Characterization of the acidic properties of mesoporous aluminosilicates synthesized from leached saponite with additional aluminum incorporation

The acidic properties of hexagonal mesoporous aluminosilicates synthesized via a new successful short time synthesis route using leached saponite and a low concentration of surfactant are thoroughly investigated. The resulting aluminosilicate mesoporous materials with high Si/Al ratios of around 11 have a maximal surface area of 1130 m(2)/g, a pore volume of 0.92 cm(3)/g, and a narrow pore size distribution at around 3 nm. The replacement of the sodium ions, present as counterions in the synthesized aluminosilicates, with protons imparts useful catalytic acidity. This acidity is extensively studied with FTIR spectroscopy after adsorption of ammonia and cyclohexylamine, while deuterated acetonitrile differentiates between Bronsted and Lewis acidity. Al-27 NMR spectroscopy determined the coordination of the aluminum in the FSM materials. Simultaneously the effect of an additional Al incorporation, utilizing sodium aluminate, aluminum nitrate, and aluminum isopropoxide is studied. From an acidic point of view, the incorporation with Al(NO3)(3) appears to be the most optimal, as the sample has a very high amount of acid sites (1.3 mmol/g). Investigating the nature of the acid sites it is found that in all samples except the one incorporated with Al(NO3)(3), more Bronsted than Lewis sites are present, both sites being quite acidic as they resist desorption temperatures up to 300 degreesC. Probing the coordination and location of the Al atoms, all the catalysts appeared to have mostly tetrahedral aluminum, up to 95% of the total Al amount for the proton exchanged AI(NO3)(3) incorporated sample.

Study of wet porous filtration

A growing demand for efficient air quality management calls for the development of technologies capable of meeting the stringent requirements now being applied in areas of chemical, biological and medical activities. Currently, filtration is the most effective process available for removal of fine particles from carrier gases. Purification of gaseous pollutants is associated with adsorption, absorption and incineration. In this paper we discuss a new technique for highly efficient simultaneous purification of gaseous and particulate pollutants from carrier gases, and investigate the utilization of Nuclear Magnetic Resonance (NMR) imaging for the study of the dynamic processes associated with gas-liquid flow in porous media. Our technique involves the passage of contaminated carrier gases through a porous medium submerged into a liquid, leading to the formation of narrow and tortuous pathways through the medium. The wet walls of these pathways result in outstanding purification of gaseous, liquid and solid alien additives. NMR imaging was successfully used to map the gas pathways inside the porous medium submerged into the liquid layer. (C) 2002 Elsevier Science B.V. All rights reserved.

Chemical characterisation of deep profile Ferrosols under sugarcane in wet tropical northern Queensland

The chemical properties of deep profile samples ( up to 12 m) of Ferrosols from northern Queensland were investigated to provide an understanding of the accumulation of nitrate ( NO3) within these soil profiles. The influence of other cations and anions present in the soil solution or on the exchange and the charge chemistry of the profiles were examined with respect to the NO3 accumulations. The major ions in the soil solution were Na, NO3, and chloride ( Cl). Distinct regions of anion accumulation were observed; SO4 accumulated in the upper profile of all cores, whereas NO3 and Cl accumulations were restricted to the lower profile of cores with appreciable AEC (> 1 cmol(c)/kg). Gaines-Thomas selectivity coefficients were used to indicate exchange preference for cations and anions, and are as follows: Al > Ca similar to Mg > K > Na and sulfate (SO4) > Cl similar to NO3. The selectivity of SO4 increased and the extractable SO4 decreased in the lower profile of all cores. This has important implications for the adsorption of NO3 and Cl. The NO3 and Cl accumulations were shown to correspond to a region of low SO4 occupancy of the exchange sites in the lower profile. Along with the high SO4 selectivity, this suggests that SO4 may control the positioning of the NO3 accumulations. It was concluded that the NO3 accumulations were relatively stable under current management practices, although the reduction in NO3 inputs would likely see the gradual replacement of NO3 with Cl as a result of their comparable selectivity for exchange sites.

Nitrate retention under sugarcane in wet tropical Queensland deep soil profiles

Nitrate leaching below the crop root-zone in variable charge soils may be adsorbed at anion exchange sites, thereby temporarily reducing the risk of contamination of water bodies. The objectives of this study were (i) to investigate whether nitrate adsorption, accumulation, and retention in the Johnstone River Catchment of Far North Queensland wet tropics is widespread; (ii) to assess the capacity of soil in the Johnstone River Catchment to retain nitrate; and (iii) to deduce the consequences of nitrate adsorption/desorption on contamination of water bodies. Soil cores ranging from 8 to 12.5 m depth were taken from 28 sites across the catchment, representing 9 Ferrosol soil types under sugarcane (Saccharum officinarum-S) cultivation for at least 50 years and from rainforest. The cores were segmented at 0.5-m depth increments and subsamples were analysed for nitrate-N, cation and anion exchange capacities, pH, exchangeable cations (Ca, Mg, K, Na), soil organic C, electrical conductivity, sulfate-S, and chloride. Nitrate-N concentration under sugarcane ranged from 0 to 72.5 mg/kg, compared with 0 to 0.31 mg/kg under rainforest, both Pin Gin soils. The average N load in 1-12 m depth across 19 highly oxidic profiles of the Pin Gin soil series was 1550 kg/ha, compared with 185 kg/ha under 8 non-Pin Gin soils and 11 kg/ha in rainforest on a Pin Gin soil. Most of the nitrate retention was observed at depth of 2-12 m, particularly at 4-10 m, indicating that the accumulation was well below the crop root-zone. The average maximum potential nitrate retention capacity was 10.8 t/ha for the Pin Gin and 4.7 t/ha for the non-Pin Gin soil. Compared with the current N load, the soils still possess a large capacity to adsorb and retain nitrate in profiles. Retention of large quantities of the leached nitrate deep in most of the profiles has reduced the risk of contamination of water bodies. However, computations show that substantial quantities of the nitrate leached below the root-zone were not adsorbed and remain unaccounted for. This unaccounted nitrate might have entered both on- and off-site water bodies and/or have been denitrified.

Surface diffusion of strongly adsorbing vapors in activated carbon by a differential permeation method

Conventional methods to determine surface diffusion of adsorbed molecules are proven to be inadequate for strongly adsorbing vapors on activated carbon. Knudsen diffusion permeability (B-k) for strongly adsorbing vapors cannot be directly estimated from that of inert gases such as helium. In this paper three models are considered to elucidate the mechanism of surface diffusion in activated carbon. The transport mechanism in all three models is a combination of Knudsen diffusion, viscous flow and surface diffusion. The collision reflection factor f (which is the fraction of molecules undergoing collision to the solid surface over reflection from the surface) of the Knudsen diffusivity is assumed to be a function of loading. It was found to be 1.79 in the limit of zero loading, and decreases as loading increases. The surface diffusion permeability increases sharply at very low pressures and then starts to decrease after it has reached a maximum (B(mum)s) at a threshold pressure. The initial rapid increase in the total permeability is mainly attributed to surface diffusion. Interestingly the B(mum)s for all adsorbates appear at the same volumetric adsorbed phase concentration, suggesting that the volume of adsorbed molecules may play an important role in the surface diffusion mechanism in activated carbon. (C) 2003 Elsevier Ltd. All rights reserved.

Molecular transport in nanopores

Simulation of the transport of methane in cylindrical silica mesopores have been performed using equilibrium and nonequilibrium molecular dynamics (NEMD) as well as dual control volume grand canonical molecular dynamics methods. It is demonstrated that all three techniques yield the same transport coefficient even in the presence of viscous flow. A modified locally averaged density model for viscous flow, combined with consideration of wall slip through a frictional condition, gives a convincing interpretation of the variation of the transport coefficient over a wide range of densities, and for various pore sizes and temperatures. Wall friction coefficients extracted from NEMD simulations are found to be consistent with momentum transfer arguments, and the approach is shown to be more meaningful than the classical slip length concept. (C) 2003 American Institute of Physics.

Solubility of selected esters in supercritical carbon dioxide

The solubility of ethyl propionate, ethyl butyrate, and ethyl isovalerate in supercritical carbon dioxide was measured at temperature ranging from 308.15 to 333.15 K and pressure ranging from 85 to 195 bar. At the same temperature, the solubility of these compounds increases with pressure. The crossover pressure region was also observed in this study. The experimental data were correlated by the semi-empirical Chrastil equation and Peng-Robinson equation of state (EOS) using several mixing rules. The Peng-Robinson EOS gives better solubility prediction than the empirical Chrastil equation. (C) 2002 Elsevier Science B.V. All rights reserved.

Variation of the pore structure of coal chars during gasification

The variation of the pore structure of several coal chars during gasification in air and carbon dioxide was studied by argon adsorption at 87 K and CO2 adsorption at 273 K. It is found that the surface area and volume of the small pores (10 Å for air gasification is constant over a wide range of conversion (>20%), while for CO2 gasification similar results are obtained using the total surface area. However, in the early stages of gasification (

Preparação e caracterização de carvão ativado quimicamente a partir da casca de arroz

This work consists in a study about the chemical activation of charred rice hulls using NaOH as the activation agent. The influence of the naturally-occurring silica was particularly evidenced. X-ray diffraction patterns showed the formation of sodium carbonate and silicates in the activated samples, whereas thermogravimetric curves revealed a strong reduction in the ash content of these samples after washing with water. Nitrogen adsorption data indicated a microporosity development only in the washed samples, with BET surface area values of 450 and 1380 m2/g achieved for the samples activated at 800 °C starting from the precursor with or without silica, respectively.

Remoção do herbicida 2,4-D por meio do tratamento convencional da água e adsorção em carvão ativado granular em instalação piloto

O crescimento populacional empurra a produção agrícola em direção ao uso intensivo dos agrotóxicos que aumentam a produtividade. Porém, seu uso incorreto pode resultar em grave problema para as estações de tratamento da água e impactar negativamente na saúde pública. Segundo estudos em escala laboratorial, o tratamento convencional, um dos mais utilizados no Brasil, apresenta remoção insignificante do 2,4-D. A adsorção em carvão ativado tem se demonstrado como tecnologia eficiente na remoção de diversos contaminantes, dentre eles os agrotóxicos. Assim, foi avaliada a remoção dos herbicidas 2,4-D e 2,4,5-T e metabólito 2,4-DCP, utilizando o tratamento convencional e a adsorção em coluna de carvão ativado granular em instalação piloto. O carvão ativado granular empregado foi o derivado da casca de coco. A concentração dos herbicidas foi analisada por cromatografia líquida de alta eficiência com detector por arranjo de diodos e extração em fase sólida. A associação do tratamento convencional com a adsorção em carvão ativado granular apresentou elevada remoção do 2,4-D (99%) atingindo concentrações finais abaixo do limite da Portaria MS n° 2914/2011. O tratamento convencional, no entanto, também apresentou remoção do 2,4-D (35 a 59%), sendo o maior percentual obtido na decantação (30 a 52%), indicando que houve interação entre a matéria orgânica natural e o 2,4-D, contribuindo para sua remoção nessa etapa. O 2,4-DCP e 2,4,5-T apresentaram concentrações abaixo do limite de detecção.

Avaliação da adsorção do herbicida 2,4-D em carvão ativado em pó utilizando água com diferentes qualidades

O 2,4-diclorofenoxiacético (2,4-D) é um dos herbicidas mais consumidos no Brasil e é preferencialmente usado devido a sua boa seletividade e baixo custo. Possui alta toxidade e baixa biodegradabilidade, oferecendo risco à saúde humana e ao meio ambiente, podendo ser encontrado em solos, águas superficiais e subterrâneas. Estudos mostram que o tratamento convencional da água possui baixa eficácia na remoção de microcontaminantes, com isso várias técnicas têm sido utilizadas na remoção de compostos em água, como a adsorção por carvão ativado. Apresenta-se a adsorção em carvão ativado tem se demonstrado como tecnologia eficiente na remoção de diversos contaminantes, dentre eles os agrotóxicos. Assim, o presente trabalho objetivou avaliar a adsorção do 2,4-D por três carvões ativados em pó (CAP) em água ultrapura e em água bruta do Rio Santa Maria da Vitória. A quantificação do herbicida foi analisada por cromatografia líquida de alta eficiência, após concentração da amostra pelo método de extração em fase sólida. Os ensaios de adsorção foram realizados com carvões ativados derivados da casca de coco (CAP-01), pinus (CAP-02) e palha de café (CAP-03), que foram caracterizados e avaliados na sua capacidade de remoção do 2,4-D nas duas matrizes de água. Dois modelos de isoterma de adsorção, Langmuir e Freundlich, foram aplicados para descrever os dados de adsorção, que indicaram o CAP-02 como o carvão que apresentou a melhor capacidade de adsorção do 2,4-D entre os carvões estudados, tanto em água ultrapura quanto em água bruta. Nos ensaios realizados em água bruta, houve redução da adsorção do 2,4-D para as três amostras de CAP, quando comparado com os ensaios realizados em água ultrapura, indicando interferência de compostos, como a matéria orgânica, no processo de adsorção.

Remoção do herbicida 2,4 diclorofenoxiacético (2,4-D) no tratamento convencional de água e associado à adsorção em carvão ativado em pó (CAP) em escala piloto

O aumento do uso de agrotóxicos no Brasil tem causado muitas preocupações, tanto em relação à questão ambiental quanto a saúde pública. Muitos desses compostos não são eficientemente removidos das águas por tratamento convencional, sendo necessárias alternativas que os removam das águas de abastecimento. Dentre as tecnologias existentes, a adsorção em CAP é considerada uma das mais efetivas e confiáveis, cujas vantagens incluem alta eficiência de remoção e facilidade de operação. O objetivo desta pesquisa é avaliar a remoção, em escala piloto, do agrotóxico 2,4-D e o seu principal metabólito 2,4-DCP em amostras de águas tratadas por adsorção em CAP associado ao tratamento convencional. Os testes foram realizados em instalação piloto na áreada ETA Carapina/CESAN. A água bruta foi a proveniente do rio Santa Maria da Vitória contaminadaatravés da adição de agrotóxico em sua fórmula comercial. Foram realizados quatro ensaios, dois sem adição de CAP e dois com adição de CAP junto à unidade de mistura rápida. Os agrotóxicos foram detectados e quantificados através da cromatografia líquida de alta eficiência, em metodologia validada. As amostras coletadas foram caracterizadas de acordo com os parâmetros: temperatura, turbidez, condutividade elétrica, absorbância em 254 nm, cor real, cor aparente, alcalinidade, carbono orgânico total, além e concentração dos agrotóxicos 2,4-D e ácido 2,4,5-T e do metabólito 2,4-DCP. Os diferentes ensaios foram avaliados em termos da taxa de remoção destes parâmetros. Como resultado no TCVcom adição de CAP o composto de interesse foi removido abaixo de 30 μg. L-1,Valor Máximo Permitido, estabelecido pela Portaria do MS n° 2.914/2011 para dosagem de 100μg.L-1e mostrou-se eficiente, também, na remoção de matéria orgânica. Em nenhum dos testes foi detectado o composto 2,4-DCP e 2,4,5-T.

Soil profile internal drainage for a central pivot fertigated coffee crop

Coffee cultivation via central-pivot fertigation can lead to fertilizer losses by soil profile internal drainage when water application is excessive and soils have low water retention and cation adsorption capacities. This study analyses the deep water losses from the top 1 m sandy soil layer of east Bahia, Brazil, cultivated with coffee at a high technology level (central-pivot fertigation), using above normal N fertilizer rates. The deep drainage (Q) estimation is made through the application of a climatologic water balance (CWB) program having as input direct measures of irrigation and rainfall, climatological data from weather stations, and measured soil water retention characteristics. The aim of the study is to contribute to the understanding of the hydric regime of coffee crops managed by central-pivot irrigation, analyzing three scenarios (Sc): i) rainfall only, ii) rainfall and irrigation full year, and iii) rainfall and irrigation dry season only. Annual Q values for the 2008/2009 agricultural year were: Sc i = 811.5 mm; Sc ii = 1010.5 mm; and Sc iii = 873.1 mm, so that the irrigation interruption in the wet season reduced Q by 15.7%, without the appearance of water deficit periods. Results show that the use of the CWB program is a convenient tool for the evaluation of Q under the cited conditions.

Templated synthesis of carbon materials mediated by porous clay heterostructures

Mesoporous carbon materials were prepared through template method approach using porous clay heterostructures (PCHs) as matrix and furfuryl alcohol as carbon precursor. Three PCHs prepared using amines with 8, 10 and 12 carbon atoms were used. The effect of several impregnation-polymerization cycles of the carbon precursor, the carbonization temperature and the need of a previous surface alumination were evaluated. The presence of two porosity domains was identified in all the carbon materials. These two domains comprise pores resulting from the carbonization of the polymer film formed in the inner structure of the PCH (domain I) and larger pores created by the clay particles aggregation (domain II). The predominance of the porosity associated to domain I or II can be achieved by choosing a specific amine to prepare the PCH matrix. Carbonization at 700 C led to the highest development of pores of domain I. In general, the second impregnation-polymerization cycle of furfuryl alcohol resulted in a small decrease of both types of porosity domains. Furthermore the previous acidification of the surface to create acidic sites proved to be unnecessary. The results showed the potential of PCHs as matrices to tailor the textural properties of carbons prepared by template mediated synthesis.

Modification of MOR by desilication treatments: Structural, textural and acidic characterization

The effect of several desilication experimental parameters (base concentration, temperature and time) on the characteristics of MOR zeolite was studied. The samples were characterized by X-ray diffraction, Al-27 and Si-29 MAS-NMR, chemical analysis, and FTIR (framework vibration region). The textural characterization was made by N-2 adsorption and the acidity was evaluated by pyridine adsorption followed by FTIR and by the catalytic model reaction of n-heptane cracking. The alkaline treatments promoted the Si extraction from the zeolite framework, without considerable loss of crystallinity and, as it was envisaged, an important increase of the mesoporous structure was attained. A linear correlation between the number of framework Si per unit cell. N-Si and the asymmetric stretching wavenumber, nu(i), was observed. The acidity characterization shows that the desilicated samples exhibit practically the same acid properties than the parent HMOR zeolite. The optimum desilication conditions were those used to obtain sample M/0.2/85/2, i.e., sample treated with 0.2 M NaOH solution at 85 degrees C for 2 h.