Resumo O objetivo do presente trabalho foi estudar argilas naturais argentinas com diferentes modificações e seu uso como dessecantes. Para tanto, as argilas bentoníticas coletadas de diferentes regiões foram caracterizadas e modificadas por tratamento térmico e adição de cálcio, e a capacidade dessecante, em forma de pó e pelotas, foi estudada. Além disso, a reversibilidade do grau de hidratação desses materiais foi estimada. A caracterização mineralógica e estrutural foi realizada por difração de raios X, espectroscopia no infravermelho com transformada de Fourier, análise térmica diferencial e análise termogravimétrica. A caracterização textural foi realizada por adsorção-dessorção de N2, composição química por fluorescência de raios X e capacidade de troca catiônica. A adsorção de água foi determinada a 25 °C entre 11-98% de umidade relativa. Os resultados indicaram que o poder dessecante tem relação estreita com o grau de pureza da argila, a secagem da amostra e o método de incorporação de cálcio.

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.

Resumo O mineral de argila de beidelita após intercalação das espécies OH-Cr(III) foi termicamente analisado até 1350 °C em atmosferas de oxigénio e nitrogênio. A OH-Cr-beidelita pode ser utilizada como um precursor de argila pilarizada para catálise ou para aplicações adsorventes. No entanto, neste trabalho, a beidelita enriquecida em cromo foi analisada em diferentes tratamentos térmicos até alta temperatura para avaliação de mudanças estruturais para possíveis aplicações cerâmicas futuras. As alterações estruturais foram acompanhadas por análise térmica e difração de raios X. O tratamento térmico da OH-Cr-beidelita em atmosferas de oxigênio e nitrogênio desenvolveu diferentes fases mineralógicas até 1050 °C, mas em temperaturas mais altas, as mesmas fases foram desenvolvidas em ambas atmosferas. A fase eskolaita (Cr2O3) apareceu na amostra após aquecimento a 400 °C em atmosfera de oxigênio, enquanto grimaldita (CrO-OH) em atmosfera de nitrogênio, mantendo as fases iniciais. Em 1000 °C, os minerais originais da argila desapareceram, como é conhecido. Em 1050 °C em atmosfera de nitrogênio, a grimaldita estava ausente e apareceu eskolaita. Em amostras calcinadas a 1350 °C em ambas as atmosferas, estavam presentes quartzo, cristobolita e mulita como fases principais e em menores teores óxido de alumínio e óxido de alumínio e cromo [(Al,Cr)2O3].

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.

Two bentonite clays with different mineralogical compositions from Mendoza, Argentine, were activated with H2SO4 solutions of 4 and 8 N at 90ºC for 3.5 hours. This treatment affected clay structural properties, as was shown by thermogravimetry, infrared spectrometry and chemical analysis. Bleaching efficiency for sunflower oil was strongly dependent on the acid concentration used for clay activation. The samples have bleaching capacity comparable to that observed with a commercial adsorbent standard. The mineralogical composition of natural clays influenced the properties of the activated clays.

Natural occurring bentonites may show very little activity for bleaching oils and fats. For that reason, acid-activation of bentonites with inorganic acids is usually carried out to promote earths' adsorptive capacity during clarification of vegetable and animal oils and fats, as well as mineral oils. In this work we used two acid-activated natural bentonites from Mendoza, Argentina, with different mineral compositions and submitted them to acid treatment with hydrochloric acid to further clarify cottonseed oil. Both clays were treated with HCl at 4 and 8N for two hours in order to evaluate important structural properties modifications that may affect oil bleaching. X-ray diffraction, thermal and chemical composition analyses were performed. Cottonseed oil clarification experiments were run in previously established appropriated laboratory conditions. It was shown that clarification efficiency is strongly dependent on the acid concentration and natural clay mineral compositions used to activate the bentonites for the clarification process.

The products of Cr-smectite clays heated to 1350 ° C in nitrogen were evaluated by X-ray diffraction and chemical analysis. Cr-smectite clays were prepared at room temperature by contact between smectite clays and Cr species contained in OH-Cr solutions. The Cr species were prepared using chromium nitrate solution by addition of NaOH solution with OH/Cr = 2. Products of firing in nitrogen at the high temperature were different (magnesia chromite, donathite, iron chromium oxide and picrochromite) depending on the type of isomorphous substitution of the smectite structure and the amount of retained chromium.

In this work, a bentonite clay from Mendoza, Argentina was activated with H2SO4 (4 and 8 N) at 90ºC for 2 and 3.5 hours. Under these conditions several cations were removed from the octahedral sheet (Mg, Al, and Fe) and the DTA-TGA curves of the solids obtained after treatment were modified. Treatment time and acid concentration increased the degree of destruction of the bentonite structure. Activated samples were tested in order to verify their capacity to bleach soybean oil and were compared to a standard commercial bleaching clay. Treated samples are more efficient in bleaching than the standard.

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.

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.

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.

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.

The clay acid activation has the purpose of increasing its adsorbent and catalytic properties. In this study, a bentonite clay sample from Mendoza (Argentine) was activated in different concentrations (4 N and 8 N) through the use of sulphuric and hydrochloric acid. To verify the influence of concentrations and the kind of acid utilized in the clay activation, it was utilized techniques of X-ray diffraction, thermogravimetric and differential thermal analysis and chemical analysis. The results have shown that the clay structure was modified after acid attack. Sulphuric and hydrochloric acid treatment in the same bentonite originated products with different structural characteristics.

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.

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.

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.

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.

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.