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N2 and CO2 gases adsorption by tetramethylammonium(TMA)-montmorillonites and hexadecylpyridinium(HDP)-montmorillonites was carried out using volumetric equipment at 25 °C and 0.1 MPa. The addition of organic compounds to montmorillonites was 1 and 4 times the cation exchange capacity (CEC) of the montmorillonites and the contact times between the TMA (or HDP) and the montmorillonites were 4 and 24 h. The adsorptions of CO2 by TMA-montmorillonites (0.383-0.477 mmol/g) were higher than those by HDP-montmorillonites (0.027-0.060 mmol/g). N2 gas retentions by organo-montmorillonites were small: in the range of 0.038-0.065 mmol/g TMA-montmorillonites and around 0.010 mmol/g HDP-montmorillonites. The interlamellar spacing of the organo-montmorillonites, the structure of the intercalated organic molecule, and the type of montmorillonites influenced the gas adsorption values.

Retention of chromium (III) from a tanning wastewater by modified Al-bentonites was studied. One bentonite from San Juan province, Argentina, was used. Al-bentonite was prepared by contact of bentonite with hydrolyzed OH-Al solutions (0.10 M in Al) for 24 hours. The modified Al-bentonites were obtained by: a) treatment with 0.5 M sodium chloride; b) with 0.5 M sodium chloride adjusted at pH 8; and c) treatment with an hexametaphosphate solution after sodium addition. Then, the samples were dried at 100 °C and heated at 500 °C. The chromium (III) retention by samples was carried out in batch system putting in contact the material with a 2000 ppm Cr tannery waste at different times. The retained chromium was characterized by analyzing the supernatant using UV-visible spectroscopy. The different chromium retention was correlated with structural characteristics of the solids.Foi estudada a retenção de cromo (III) de águas residuais por meio de Al-bentonitas modificadas. Foi usada uma bentonita da província de San Juan, Argentina. As bentonitas-Al forma preparadas colocando-as em contato com soluções (0,10 M Al) hydrolizadas de OH-Al durante 24 horas. As bentonitas-Al modidicadas foram obtidas por meio de: a) tratamento com cloreto de sódio 0,5 M; b) com cloreto de sódio 0,5 M sodium com pH ajustado para 8; e c) tratamento com uma solução de hexametafosfato após a adição de sódio. As amostras foram então secas a 100 °C e aquecidas a 500 °C. A retenção do cromo (III) pelas amostras foi feita em lotes colocando o material em contato em diferentes tempos com um resíduo contendo 2000 ppm de cromo. O cromo retido foi caracterizado por meio de análise do sobrenadante usando espectroscopia UV-visível. As diferentes retenções de cromo foram correlacionadas com características estruturais dos sólidos.

A ativação ácida de uma argila tem por finalidade aumentar as suas propriedades adsortivas e catalíticas. Nesse estudo, uma amostra de argila bentonítica, proveniente da Província de Mendoza (Argentina), foi ativada com diferentes concentrações (4 e 8 N) por ácido sulfúrico e clorídrico. Para verificar a influência das concentrações e do tipo de ácido usado na ativação da argila, utilizou-se técnicas de difração de raios X, análise térmica diferencial e termogravimétrica e análise química. Os resultados mostraram que houve modificação na estrutura do material argiloso após o ataque ácido. O tratamento com ácido sulfúrico e clorídrico sobre uma mesma bentonita originou produtos com diferentes características estruturais.

Rheological changes were found in smectite (Wyoming- and Cheto-type montmorillonites) suspensions after structural modifications. The effect of the particle size and Na+ exchange on the flow curves of 6% wt/wt suspensions of smectites with and without Na2CO3 were examined. Mineralogical, structural and physicochemical characteristics were studied by X-ray diffraction (XRD), infrared spectroscopy (IR), cationic exchange capacity (CEC), Mg2+, Al3+ determinations, particle size distribution and swelling index (SI). Grinding in an oscillating mill modified the particle sizes. The montmorillonite grain size and the structural disorder increased after larger grinding times. The grinding treatment modified the apparent viscosity and the yield stress of the montmorillonite suspensions. The homoionic Na Cheto-type montmorillonite with fine particle size (obtained by grinding) increased the flow properties. Nevertheless, rheological properties were lower than those of suspensions of the Wyoming-type montmorillonite. Montmorillonite-types reacted differently with Na2CO3 additions and this behavior may be related to their structural composition. The Na2CO3 activation improved the flow properties of the original Wyoming-type montmorillonite and after 30 s grinding.Foram encontradas mudanças reológicas em suspensões de esmectitas (montmorillonitas tipos Wyoming e Cheto) após modificações estruturais. Foi examinado o efeito do tamanho de partícula e troca de Na+ nas curvas de escoamento de suspensões de esmectitas 6% peso com e sem Na2CO3. As características mineralógicas, estructurais e físico-químicas foram estudadas por difração de raios X (DRX), espectroscopia no infravermelho (IV), capacidade de troca catiônica (CTC), determinações de Mg2+ e Al3+, de distribuição de tamanho de partículas e de índice de expansão (swelling index - SI). Moagem em moinho oscilatório modificou o tamanho das partículas. O tamanho de grão da montmorillonita e a desordem estrutural aumentaram após maiores tempos de moagem. O tratamento por moagem modificou a viscosidade aparente e o limite de escoamento das suspensões de montmorillonita. A montmorillonita homoiônica de Na do tipo Cheto com pequeno tamanho de partícula (obtido por moagem) melhorou as propriedades de escoamento. Entretanto, as propriedades reológicas foram piores que as de suspensões de montmorillonita do tipo Wyoming. Os diferentes tipos de montmorillonitas reagiram de modo diferente com adições de Na2CO3 e este comportamento pode estar relacionado com suas composições estruturais. A ativação por Na2CO3 melhorou as propriedades de escoamento da montmorillonita tipo Wyoming original após moagem por 30 s.

Organo-clays were prepared by exchange cations of the montmorillonite with tetramethylammonium (TMA)- and hexadecylpyridinium (HDP)-chloride. Two different montmorillonite types were studied. Two amounts of each organic substances (1 and 4 cation exchange capacity times of montmorillonite) were contacted with each montmorillonite clay for 1 and 24 h. The solids were characterized by X-ray diffraction and swelling index. The swelling was measured in water and toluene media. The structural characteristics of montmorillonites changed after organo treatment and showed different behaviour in water and toluene media. The type of montmorillonite, the organic cation intercalates (TMA, HDP) and condition of treatment influenced in the different swelling in water and toluene media.

The adsorption of sulphuric acid on smectite from acidic aqueous solutions was studied. The amounts of cations dissolved in each equilibrium solution were determined by chemical analysis. Simultaneously, the original smectite and the smectite after each test were characterized by infrared, X-ray diffraction and swelling index. The results obtained permitted us to determine that the substitutions of the exchange cations and the chemical attack occurred at very different acid concentrations and treatment times. It was established that during the acid treatment of the smectite, a progressive damage of its crystalline structure was produced. Finally, the influences of the substitution of exchange cations and of the chemical attack in the swelling index were determined.A adsorção de ácido sulfúrico em esmectita de soluções aquosas ácidas é estudada. As concentrações de cátions dissolvidos em cada solução em equilíbrio foram determinadas por análise química. As esmectitas original e após cada teste foram simultaneamente caracterizadas por infravermelho, difração de raios X e índice de crescimento. Os resultados obtidos permitiram determinar que as substituições dos cátions de troca e o ataque químico ocorreram em diferentes concentrações de ácido e tempos de tratamento. Foi verificado que durante o tratamento em ácido da esmectita foi produzido um dano progressivo da sua estrutura cristalina. Finalmente foram determinadas as influências da substituição dos cátions de troca e do ataque químico no índice de crescimento.

Abstract Beidellite clay mineral after intercalation of OH-Cr(III) species were thermally analyzed up to 1350 °C in oxygen and nitrogen atmospheres. OH-Cr-beidellite can be used as a pillared clay precursor for catalysis or as adsorbent applications. However, in this paper beidellite enriched in chromium were analyzed at different thermal treatments up to high temperature for evaluating structural changes for possible future ceramic applications. The structural changes were followed by thermal analysis and X-ray diffraction. The thermal treatment of OH-Cr-beidellite in oxygen and nitrogen atmospheres developed different mineralogical phases up to 1050 °C, but at higher temperatures, the same phases were developed in both atmosphere treatments. Eskolaite phase (Cr2O3) appeared in the sample after heating at 400 °C in oxygen atmosphere, whereas grimaldite (CrO-OH) in nitrogen atmosphere, maintaining the starting phases. At 1000 °C the raw clay minerals disappeared, as it is knew. At 1050 °C in nitrogen atmosphere, grimaldite was absent and eskolaite appeared. At 1350 °C in the samples calcined in both atmospheres, quartz, cristobalite and mullite as the main phases and in lower contents aluminum oxide and aluminum-chromium oxide [(Al,Cr)2O3] were present.

Abstract The aim of the present work was to study Argentinean natural clays with different modifications and their use as desiccants. To this end, bentonite clays collected from different regions were characterized and modified by heat treatment and calcium addition, and the desiccant capacity, in the form of powder and pellets, was studied. In addition, the hydration degree reversibility of these materials was estimated. The mineralogical and structural characterization was performed by X-ray diffraction, Fourier-transform infrared spectroscopy, differential thermal analysis, and thermogravimetric analysis. The textural characterization was performed by adsorption-desorption of N2, chemical composition by X-ray fluorescence and cation exchange capacity. The water adsorption was determined at 25 °C between 11-98% relative humidity. The results indicated that the desiccant power has a close relationship with the degree of clay purity, drying of the sample and the method of calcium incorporation.

Modified kaolin clays were used as adsorbents for SO(2) gas adsorptions. The clays were heated up to 900 °C previous to acid treatments with 0.5 N sulfuric acid solutions at boiling temperature during different times up to 1440 min. Equilibrium adsorption at 25 °C and 0.1 MPa was carried out by using a volumetric apparatus. The samples were characterized by chemical analysis, X-ray diffraction and infrared analysis. The heating of the clays followed by acid treatment improved the adsorption capacity of the kaolin clays. The presence of amorphous silica and hydroxyl in the final products improved SO(2) adsorption capacity. Better properties for SO(2) adsorption were found in kaolin rich in not well ordered kaolinite clay mineral., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

The retention of chromium(III) from a 2,000 ppm chromium basic sulfate and tannery waste solution at pH 4.5 using modified hydroxy-aluminum bentonites (OH-Al bentonites) as adsorbents was studied. OH-Al bentonite was prepared by mixing clay with a hydrolyzed commercial chlorohydroxy Al solution. The modified Al bentonites were obtained by (a) a treatment with 0.5M sodium chloride and (b) a treatment with a Na-hexametaphosphate solution (HMP) after adding sodium chloride. The effect of heating the adsorbents at 100, 500, 700 and 800 degrees C on Cr retention as a function of time was also analyzed. Cr retention by modified OH-Al bentonite with HMP increased with time (up to 100 mg Cr/g) where modified OH-Al bentonite was twice that of untreated bentonite. The relatively high uptake of metal from the salt solution by modified OH-Al bentonite treated at 800 degrees C, in which a complete interlayer collapse occurred, indicated the importance of the contribution of external surface sites to the retention capacity. The maximum Cr uptake from a water waste was 24 mg/g, due to interferences and different chromium species in the industrial solution.

Intercalated montmorillonite clays with different amounts of organic hexadecyltrimethylammonium (HDTMA) cations were studied to analyse their CO, CH(4), and SO(2) gas retentions. Equilibrium adsorption was measured by using a standard volumetric apparatus at 25 degrees C and 0.1 MPa. The solids were characterised by X-ray diffraction. The levels of adsorption of SO(2) by organo-montmorillonites (0.3595-1.6403 mmol/g) were higher than those of CO (up to 0.0202 mmol/g) and CH(4) (up to 0.0273 mmol/g) gases. HDTMA montmorillonites may be effective adsorbents for removing SO(2) and for its potential separation in the presence of CO and/or CH(4) molecules, which can be present in contaminated air.