe2O3 biến tính nitơ được phủtrên đá ong bằng phương pháp thủy luyện. Vật liệu nano thu được có kích thước 20-30 nm. Vật liệu thu được không những có khả năng hấp phụ các hợp chất của asen mà còn có khả năng khử As (III) hoặc As (V) thành Asokhi được chiếu sáng. Sử dụng ánh sáng mặt trời chiếu vào hệ thống xử lý trong thời gian 180 phút có thể loại bỏ được gần như hoàn toàn asen ra khỏi nước mặc dù hàm lượng đầu vào là 10 mg/l. Việc phủ vật liệu TiO2.Fe2O3 nano lên đá ong đã mang lại hiệu quả kinh tế cao, một mặt nó tiết kiệm được vật liệu, mặt khác, vật liệu có thể sử dụng một cách liên tục mà không cần phải tách bằng phương pháp ly tâm.

[pt] A redução por hidrogênio e a decomposição térmica de um minério laterítico saprolítico foram estudadas utilizando a técnica de termogravimetria (TGA). A identificação das fases minerais formadas após o processamento foi feita utilizando as técnicas de difração de raios X (DRX) e microscopia eletrônica de varredura acoplada a espectrômetro de energia dispersiva (MEV/EDS). O produto obtido manteve o níquel aprisionado na estrutura do material e forneceu um baixo índice de extração desse metal (em torno de 3 porcento) na etapa de lixiviação amoniacal. Desta forma, novos experimentos de redução foram conduzidos na presença de diferentes reagentes químicos (Na2CO3, S8 e NaCl) visando a aumentar a solubilidade do níquel. Observou-se que todos os reagentes químicos utilizados viabilizaram o aumento da extração de Ni, sendo o maior deles para os testes utilizando 10 porcento de NaCl. Então, experimentos de redução por hidrogênio e decomposição térmica, do mesmo minério, na presença de NaCl, foram feitos utilizando a técnica de termogravimetria, com as fases minerais e alguns produtos gasosos formados sendo identificados utilizando as técnicas de DRX e MEV/EDS. Tais experimentos e caracterizações sugerem que a presença do NaCl no sistema promove a segregação do níquel, e a sua consequente solubilização posterior, em função da ocorrência das seguintes reações: (1o) Redução do óxido de níquel pelo hidrogênio: NiO + H2(g) → Ni + H2O(g); (2o) Formação de HCl: Al2SiO5 + 2NaCl + SiO2 + H2O(g) à 2HCl(g) + 2NaAlSiO4; (3o) Cloração do níquel metálico pelo HCl: Ni + 2HCl(g) → NiCl2 + H2(g);(4o) Redução do cloreto de níquel pelo hidrogênio: NiCl2 + H2(g) → Ni + 2HCl(g). A influência da temperatura e da porcentagem de NaCl no forno de redução no rendimento da etapa de lixiviação amoniacal foram avaliadas e os resultados mostraram que a presença de apenas 1 porcento de NaCl aumentou os valores de extração para níveis próximos de 90 porcento, quando os experimentos de redução foram conduzidos à temperatura de 850°C. / [en] The reduction by hydrogen and the thermal decomposition of a lateritic saprolite nickel ore were studied using the thermogravimetric technique (TGA). The identification of the mineral phases generated after the processing was carried out using X-ray diffraction (XRD) and scanning electron microscopy coupled to a dispersive energy spectrometer (SEM/EDS) techniques. The reduced ore was leached in amoniacal solution and the low value of nickel extraction (≈3 percent) were attributed to the formation of forsterite and enstatite. Thus reduction test were carried out in the presence of chemicals (Na2CO3, NaCl and S8) and the highest extractions values were found for the tests using 10 percent NaCl. Finally, reduction tests on H2 atmosphere in rotary kiln were performed in the presence of NaCl and the product of the reaction was leached in ammoniacal solution. The presence of only 1 percent of NaCl in the furnace increased the nickel extraction values from ≈3 percent to ≈ 90 percent when the experiment was carried out at 850°C. According to the results of X ray diffractometry (XRD) and thermogravimetric analysis (TGA) the presence of NaCl in the system and the reducing atmosphere of H2 promote the segregation of nickel according to the following steps: 1).. Nickel oxide reduction by hydrogen: NiO + H2(g) → Ni + H2O(g). 2) Formation of HCl: Al2SiO5 + 2NaCl + SiO2 + H2O à 2HCl(g) + 2NaAlSiO4. 3). Chlorination of metallic nickel by HCl: Ni + 2HCl(g) → NiCl2 + H2(g). 4). Reduction of nickel chloride by hydrogen: NiCl2 + H2(g) → Ni + 2HCl(g).

Η επεξεργασία των νικελιούχων λατεριτικών μεταλλευμάτων της χώρας μας για την παραγωγή σιδηρονικέλιου στη Λάρυμνα συνοδεύεται με την εκπομπή 200000t/y λεπτομερούς σκόνης που συλλέγεται στα συστήματα αντιρρύπανσης των περιστροφικών κάμινων (Π/Κ), μέσης περιεκτικότητας 1.2-1.5% σε Ni και 4-5% σε C. Η διατριβή αυτή συνέβαλε στην ανάπτυξη μεθόδου ανακύκλωσης της σκόνης αυτής με απευθείας αναγωγική της τήξη σε ηλεκτρική κάμινο συννεχούς ρεύματος (DC-HEP) με εμφυσησή της μέσω του κεντρικού διάτρητου γραφιτικού ηλκετρόδιου. Την προκαταρκτική θεωρητική διερεύνηση και τις εργαστηριακές προδοκιμές ακολούθησαν βιομηχανικές δοκιμές στην κάμινο 125t DC-HEP στη χαλυβουργία Georgsmarienhutte της Γερμανίας, όπου έλαβε χώρα τήξη 70t σκόνης και 2.5t φιλομερούς μεταλλεύματος.Η ανάκτηση Ni ήταν πολύ υψηλή 93-99%. Παρήχθησαν χάλυβες χαμηλής κραμάτωσης σε σε Ni καθώς και ποικίλοι τύποι σκωρίας προς διερεύνηση της χρήσης τους στην παραγωγή σύνθετων τσιμέντων Portland και σκωριωτσιμέντων. Πραγματοποιήθηκε μεταλλουργική αξιολόγηση των δοκιμών και αναπτύχθηκε μοντέλο προσομοίωσης της αναγωγικής τήξης της σκόνης. / The tratment of the laterite nickel ferrous ores in Hellas for the production of ferronickel at Larymna is associated with the emission of 200000t/y of fine dust collected in the gas cleaning systems of the rotary kilns (R/Ks), with 1.2-1.5% and 4-5% . Average Ni and C contents respectively . This thesis contributed to the development of a method for the recycling of this dust by means of its direct reduction smelting in a DC-HEP furnace (Direct Current-Hollow Electrode Powder) by its injection through the central hollow graphite electrode. The preliminary theoretical study and the laboratory trials were followed by industrial heat campaigns in the 12st DC-HEP furnace at georgsmarienhutte steelwork in Germany, where around 70t of dust and 2.5t of ore fines were smelted. The Ni-recovery was very high 93-99.9%. Low Nickel alloyed steel grades were produced and various slag types for the investigation of their utilization for the production of composite-portland cements and slag cements. The metallurgical evaluation of the trials was performed and model for the dust reduction smelting process was developed.