Liquid phase benzylation of o-xylene over pillared clays

Iron, aluminium and mixed iron aluminium pillared clays have been prepared by partial hydrolysis method and doped with IO% Mo, V and Cr. The samples have been characterised by XRD, FTIR and surface area and pore Volume measurements. The surface acid site distribution has been determined by temperature programmed desorption of ammonia. Vanadia incorporated systems show maximum acidity. Benzylation of o-xylene has been done as probe reaction to test catalytic activity. Benzyl chloride is a superior benzylating agent compared to benzyl alcohol in activity and selectivity. Cent percent selectivity towards monobenzylated product is obtained in all the cases. Fe pillared systems exhibit maximum activity. The catalytic activities of the systems can be correlated with the amount of strong add sites. The effects of various reaction variables on the reaction have been studied. Presence of moisture has a diminishing effect on the reaction rate.

Wet peroxide oxidation of phenol over mixed pillared montmorillonites

Wet peroxide oxidation (WPO) of phenol is an effective means for the production of diphenols, which are of great industrial importance. An added advantage of this method is the removal of phenol from wastewater effluents. Hydroxylation of phenol occurs efficiently over mixed iron aluminium pillared montmorillonites. An initial induction period is noticed in all cases. A thorough study on the reaction variables suggests free radical mechanism for the reaction.

Characterisation of the acid-base properties of pillared montmorillonites

Iron and mixed iron aluminium pillared montrnorillonites prepared by partial hydrolysis method were subjected to room temperature exchange with transition metals of the first series. The resulting materials were characterised by different spectroscopic techniques and surface area measurements. About 1-3% transition metals were incorporated into the porous network. The structural stability of the porous network was not affected by exchange. XRD and AI NMR spectroscopy evidenced the presence of iron substituted Al13 like polymers in FeAl pillared systems. Acidity and basicity benefited much as a result of metal exchange. Acidity and basicity were quantified by model reactions, viz., cumene cracking and cyclohexanol decomposition respectively. The presence of basic sites in otherwise acidic pillared clays, though diminutive in amount can be of much importance in acid base catalysed reactions.

Síntese e caracterização de argilas pilarizadas com pilares mistos Al/Co

Two pillaring methods were tested to synthesize pillared clays containing mixed Al/Co pillars. Using the first method, based on the traditional procedure, were obtained materials containing different Co concentrations: 10, 25, 50, 75 and 100 % of Co in the pillaring solution. Just the experiments with low concentrations (10 and 25 % of Co) has formed pillared clays, whereas the sample with 25 % of cobalt showed best results compared with the one obtained just using Al as pillaring agent (basal spacing higher than 18 Å and surface area bigger than 300 m²/g). The 27Al NMR results pointed out the formation of mixed Al/Co pillars due to decreased between the intensities of AlVI/AlIV signals, indicating that the AlIV content decreased while Co content increased, suggesting the isomorphic substitution of Al atoms for Co in the Keggin ion structure (pillaring agent). For the samples containing 75 and 100 % of cobalt, it was verified the formation of others materials, which could be identified as hydrotalcite like compounds. The second pillarization method was named mixed layers, because the objective was to intercalate clay layers with hydrotalcite layers. Thus, after calcination, the hydrotalcite layers would dehydroxylate, resulting just in the metals oxides, intercalated between the clay sheets, thus generating, a pillared clay. For this purpose, were tested 4 synthesis procedures: physical mixture, mixture in water, ionic exchange under reflux and in situ synthesis. Of these, the method which showed the best results was the in situ synthesis, in which basal spacings of 14 Å (after calcination) were obtained, indicating that the samples are intercalated with metal oxides (Mg and Al). This procedure was reproduced with a Co-Al LDH (layered double hydroxide) and similar results were obtained, testifying the method reproducibility

Aplicação de Al-PILC na adsorção de Cu2+, Ni2+ e Co2+ utilizando modelos físico-químicos de adsorção

Amostra de esmectita pertencente a Serra de Maicuru (Estado do Pará, Norte do Brasil, região amazônica) foi pilarizada com Al₁₃, A Argila pilarizada com alumínio (Al-PILC) foi caracterizada por DRX, MEV e EDS. Para a análise textural foram utilizadas isotermas de adsorção-desorção utilizando o nitrogênio. Este artigo é dirigido ao estudo da adsorção de metais pesados. A adsorção dos íons de Cu²⁺, Ni²⁺e Co²⁺ foi realizadas com a matriz Al-PILC em temperatura ambiente com soluções aquosas contendo os íons metálicos. Os modelos de adsorção adotados foram os de Langmuir, Freundlich e Temkin que foram aplicados aos valores obtidos experimentalmente com regressão linear. A equação de Langmuir foi o melhor modelo de linearização com r = 0,999. A equação de Freundlich apresentou limitações em altas concentrações, mas foram obtidos valores (K_f e n) bastante aceitáveis utilizando este modelo. Os parâmetros foram utilizados para calcular a quantidade de N_f em função de Cs.

Geochemical analysis of bulk sediment and interstitial water of sediment cores from the North-West African continental margin

Molybdenum and vanadium were analysed in 9 scediment cores recovered from the continental slope and rise off NW Africa. Additionall chemical and sedimentological parameters as well as isotope stage boundaries were available for the same core profiles from other investigations. Molybdenum, ranging between <1 and 10 ppm, occurs in two associateions, either with organic carbon and sulphides in sediments with reducing conditions or with Mn oxides in oxidized near-surface core sections. Highest values (between 4 and 10 ppm Mo) are found in sulphide-rich core sections deposited during glacial times in a core from 200 m water depth. The possibility of anoxic near-bottom water conditions prevailing at thhis site during certain glacial intervals is discussed. In oxidized near-surface core sections, the diagenetic mobility of Mo becomes evident from strong Mo enrichment together with Mn oxides (values up to 4 ppm Mo). This enrichment is probably due to coprecipitation and/or adsorption of Mo from interstitial water to the diagenetically forming Mn oxides. The close relation between Mo and Corg results in strongly covarying sedimentation rates in both components reaching up to 10 times the rates in glacial compared to interglacial core sections. Vanadium (values between 20 and 100 ppm) does not show clear relations to climate and near-bottom or sediment milieu. It occurs mainly bound to the fine grained terrigenous fraction, associated with aluminium silicates (clay minerals) and iron oxides. Additionally positive covariation of vanadium with phosphorus in most core profiles suggest that some V may be bound to phosphates.

Incorporación de escorias de aluminio en la fabricación de productos de Arcilla cocida

Las sociedades desarrolladas generan una gran cantidad de residuos, que necesitan una adecuada gestión. Esta problemática requiere, de este modo, una atención creciente por parte de la sociedad, debido a la necesidad de proteger el medio ambiente. En este sentido, los esfuerzos se centran en reducir al máximo la generación de residuos y buscar vías de aprovechamiento de aquellos que son inevitables, soluciones mucho más aconsejables desde el punto de vista técnico, ecológico y económico que su vertido o destrucción. Las industrias deben adoptar las medidas precisas para fomentar la reducción de estos residuos, desarrollar tecnologías limpias que permitan el ahorro de los recursos naturales que poseemos, y sobre todo buscar métodos de reutilización, reciclado, inertización y valorización de los residuos generados en su producción. La industria de la construcción es un campo muy receptivo para el desarrollo de nuevos materiales en los que incorporar estos residuos. La incorporación de diferentes residuos industriales en matrices cerámicas se plantea como una vía barata de fijar las diferentes especies metálicas presentes en transformación de rocas ornamentales, lodos de galvanización o metalúrgicos, etc. En todos los casos, la adición de estos residuos requiere su caracterización previa y la optimización de las condiciones de conformado y cocción en el caso de su incorporación a la arcilla cocida. Entre los residuos incorporados en materiales de construcción se encuentran las escorias de aluminio. La industria metalúrgica produce durante sus procesos de fusión diferentes tipos de escorias. Su reciclado es una de las líneas de interés para estas industrias. En el caso de las escorias de aluminio, su tratamiento inicial consiste en una recuperación del aluminio mediante métodos mecánicos seguido de un tratamiento químico, o plasma. Este método conduce a que la escoria final apenas contenga aluminio y sea rica en sales solubles lo que limita su almacenamiento en escombreras. La escoria es una mezcla de aluminio metal y productos no metálicos como óxidos, nitruros y carburos de aluminio, sales y otros óxidos metálicos. En este estudio se ha analizado la posibilidad de la adición de escorias de aluminio procedentes de la metalurgia secundaria en materiales de construcción, de forma que tras un procesado de las mismas permita la obtención de materiales compuestos de matriz cerámica. En la presente Tesis Doctoral se ha analizado la viabilidad técnica de la incorporación de las escorias de aluminio procedentes de la metalurgia secundaria en una matriz de arcilla cocida. Para ello se han aplicado diferentes tratamientos a la escoria y se han aplicado diferentes variables en su procesado como la energía de molienda o la temperatura de sinterizacion, además del contenido de escoria. Su compactación con agua entre el 5-10 %, secado y sinterización permite obtener piezas rectangulares de diverso tamaño. Desde el punto de vista del contenido de la escoria, se incorporó entre un 10 y 40% de escoria TT, es decir sometida una calcinación previa a 750ºC en aire. Los mejores resultados alcanzados corresponden a un contenido del 20% ESC TT, sinterizada a 980ºC, por cuanto altos contenidos en escoria condicen a piezas con corazón negro. Los productos obtenidos con la adición de 20% de escoria de aluminio a la arcilla, presentan una baja expansión tras sinterización, mejores propiedades físicas y mecánicas, y mayor conductividad térmica que los productos obtenidos con arcilla sin adiciones. Aumenta su densidad, disminuye su absorción y aumenta sus resistencias de flexión y compresión, al presentar una porosidad cerrada y una interacción escoria-matriz. En todos los casos se produce una exudación superficial de aluminio metálico, cuyo volumen está relacionado con la cantidad de escoria adicionada. Mediante la incorporación de este contenido de escoria, tras un tratamiento de disolución de sales y posterior calcinación (ESC TTQ), se mejoran las propiedades del material compuesto, no sólo sobre la de la escoria calcinada (ESC TT), sino también, sobre la escoria sin tratamiento (ESC). Si además, la adición del 20% de escoria añadida, está tratada, no sólo térmicamente sino también químicamente (ESC TTQ), éstas mejoran aún más las propiedades del material compuesto, siendo el producto más compacto, con menos poros, por lo que los valores de densidad son más elevados, menores son las absorciones y mayores resistencias de flexión y compresión, que los productos obtenidos con la adición de escoria sólo tratada térmicamente. Alcanzando valores de resistencias características a compresión del orden de 109 MPa. Los valores de conductividad térmica obtenidos también son mayores. Los ensayos tecnológicos con piezas de 160 x 30 x 5 mm y el material compuesto optimizado de arcilla+ 20%ESCTTQ, consistieron en la determinación de su expansión por humedad, eflorescencia y heladicidad, mostrando en general un mejor comportamiento que la arcilla sin adiciones. Así, se han obtenido nuevos materiales compuestos de matriz cerámica para la construcción, mejorando sus propiedades físicas, mecánicas y térmicas, utilizando escorias de aluminio procedentes de la metalurgia secundaria, como opción de valorización de estos residuos, evitando así, que se viertan a vertederos y contaminen el medio ambiente. ABSTRACT Developed societies generate a lot of waste, which need proper management. Thus, this problem requires increased attention from the society, due to the need to protect the environment. In this regard, efforts are focused on to minimize the generation of waste and find ways of taking advantage of those who are inevitable, much more advisable solutions from the technical, ecological and economic viewpoint to disposal or destruction. Industries should adopt precise measures to promote waste reduction, develop clean technologies that allow the saving of natural resources that we possess, and above all seek methods of reuse, recycling, recovery and valorisation of the waste generated in their production. The industry of the construction is a very receptive field for the development of new materials in which to incorporate these residues. The incorporation of different industrial residues in ceramic counterfoils appears as a cheap route to fix the different metallic present species in transformation of ornamental rocks, muds of galvanization or metallurgical, etc. In all the cases, the addition of these residues needs his previous characterization and the optimization of the conditions of conformed and of baking in case of his incorporation to the baked clay. Residues incorporated into construction materials include aluminium slag. The metallurgical industry produces during their fusion processes different types of slags. Recycling is one of the lines of interest to these industries. In the case of aluminium slag, their initial treatment consists of a recovery of the aluminium using mechanical methods followed by chemical treatment, or plasma. This method leads to that final slag just contains aluminium and is rich in soluble salts which limits storage in dumps. The slag is a mixture of aluminium metal and non-metallic such as oxides, nitrides and carbides of aluminium salts products and other metal oxides. The present Doctoral thesis has analysed the technical viability of the incorporation of aluminium slag from secondary Metallurgy in an array of baked clay. So they have been applied different treatments to the slag and have been applied different variables in its processing as the temperature of sintering, in addition to the content of slag or energy grinding. Its compaction with water between 5-10%, drying and sintering allows rectangular pieces of different size. From the point of view of the content of the slag, it is incorporated between 10 and 40% slag TT, that is to say, submitted a calcination prior to 750 ° C in air. The best results achieved correspond to 20% ESC TT, sintered at 980 ° C, as high levels of slag in accordance to pieces with black heart. The products obtained with the addition of 20% of slag from aluminium to clay, present a low expansion after sintering, better physical properties and mechanical, and higher thermal conductivity than the products obtained with clay, without addictions. Its density increases, decreases its absorption and increases its resistance to bending and compression, introducing a closed porosity and slag-matrix interaction. In all cases there is a superficial exudation of metallic aluminium, whose volume is related to the amount of slag added. By incorporating this content of slag, following a treatment of salt solution and subsequent calcination (ESC TTQ), are improved the properties of composite material not only on the calcined slag (ESC TT), but also in the slag without treatment (ESC). If the addition of 20% of slag added, is also treated, not only thermally but also chemically (ESC TTQ), they further improve the properties of the composite material, the product is more compact, less porous, so the values are higher density, minors are absorptions and greater resistance in bending and compression, to the products obtained with the addition of slag only treated thermally. Reaching values of compressive resistance characteristic of the order of 109 MPa. The thermal conductivity values obtained are also higher. Testing technology with pieces of 160 x 30 x 5 mm and optimized composite material of clay 20% ESCTTQ, consisted in the determination of its expansion by moisture, efflorescence and frost resistance, in general, showing a better performance than the clay without additions. Thus, we have obtained new ceramic matrix composite materials for construction, improving its physical, mechanical and thermal properties, using aluminium slag secondary metallurgy, as an option Valuation of these wastes, thus preventing them from being poured to landfills and pollute environment.

Chemical modification of smectite clays

Today, speciality use organoclays are being developed for an increasingly large number of specific applications. Many of these, including use in cosmetics, polishes, greases and paints, require that the material be free from abrasive impurities so that the product retains a smooth `feel'. The traditional `wet' method preparation of organoclays inherently removes abrasives naturally present in the parent mineral clay, but it is time-consuming and expensive. The primary objective of this thesis was to explore the alternative `dry' method (which is both quicker and cheaper but which provides no refining of the parent clay) as a process, and to examine the nature of the organoclays produced, for the production of a wide range of commercially usable organophilic clays in a facile way. Natural Wyoming bentonite contains two quite different types of silicate surface (that of the clay mineral montmorillonite and that of a quartz impurity) that may interact with the cationic surfactant added in the `dry' process production of organoclays. However, it is oil shale, and not the quartz, that is chiefly responsible for the abrasive nature of the material, although air refinement in combination with the controlled milling of the bentonite as a pretreatment may offer a route to its removal. Ion exchange of Wyoming bentonite with a long chain quaternary ammonium salt using the `dry' process affords a partially exchanged, 69-78%, organoclay, with a monolayer formation of ammonium ions in the interlayer. Excess ion pairs are sorbed on the silicate surfaces of both the clay mineral and the quartz impurity phases. Such surface sorption is enhanced by the presence of very finely divided, super paramagnetic, Fe2O3 or Fe(O)(OH) contaminating the surfaces of the major mineral components. The sorbed material is labile to washing, and induces a measurable shielding of the 29Si nuclei in both clay and quartz phases in the MAS NMR experiment, due to an anisotropic magnetic susceptibility effect. XRD data for humidified samples reveal the interlamellar regions to be strongly hydrophobic, with the by-product sodium chloride being expelled to the external surfaces. Many organic cations will exchange onto a clay. The tetracationic cyclophane, and multipurpose receptor, cyclobis(paraquat-p-phenylene) undergoes ion exchange onto Wyoming bentonite to form a pillared clay with a very regular gallery height. The major plane of the cyclophane is normal to the silicate surfaces, thus allowing the cavity to remain available for complexation. A series of group VI substituted o-dimethoxybenzenes were introduced, and shown to participate in host/guest interactions with the cyclophane. Evidence is given which suggests that the binding of the host structure to a clay substrate offers advantages, not only of transportability and usability but of stability, to the charge-transfer complex which may prove useful in a variety of commercial applications. The fundamental relationship between particle size, cation exchange capacity and chemical composition of clays was also examined. For Wyoming bentonite the extent of isomorphous substitution increases with decreasing particle size, causing the CEC to similarly increase, although the isomorphous substitution site: edge site ratio remains invarient throughout the particle size range studied.

Pillaring of smectites using an aluminium oligomer: A study of pillar density and thermal stability

Two smectite samples having different layer charges were pillared using hydroxy aluminium oligomers at a OH/Al ratio of 2.5 and at pH 4.3 to 4.6. Pillaring was carried out at different conditions such as ageing, temperature and base addition time of the pillaring solution, and also in the presence of nonionic surfactant polyoxyethylene sorbitanmonooleate (Tween-80). The primary objective of preparing at different conditions was to introduce varied quantities of aluminium oligomer between the layers and to study its effect on the properties of the pillared products. A simple method has been followed to estimate the amount of interlayer aluminium. A quantity called pillar density number (PDN) based on the ratio of interlayer Al adsorbed to CEC of the parent clay has been effectively used to evaluate the nature of the resulting pillared product. PDN, for a given clay, was found to correlate well with the sharpness of the d(001) peaks for the air dried samples. The calculated number of pillars, varied from 3.00 x 10(18) to 5.32 x 10(18) per meq charge. The present study shows that a higher value of PDN is indicative of better thermal stability. Pillar density number may be conveniently used as a measure of the thermal stability of pillared samples.

Mechanism of p-nitrophenol adsorption from aqueous solution by HDTMA+-pillared montmorillonite : implications for water purification

HDTMA+ pillared montmorillonites were obtained by pillaring different amounts of the surfactant hexadecyltrimethylammonium bromide (HDTMAB) into sodium montmorillonite (Na-Mt) in an aqueous solution. The optimum conditions and batch kinetics of sorption of p-nitrophenol from aqueous solutions were reported. The solu-tion pH had a very important effect on the sorption of p-nitrophenol. The maximum p-nitrophenol absorption/adsorption occurs when solution pH (7.15~7.35) is approx-imately equal to the pKa (7.16) of the p-nitrophenol ion deprotonation reaction. X-ray diffraction analysis showed that surfactant cations had been pillared into the interlayer and the p-nitrophenol affected the arrangement of surfactant. With the increased con-centration of surfactant cations, the arrangement of HDTMA+ within the clay inter-layer changes and the sorption of p-nitrophenol increases. HDTMA+ pillared mont-morillonites are more effective than Na-Mt for the adsorption of p-nitrophenol from aqueous solutions. The Langmuir, Freundlich and dual-mode sorption were tested to fit the sorption isotherms.

Practical applications for clay-derived zeolite N : an ammonium-selective ion exchanger for industry use

Over the past ten years, scaled-up utilisation of a previously under-exploited zeolite, Zeolite N1, has been demonstrated for selective ion exchange of ammonium and other ions in aqueous environments. As with many zeolite syntheses, the required source material should contain predictable levels of aluminium and silicon and, for full-scale industrial applications, kaolin and/or montmorillonite serve such a purpose. Field, pilot and commercial scale trials of kaolin-derived Zeolite N have focused on applications in agriculture and water treatment as these sectors are primary producers or users of ammonium. The format for the material – as fine powders, granules or extrudates – depends on the specific application albeit each has been evaluated.

A SEM, EDS and vibrational spectroscopic study of the clay mineral fraipontite

The mineral fraipontite has been studied by using a combination of scanning electron microscopy with energy dispersive analysis and vibrational spectroscopy (infrared and Raman). Fraipontite is a member of the 1:1 clay minerals of the kaolinite-serpentine group. The mineral contains Zn and Cu and is of formula (Cu,Zn,Al)3(Si,Al)2O5(OH)4. Qualitative chemical analysis of fraipontite shows an aluminium silicate mineral with amounts of Cu and Zn. This kaolinite type mineral has been characterised by Raman and infrared spectroscopy; in this way aspects about the molecular structure of fraipontite clay are elucidated.

Simultaneous adsorption of Cd(II) and phosphate on Al13 pillared montmorillonite

Al13 pillared montmorillonites (AlPMts) prepared with different Al/clay ratios were used to remove Cd(II) and phosphate from aqueous solution. The structure of AlPMts was characterized by X-ray diffraction (XRD), Thermogravimetric analysis (TG), and N2 adsorption–desorption. The basal spacing, intercalated amount of Al13 cations, and specific surface area of AlPMts increased with the increase of the Al/clay ratio. In the single adsorption system, with the increase of the Al/clay ratio, the adsorption of phosphate on AlPMts increased but that of Cd(II) decreased. Significantly enhanced adsorptions of Cd(II) and phosphate on AlPMts were observed in a simultaneous system. For both contaminants, the adsorption of one contaminant would increase with the increase of the initial concentration of the other one and increase in the Al/clay ratio. The enhancement of the adsorption of Cd(II) was much higher than that of phosphate on AlPMt. This suggests that the intercalated Al13 cations are the primary co-adsorption sites for phosphate and Cd(II). X-ray photoelectron spectroscopy (XPS) indicated comparable binding energy of P2p but a different binding energy of Cd3d in single and simultaneous systems. The adsorption and XPS results suggested that the formation of P-bridge ternary surface complexes was the possible adsorption mechanism for promoted uptake of Cd(II) and phosphate on AlPMt.