Studies on the acid activation of Brazilian smectitic clays

Fuller's earth and acid activated smectitic clays are largely used as bleaching earth for the industrial processing of vegetable, animal and mineral oils and waxes. The paper comments about the nomenclature used for these materials, the nature of the acid activation of smectitic clays (bentonites), activation laboratory procedures and presents a review of the acid activation of bentonites from 20 deposits from several regions of Brazil. The activated clays were tested and show good decolorizing power for soybean, castor, cottonseed, corn and sunflower oils.

Potential Role of Adenosine Signaling in Acetic Acid Activation of Murine Sensory Neurons

Chronic respiratory illnesses are a significant cause of morbidity and mortality, and acute changes in respiratory function often lead to hospitalization. Air pollution is known to exacerbate asthma, but the molecular mechanisms of this are poorly understood. The current studies were aimed at clarifying the roles of nerve subtypes and purinergic receptors in respiratory reflex responses following exposure to irritants. In C57Bl/6J female mice, inspired adenosine produced sensory irritation, shown to be mediated mostly by A-delta fibers. Secondly, the response to inhaled acetic acid was discovered to be dually influenced by C and A-delta fibers, as indicated by the observed effects of capsaicin pretreatment, which selectively destroys TRPV1-expressing fibers (mostly C fibers) and pretreatment with theophylline, a nonselective adenosine receptor antagonist. The responses to both adenosine and acetic acid were enhanced in the ovalbumin-allergic airway disease model, although the particular pathway altered is still unknown.

Overexpression of csk inhibits acid-induced activation of NHE-3.

Opossum kidney OKP cells express an apical membrane Na+/H+ antiporter that is encoded by NHE-3 (for Na+/H+ exchanger 3) and is similar in many respects to the renal proximal tubule apical membrane Na+/H+ antiporter. Chronic incubation of OKP cells in acid medium for 24 hr increases Na+/H(+)-antiporter activity and NHE-3 mRNA abundance. The increase in Na+/H(+)-antiporter activity was not prevented by H7, a protein kinase C/protein kinase A inhibitor, but was prevented by herbimycin A, a tyrosine kinase inhibitor. Incubation of cells in acid medium increased c-src activity, and this was inhibited by herbimycin A. To determine the role of the src family of nonreceptor protein-tyrosine kinases, Csk (for carboxyl-terminal src kinase), a physiologic inhibitor of these kinases, was overexpressed in OKP cells. In three clones overexpressing csk, acid-induced increases in Na+/H(+)-antiporter activity and NHE-3 mRNA abundance were inhibited. In these clones, inhibition of acid activation of Na+/H(+)-antiporter activity paralleled inhibition of acid activation of c-src. Neither herbimycin A nor overexpression of csk inhibited dexamethasone-induced increases in Na+/H(+)-antiporter activity. These studies show that decreases in pH activate c-src and that the src family nonreceptor protein-tyrosine kinases play a key role in acid activation of NHE-3.

Characterization of Unye bentonite after treatment with sulfuric acid

Unye bentonite was found to consist predominantly of a dioctahedral smectite along with quartz, tridymite, cristobalite, and minor fractions of feldspar and anatase. A considerable amount of Al was retained as a constituent in acid-resistant impurities following the decomposition of the montmorillonite via acid treatment at an acid/clay ratio of 0.4. These impurities were mesoporous with a maximum surface area of 303.9±0.4 m² g-1. A sharp decrease in the d001 lattice spacing of the montmorillonite to 15.33 Å reflected the reduction of the crystallinity in the activated products. In addition, the increase in the ease with which newly formed hydroxyl groups were lost paralleled the severity of the acid treatment.

Molecular cloning and expression of the 32-kDa subunit of human TFIID reveals interactions with VP16 and TFIIB that mediate transcriptional activation.

Transcription factor TFIID consists of TATA binding protein (TBP) and at least eight TBP-associated factors (TAFs). As TAFs are required for activated but not basal transcription, we have proposed that TAFs act as coactivators to mediate signals between activators and the basal transcription machinery. Here we report the cloning, expression, and biochemical characterization of the 32-kDa subunit of human (h) TFIID, termed hTAFII32. We find that hTAFII32 is the human homologue of Drosophila TAFII40. In vitro protein-protein interaction assays reveal that as observed with Drosophila TAFII40, hTAFII32 interacts with the C-terminal 39-amino acid activation domain of the acidic transactivator viral protein 16 (VP16) as well as with the general transcription factor TFIIB. Moreover, a partial recombinant TFIID complex containing hTAFII32 was capable of mediating in vitro transcriptional activation by the VP16 activation domain. These findings indicate that specific activator-coactivator interactions have been conserved between human and Drosophila and provide additional support for the function of these interactions in mediating transcriptional activation.

Spherical carbons: Synthesis, characterization and activation processes

Spherical carbons have been prepared through hydrothermal treatment of three carbohydrates (glucose, saccharose and cellulose). Preparation variables such as treatment time, treatment temperature and concentration of carbohydrate have been analyzed to obtain spherical carbons. These spherical carbons can be prepared with particle sizes larger than 10 μm, especially from saccharose, and have subsequently been activated using different activation processes (H3PO4, NaOH, KOH or physical activation with CO2) to develop their textural properties. All these spherical carbons maintained their spherical morphology after the activation process, except when KOH/carbon ratios higher than 4/1 were used, which caused partial destruction of the spheres. The spherical activated carbons develop interesting textural properties with the four activating agents employed, reaching surface areas up to 3100 m2/g. Comparison of spherical activated carbons obtained with the different activating agents, taking into account the yields obtained after the activation process, shows that phosphoric acid activation produces spherical activated carbons with higher developed surface areas. Also, the spherical activated carbons present different oxygen groups’ content depending on the activating agent employed (higher surface oxygen groups content for chemical activation than for physical activation).

Production, characterization and application of activated carbon from brewer`s spent grain lignin

Different types of activated carbon were prepared by chemical activation of brewer`s spent grain (BSG) lignin using H(3)PO(4) at various acid/lignin ratios (1, 2, or 3 g/g) and carbonization temperatures (300, 450, or 600 degrees C), according to a 2(2) full-factorial design. The resulting materials were characterized with regard to their surface area, pore volume, and pore size distribution, and used for detoxification of BSG hemicellulosic hydrolysate (a mixture of sugars, phenolic compounds, metallic ions, among other compounds). BSG carbons presented BET surface areas between 33 and 692 m(2)/g, and micro- and mesopores with volumes between 0.058 and 0.453 cm(3)/g. The carbons showed high capacity for adsorption of metallic ions, mainly nickel, iron, chromium, and silicon. The concentration of phenolic compounds and color were also reduced by these sorbents. These results suggest that activated carbons with characteristics similar to those commercially found and high adsorption capacity can be produced from BSG lignin. (C) 2009 Elsevier Ltd. All rights reserved.

Argilas modificadas como catalisadores ácidos sólidos

Important bentonitic deposits are present in Porto Santo Island, part of the Madeira Archipelago. Several locations were selected and samples were collected and characterised. The bentonite obtained at Serra de Dentro (SD) was selected for further laboratorial work. The fine fraction of SD bentonite was purified using several methods and the sodium homoionic form was prepared. This was the starting material used in the three generic types of modifications: metal exchange, acid activation and pillaring. These modifications produce materials with markedly different acidic (e.g. Brönsted and/or Lewis acidity), textural (e.g. increase of the surface area and active site accessibility) or structural (e.g. creation of permanent porous structures) properties. The wide range of materials obtained (including reference clays counterparts) was characterised in terms of chemical, structural, textural and catalytic properties. Limonene is an important raw material produced in Portugal, and its aromatisation reaction was chosen for the catalytic characterisation of the clay catalysts prepared.

Caracterização e aplicação de vermicultura natural e quimicamente modificada na adsorção de azul de metileno

Chemical modification of clays has been extremely studied in the search for improvements of their properties for use in various areas, such as in combating pollution by industrial effluents and dyes. In this work, the vermiculite was chemically modified in two ways, characterized and evaluated the adsorption of methylene blue dye. First was changed with the addition of a surfactant (hexadecyltrimethylammonium bromide, BHTA) making it an organophilic clay and then by adding an acid (HCl) by acid activation. Some analyzes were performed as X-ray fluorescence (FRX), X-ray diffraction (DRX), adsorption isotherms of methylene blue dye, infrared (FTIR) , scanning electron microscopy (SEM), thermal gravimetric analysis and spectroscopy energy dispersive (EDS). Analysis by FRX of natural vermiculite indicates that addition of silicon and aluminum, clay presents in its structure the magnesium, calcium and potassium with 16 % organic matter cations. The DRX analyzes indicated that the organic vermiculite was an insertion of the surfactant in the space between the lamellae, vermiculite and acid partial destruction of the structure with loss of crystallinity. The adsorption isotherms of methylene blue showed that there was a significant improvement in the removal of dye to the vermiculite with the addition of cationic surfactant hexadecyltrimethylammonium bromide and treatment with acid using HCl 2 mol/L. In acid vermiculites subsequently treated with surfactant, the adsorption capacity increased with respect to natural vermiculite, however was much lower compared vermiculite modified with acid and surfactant separately. Only the acidic vermiculite treated with surfactant adjusted to the Langmuir model. As in the infrared spectrometry proved the characteristics of natural vermiculite. In the organic vermiculite was observed the appearance of characteristic bands of CH3, CH2, and (CH3)4N. Already on acid vermiculite, it was realized a partial destruction with decreasing intensity of the characteristic band of vermiculite that is between 1074 and 952 cm-1. In the SEM analysis, it was observed that there was partial destruction to the acid treatment and a cluster is noted between the blades caused by the presence of the surfactant. The TG shows that the higher mass loss occurs at the beginning of the heating caused by the elimination of water absorbed on the surface between layers. In the organic vermiculite also observed a loss of mass between 150 and 300 °C caused decomposition of the alkylammonium molecules (surfactants)

Caracterização de argilas e biomassa da cana-de-açúcar e utilização como adsorventes na remoção de BTX

Pós-graduação em Química - IBILCE

Capacidad y comportamiento de la adsorción de fenol en caolines naturales y modificados

En la actualidad las industrias químicas, farmacéuticas y clínicas, originan contaminantes en aguas superficiales, aguas subterráneas y suelos de nuestro país, como es el caso del fenol, contaminante orgánico común y altamente dañino para los organismos, incluso a bajas concentraciones. Existen en el mercado diferentes metodologías para minimizar la contaminación pero muchos de estos procesos tienen un alto coste, generación de contaminantes, etc. La adsorción de contaminantes por medio de arcillas es un método ampliamente utilizado, encontrándose eficaz y económico. Pero la dificultad de adsorber un contaminante orgánico como el fenol motiva la creación de un material llamado organoarcillas. Las organoarcillas son arcillas modificadas con un surfactante, a su vez, los surfactantes son moléculas orgánicas que confieren a la superficie de la arcilla carga catiónica en lugar de aniónica, haciendo más fácil la adsorción de fenol. Para esta tesis se ha elegido el caolín como material adsorbente, fácilmente disponible y relativamente de bajo coste. Se ha trabajado con: arenas de caolín, material directo de la extracción, y caolín lavado, originado del proceso de lavado de las arenas de caolín. Ambos grupos se diferencian fundamentalmente por su contenido en cuarzo, ampliamente mayor en las arenas de caolín. Con el objetivo de desarrollar un material a partir del caolín y arenas de éste con capacidad de retención de contaminates, en concreto, fenol, se procedió a modificar los materiales de partida mediante tratamientos térmicos, mecánicos y/o químicos, dando lugar a compuestos con mayor superficie química reactiva. Para ello se sometió el caolín y las arenas caoliníferas a temperaturas de 750ºC durante 3h, a moliendas hasta alcanzar su amorfización, y/o a activaciones con HCl 6M o con NaOH 5M durante 3h a 90ºC. En total se obtuvieron 18 muestras, en las que se estudiaron las características físico-químicas, mineralógicas y morfológicas de cada una de ellas con el fin de caracterizarlas después de haber sufrido los tratamientos y/o activaciones químicas. Los cambios producidos fueron estudiados mediante pH, capacidad de intercambio catiónico (CEC), capacidad de adsorción de agua (WCU y CWC), distribución de tamaño de partícula (PSD), área de superficie específica (SBET), difracción de rayos X (XRD), espectroscopía infrarroja por transformada de Fourier (FTIR), métodos térmicos (TG, DTG y DTA), y microscopía electrónica de transmisión y barrido (SEM y TEM). Además se analizó los cambios producidos por los tratamientos en función de las pérdidas de Al y Si que acontece en las 18 muestras. Los resultados para los materiales derivados de la arenas caoliníferas fueron similares a los obtenidos para los caolines lavados, la diferencia radica en la cantidad de contenido de caolinita en los diferente grupos de muestras. Apoyándonos en las técnicas de caracterización se puede observar que los tratamientos térmico y molienda produce materiales amorfos, este cambio en la estructura inicial sumado a las activaciones ácida y alcalina dan lugar a pérdidas de Si y Al, ocasionando que sus propiedades físico-químicas, mineralógicas y morfológicas se vean alteradas. Un fuerte aumento es observado en las áreas superficiales y en la CEC en determinadas muestras, además entre los cambios producidos se encuentra la producción de diferentes zeolitas en porcentajes distintos con el tratamiento alcalino. Para la obtención de las organoarcillas, las 18 muestras se sometieron a la surfactación con hexadeciltrimetil amonio (HDTMA) 20 mM durante 24h a 60ºC, esta concentración de tensioactivo fue más alta que la CEC de cada muestra. Los camext bios anteriormente producidos por los tratamientos y activaciones, afectan de forma diferente en la adsorción de HDTMA, variando por tanto la adsorción del surfactante en la superficie de las muestras. Se determinó el tensioactivo en superficie por FTIR, además se realizó un análisis de componentes principales (PCA) para examinar la dependencia entre las relaciones Si/Al de las muestras en la capacidad de adsorción de tensioactivo, y para el estudio de la adsorción de HDTMA en las muestras se realizaron además del análisis termogravimétrico, aproximaciones con los modelos de Freundllich y Langmuir. Se persigue conocer las diferentes formas y maneras que tiene el tensioactivo de fijarse en la superficie de las muestras. En las organoarcillas resultantes se cuantificó el fenol adsorbido cuando éstas fueron puestas en contacto con diferentes concentraciones de fenol: 50, 500, 1000, 2000, y 2500 mg/l durante 24h. El contaminante sorbido se calculó por medio de cromatografía de gases, y se realizaron aproximaciones con los modelos de Freundllich y Langmuir. El comportamiento de adsorción de fenol en arcillas orgánicas es regido por las características de las muestras. De forma general se puede decir que las muestras de caolines lavados tienen más capacidad de adsorción de fenol que las muestras de arenas de caolín y que la activación alcalina ha proporcionado una mejora en la adsorción de fenol en los dos grupos. En consecuencia se han obtenido materiales adsorbentes heterogéneos y por tanto, con propiedades diferentes. Se ha evaluado el comportamiento global de las arenas de caolín por un lado y del caolín lavado por otro. Las arenas de caolín presentan altos niveles de cuarzo y su uso para ciertos tipos de industrias no son recomendados en ocasiones por el alto costo que el proceso de limpieza y purificación implicaría. Por ello es importante reseñar en este proyecto las aplicaciones que ofrecen algunas muestras de este grupo. Los ensayos acontecidos en esta tesis han dado lugar a las siguientes publicaciones: • Pérdida de Al y Si en caolines modificados térmica- o mecánicamente y activados por tratamientos químicos. A. G. San Cristóbal, C Vizcayno, R. Castelló. Macla 9, 113-114. (2008). • Acid activation of mechanically and thermally modfied kaolins. A. G. San Cristóbal, R. Castelló, M. A. Martín Luengo, C Vizcayno. Mater. Res. Bull. 44 (2009) 2103-2111. • Zeolites prepared from calcined and mechanically modified kaolins. A comparative study. A. G San Cristóbal, R. Castelló, M. A. Martín Luengo, C Vizcayno. Applied Clay Science 49 (2010) 239-246. • Study comparative of the sorption of HDTMA on natural and modified kaolin. A. G San Cristóbal, R. Castelló, J. M. Castillejo, C Vizcayno. Aceptada en Clays and Clay minerals. • Capacity of modified kaolin sand and washed kaolin to adsorb phenol. A. G San Cristóbal, R. Castelló, C Vizcayno. Envío a revista sujeto a la publicación del artículo anterior. ABSTRACT Today’s chemical, pharmaceutical and clinical industries generate pollutants that affect the soils and surface and ground waters of our country. Among these, phenol is a common organic pollutant that is extremely harmful to living organisms, even at low concentrations. Several protocols exist to minimize the effects of pollutants, but most are costly procedures or even generate other pollutants. The adsorption of hazardous materials onto clays is perhaps the most used, efficient and cost-saving method available. However, organic compounds such as phenol are difficult to adsorb and this has led to the development of materials known as organoclays, which are much better at remediating organic compounds. Organoclays are clays that have been modified using a surfactant. In turn, surfactants are organic molecules that confer a cationic rather than anionic charge to the clay surface, improving it’s capacity to adsorb phenol. For this doctorate project, kaolin was selected as an adsorbent material for the removal of phenol given its easy sourcing and relatively low cost. The materials investigated were kaolin sand, a directly extracted material, and washed kaolin, which is the byproduct of the kaolin sand washing process. The main difference between the materials is their quartz content, which is much higher in the kaolin sands. To generate a product from kaolin or kaolin sand capable of retaining organic pollutants such as phenol, both materials were subjected to several heat, chemical and/or mechanical treatments to give rise to compounds with a greater reactive surface area. To this end the two starting materials underwent heating at 750ºC for 3 h, grinding to the point of amorphization and/or activation with HCl 6M or NaOH 5M for 3 h at 90ºC. These treatments gave rise to 18 processed samples, which were characterized in terms of their morphological, mineralogical, and physical-chemical properties. The behaviour of these new materials was examined in terms of their pH, cation exchange capacity (CEC), water adsorption capacity (WCU and WCC), particle size distribution (PSD), specific surface area (SBET), and their X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), thermal (DTG, DTA) and scanning and transmission electron microscopy (SEM and TEM) properties. The changes conferred by the different treatments were also examined in terms of Al and Si losses. Results for the materials derived from kaolin sands and washed kaolin were similar, with differences attributable to the kaolinite contents of the samples. The treatments heat and grinding produced amorphous materials, which when subjected to acid or alkali activation gave rise to Si and Al losses. This in turn led to a change in physico- chemical, mineralogical and morphological properties. Some samples showed a highly increased surface area and CEC. Further, among the changes produced, alkali treatment led to the generation of zeolites in different proportions depending on the sample. To produce the organoclays, the 18 samples were surfacted with hexadecyltrimethylammonium (HDTMA) 20 mM for 24 h at 60ºC. This surfactant concentration is higher than the CEC of each sample. The amount of HDTMA adsorbed onto the surface of each sample determined by FTIR varied according to treatment. A principle components analysis (PCA) was performed to examine correlations between sample Si/Al ratios and surfactant adsorption capacity. In addition, to explore HDTMA adsorption by the samples, DTG and DTA data were fitted to Freundllich and Langmuir models. The mechanisms of surfactant attachment to the sample surface were also addressed. The amount of phenol adsorbed by the resultant organoclays was determined when exposed to different phenol concentrations: 50, 500, 1000, 2000, and 2500 mg/l for 24 h. The quantity of adsorbed pollutant was estimated by gas chromatography and the data fitted to the models of Freundllich and Langmuir. Results indicate that the phenol adsorption capacity of the surfacted samples is dependent on the sample’s characteristics. In general, the washed kaolin samples showed a greater phenol adsorption capacity than the kaolon sands and alkali activation improved this capacity in the two types of sample. In conclusion, the treatments used gave rise to adsorbent materials with varying properties. Kaolin sands showed high quartz levels and their use in some industries is not recommended due to the costs involved in their washing and purification. The applications suggested by the data obtained for some of the kaolin sand samples indicate the added value of this industrial by-product. The results of this research project have led to the following publications: • Pérdida de Al y Si en caolines modificados térmica- o mecánicamente y activados por tratamientos químicos. A. G. San Cristóbal, C Vizcayno, R. Castelló. Macla 9, 113-114. (2008). • Acid activation of mechanically and thermally modfied kaolins. A. G. San Cristóbal, R. Castelló, M. A. Martín Luengo, C Vizcayno. Mater. Res. Bull. 44 (2009) 2103-2111. • Zeolites prepared from calcined and mechanically modified kaolins. A comparative study. A. G. San Cristóbal, R. Castelló, M. A. Martín Luengo, C Vizcayno. Applied Clay Science 49 (2010) 239-246. • Study comparative of the sorption of HDTMA on natural and modified kaolin. A. G. San Cristóbal, R. Castelló, J. M. Castillejo, C Vizcayno Accepted in Clays and Clay minerals. • Capacity of modified kaolin sand and washed kaolin to adsorb phenol. A. G San Cristóbal, R. Castelló, C Vizcayno. Shipment postponed, subject to the publication of the previous article.

Misactivated amino acids translocate at similar rates across surface of a tRNA synthetase

Certain aminoacyl-tRNA synthetases have a second active site that destroys (by hydrolysis) errors of amino acid activation. For example, isoleucyl-tRNA synthetase misactivates valine (to produce valyl adenylate or Val-tRNAIle) at its active site. The misactivated amino acid is then translocated to an editing site located >25 Å away. The role of the misactivated amino acid in determining the rate of translocation is not known. Valyl-tRNA synthetase, a close homolog of isoleucyl-tRNA synthetase, misactivates threonine, α-aminobutyrate, and cysteine. In this paper, we use a recently developed fluorescence-energy-transfer assay to study translocation of misactivated threonine, α-aminobutyrate, and cysteine. Although their rates of misactivation are clearly distinct, their rates of translocation are similar. Thus, the rate of translocation is independent of the nature of the misactivated amino acid. This result suggests that the misactivated amino acid per se has little or no role in directing translocation.

Mechanism of attenuation of angiotensin-II-induced protein degradation by insulin-like growth factor-I (IGF-I)

Insulin-like growth factor-I (IGF-I) has been shown to attenuate protein degradation in murine myotubes induced by angiotensin II through downregulation of the ubiquitin-proteasome pathway, although the mechanism is not known. Angiotensin II is known to upregulate this pathway through a cellular signalling mechanism involving release of arachidonic acid, activation of protein kinase Cα (PKCα), degradation of inhibitor-κB (I-κB) and nuclear migration of nuclear factor-κB (NF-κB), and all of these events were attenuated by IGF-I (13.2 nM). Induction of the ubiquitin-proteasome pathway has been linked to activation of the RNA-activated protein kinase (PKR), since an inhibitor of PKR attenuated proteasome expression and activity in response to angiotensin II and prevented the decrease in the myofibrillar protein myosin. Angiotensin II induced phosphorylation of PKR and of the eukaryotic initiation factor-2 (eIF2) on the α-subunit, and this was attenuated by IGF-I, by induction of the expression of protein phosphatase 1, which dephosphorylates PKR. Release of arachidonic acid and activation of PKCα by angiotensin II were attenuated by an inhibitor of PKR and IGF-I, and the effect was reversed by Salubrinal (15 μM), an inhibitor of eIF2α dephosphorylation, as was activation of PKCα. In addition myotubes transfected with a dominant-negative PKR (PKRΔ6) showed no release of arachidonate in response to Ang II, and no activation of PKCα. These results suggest that phosphorylation of PKR by angiotensin II was responsible for the activation of the PLA2/PKC pathway leading to activation of NF-κB and that IGF-I attenuates protein degradation due to an inhibitory effect on activation of PKR. © 2007 Elsevier Inc. All rights reserved.

Estudo da intercalação de fontes de potássio em caulinita pura, com tratamento térmico e ativação ácida

The chemical changes in clay minerals has been widely studied in order to improve its properties for use in various applications. However kaolinite has strong hydrogen bonds between their adjacent layers hindering the process changes in its structure. With the objective to facilitate the process of intercalation monobasic potassium phosphate, bibasic potassium phosphate and potassium acetate we was performed on kaolinite heat treatment at 600 °C and activated acidic with phosphoric acid and 5 to 10 mol L-1. The samples they were characterized by energy dispersive spectroscopy (EDS), X-Ray Diffraction (XRD), Infrared Spectroscopy Fourier Transform (FTIR) and Thermogravimetric Analysis (TG) and Differential Thermal Analysis (DTG) and the superficial and textural changes the samples with heat treatment and acid activation they were characterized by scanning electron microscopy (SEM) and Textural Analysis of Adsorption/desorption N2. With the help of the techniques found that, the heat treatment becomes more susceptible to acid activation kaolinite making the samples with two treatments show larger amounts of phosphorus. It was also found that bibasic potassium phosphate binds more strongly the structure of kaolinite by having a structure with two-coordinating oxygens and intercalation with potassium acetate in acid-activated kaolin increases the interlayer distance of the kaolinite and the intercalation occurs with higher response index (RI) for samples with acid activation to 5 mol /L.

Stability of clay-based catalysts in contact with water vapour

The search for cleaner processes is one of the major challenges in modern chemical industries. In this context clay derived materials are environmentally friendly catalysts that can be easily tailored to optimize their catalytic activity for a precise reaction of interest. Furthermore, clay-based catalysts can be easily separated, recovered and reused and their versatility, low cost, high catalytic activity and/or selectivity render them very attractive materials. Considering that the stability towards water vapour is a crucial aspect for catalytic performance and reuse of the catalysts, we present a study of the pore structure stability, in the presence of water vapour, of clay catalysts prepared by acid activation with HCl solutions and ion-exchange with sodium, aluminium and iron, from a natural clay collected at Serra de Dentro (Porto Santo Island, Portugal) [1]. For elucidating the influence of water vapour on the pore structure stability, water vapour adsorption- -desorption isotherm, at 298 K, was determined on each sample by gravimetric method as well as n-pentane adsorption−desorption isotherms, at 298 K, which were determined before and after the corresponding water adsorption-desorption isotherms. Prior to the measurements, the samples were outgassed during 5 h at 473 K and the adsorptives were outgassed by repeated freeze–thaw cycles. The results to be reported in the communication allow us to state that, upon contact with water vapour, the less acid activated catalysts suffered some reduction in pore volume reflecting changes in the pore structure, while the more acid activated catalysts and those prepared by ion-exchange presented excellent stability upon one cycle of water vapour adsorption-desorption. The results are corroborated by nitrogen adsorption-desorption isotherms determined, at 77 K, before and after the water and n-pentane adsorption-desorption measurements.