clay and 4-nitrophenol

The present research highlights the use of a montmorillonite clay to remove p-nitrophenol (PNP) from aqueous solution. The montmorillonite clay was characterized using powder X-ray diffraction, Fourier-transformed infrared spectroscopy, scanning electron microscopy, X-ray fluorescence, Brunauer-Emmett-Teller analyses, and zero point charge in order to establish the adsorption behavior-properties relationship. The physiochemical parameters like pH, initial PNP concentration, and adsorbent dose as well as their binary interaction effects on the PNP adsorption yield were statistically optimized using response surface methodology. As a result, 99.5% removal of PNP was obtained under the optimal conditions of pH 2, adsorbent dose of 2 g/l, and PNP concentration of 20 mg/l. The interaction between adsorbent dose and initial concentration was the most influencing interaction on the PNP removal efficiency. The mass transfer of PNP at the solution/adsorbent interface was described using pseudo-first-order and intraparticle diffusion. Langmuir isotherm well fitted the experimental equilibrium data with a satisfactory maximum adsorption capacity of 122.09 mg/g. The PNP adsorption process was thermodynamically spontaneous and endothermic. The regeneration study showed that the montmorillonite clay exhibited an excellent recycling capability. Overall, the montmorillonite clay is very attractive as an efficient, low-cost, eco-friendly, and recyclable adsorbent for the remediation of hazardous phenolic compounds in industrial effluents.

Topics: Adsorption; Bentonite; Clay; Diffusion; Hydrogen-Ion Concentration; Kinetics; Nitrophenols; Surface Properties; Thermodynamics; Water Pollutants, Chemical; Water Purification

Organoclays are effective sorbents for removal of organic contaminants from water, but their regeneration capacity limits their practical use as a biotechnological process for bioremediation. Here, the sorption of p-nitrophenol (PNP) to crystal violet (CV)-modified montmorillonite and its biodegradation by the bacterium Arthrobacter sp. 4Hβ were studied in a batch aqueous system. The degree of PNP sorption was dependent on the degree of CV modification (loaded at 80 % or 100 % of the clay's cation-exchange capacity-CVM80 and CVM100, respectively). CV sorption to the clay reduced its toxicity to bacteria. PNP at an initial concentration of 0.72 mM was degraded at rates of 65 % and 42 % in CVM80 and CVM100 suspensions, respectively. Both free and CV-clay-adsorbed PNP concentrations were reduced by the bacteria at rates proportional to the degree of CV modification. Three successive cycles of PNP reloading-degradation in the organoclay suspension demonstrated the potential of this matrix's regeneration and reuse toward maximal removal efficiency of organic pollutants.

Topics: Adsorption; Aluminum Silicates; Arthrobacter; Clay; Gentian Violet; Nitrophenols; Water Purification

Montmorillonite (MMT) was converted to organoclays by intercalation of cationic surfactants into its interlayer space. Two types of organoclays were prepared from different surfactants (DDTMA and DDDMA) at different surfactant loadings, and the structural changes in the clays investigated using various techniques. The arrangements of surfactant molecules in the interlayer space was visually aided by molecular mechanical calculation (MM calculation), and the adsorption capacities of MMT and the organoclays for the removal of p-chlorophenol (PCP) and p-nitrophenol (PNP) from aqueous solutions were tested under different conditions. Two adsorption isotherm models (Langmuir and Freundlich isotherms) were used to determine the best fit model and the Freundlich isotherm was found to provide better fit for both PCP and PNP. Due to its hydrophobic properties, the adsorption is more favourable for PNP than PCP. Overall, the adsorption capacity of the organoclays was significantly improved by intercalation with large surfactant molecules as well as highly loaded surfactants as the intercalation with large surfactant molecules created the partitioning phase, which strongly attracted large amounts of organic pollutants. Possible mechanisms and the implications of the results for the use of these organoclays as adsorbents for the removal of phenols from the environment are discussed.

Topics: Adsorption; Aluminum Silicates; Bentonite; Chlorophenols; Clay; Nitrophenols; Phenols; Quaternary Ammonium Compounds; Surface-Active Agents; Water Pollutants, Chemical; X-Ray Diffraction

Modified montmorillonite was prepared at different surfactant (HDTMA) loadings through ion exchange. The conformational arrangement of the loaded surfactants within the interlayer space of MMT was obtained by computational modelling. The conformational change of surfactant molecules enhance the visual understanding of the results obtained from characterization methods such as XRD and surface analysis of the organoclays. Batch experiments were carried out for the adsorption of p-chlorophenol (PCP) and different conditions (pH and temperature) were used in order to determine the optimum sorption. For comparison purpose, the experiments were repeated under the same conditions for p-nitrophenol (PNP). Langmuir and Freundlich equations were applied to the adsorption isotherm of PCP and PNP. The Freundlich isotherm model was found to be the best fit for both of the phenolic compounds. This involved multilayer adsorptions in the adsorption process. In particular, the binding affinity value of PNP was higher than that of PCP and this is attributable to their hydrophobicities. The adsorption of the phenolic compounds by organoclays intercalated with highly loaded surfactants was markedly improved possibly due to the fact that the intercalated surfactant molecules within the interlayer space contribute to the partition phases, which result in greater adsorption of the organic pollutants.

Topics: Adsorption; Aluminum Silicates; Cetrimonium; Cetrimonium Compounds; Chlorophenols; Clay; Molecular Dynamics Simulation; Molecular Structure; Nitrophenols; Surface Properties; Surface-Active Agents

Organoclays were synthesised through ion exchange of a single surfactant for sodium ions, and characterised by a range of method including X-ray diffraction (XRD), BET, X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FT-IR), and transmission electron microscopy (TEM). The change in surface properties of montmorillonite and organoclays intercalated with the surfactant, tetradecyltrimethylammonium bromide (TDTMA) were determined using XRD through the change in basal spacing and the expansion occurred by the adsorbed p-nitrophenol. The changes of interlayer spacing were observed in TEM. In addition, the surface measurement such as specific surface area and pore volume was measured and calculated using BET method, this suggested the loaded surfactant is highly important to determine the sorption mechanism onto organoclays. The collected results of XPS provided the chemical composition of montmorillonite and organoclays, and the high-resolution XPS spectra offered the chemical states of prepared organoclays with binding energy. Using TGA and FT-IR, the confirmation of intercalated surfactant was investigated. The collected data from various techniques enable an understanding of the changes in structure and surface properties. This study is of importance to provide mechanisms for the adsorption of organic molecules, especially in contaminated environmental sites and polluted waters.

Topics: Adsorption; Aluminum Silicates; Clay; Nitrophenols; Surface Properties; Surface-Active Agents; Trimethyl Ammonium Compounds

Sorption properties of an iron surfactant-modified pillared montmorillonite (Fe-SMPM) toward two organic pollutants, basic yellow 28 dye (BY28) and 4-nitrophenol (4-NP), were studied at different pH values in both single component and binary pollutant systems. The pseudo-first-order model fits well with the kinetic data obtained in single component studies and sorption capacities of both BY28 and 4-NP increased with the pH value. A sorption synergetic mechanism was observed in binary systems; 4-nitrophenol adsorption was enhanced by the presence of BY28 in the mixture and increased with dye concentrations. Isotherms were described using the Freundlich model in single component systems and the Sheindorf-Rebhun-Sheintuch (SRS) model, an extended Freundlich model, in binary mixtures systems. Hydrophobic interactions between the surfactant-modified pillared clay and the pollutants were suggested to explain the sorption mechanisms.

Topics: Adsorption; Aluminum Silicates; Azo Compounds; Bentonite; Clay; Coloring Agents; Iron; Kinetics; Molecular Structure; Nitrophenols; Organic Chemicals

The adsorption and degradation of 4,6-o-dinitrocresol (DNOC) and p-nitrophenol (PNP) in SWy-2 montmorillonite clay slurry were investigated. The pH and type of cation of the slurry were varied. Results showed that adsorption of DNOC and PNP increased at lower pH values, and when pH < pKa(4.4) of DNOC, DNOC was almost completely adsorbed on the clay under given experimental conditions. The specific cation also had a significant effect on adsorption, which was dramatically enhanced in the presence of K+ and NH4+, compared with the presence of Na+ or Ca2+. Anodic Fenton treatment (AFT) degradation of DNOC and PNP in the clay slurry was studied, and it was found that DNOC degradation rates were greatly affected by the initial pH and the types of electrolytes. Due to the higher adsorption, the degradation rate substantially decreased in the clay slurry system in the presence of K+ and low pH, with a large amount of DNOC residue remaining after 60 min treatment. AFT degradation of PNP was completed within 30 min treatment. Based on LC-MS data, a DNOC degradation pathway was proposed. Overall, the results showed the inhibition effect of adsorption on the degradation of nitroaromatic compounds in montmorillonite clay slurry by AFT, providing important implications for water and soil remediation.

Topics: Adsorption; Aluminum Silicates; Bentonite; Chromatography, Liquid; Clay; Dinitrocresols; Electrodes; Electrolytes; Hydrogen Peroxide; Hydrogen-Ion Concentration; Iron; Mass Spectrometry; Nitrogen; Nitrophenols; Sewage; Temperature; Time Factors; X-Ray Diffraction

Infrared spectroscopy has been used to study the adsorption of para-nitrophenol on mono-, di- and tri-alkyl surfactant intercalated montmorillonite. Organoclays were obtained by the cationic exchange of mono-, di- and tri-alkyl chain surfactants for sodium ions [hexadecyltrimethylammonium bromide (HDTMAB), dimethyldioctadecylammonium bromide (DDOAB), methyltrioctadecylammonium bromide (MTOAB)] in an aqueous solution with Na-montmorillonite. Upon formation of the organoclay, the properties change from strongly hydrophilic to strongly hydrophobic. This change in surface properties is observed by a decrease in intensity of the OH stretching vibrations assigned to water in the cation hydration sphere of the montmorillonite. As the cation is replaced by the surfactant molecules, the para-nitrophenol replaces the surfactant molecules in the clay interlayer. Bands attributed to CH stretching and bending vibrations change for the surfactant intercalated montmorillonite. Strong changes occur in the HCH deformation modes of the methyl groups of the surfactant. These changes are attributed to the methyl groups locking into the siloxane surface of the montmorillonite. Such a concept is supported by changes in the SiO stretching bands of the montmorillonite siloxane surface. This study demonstrates that para-nitrophenol will penetrate into the untreated clay interlayer and replace the intercalated surfactant in surfactant modified clay, resulting in the change of the arrangement of the intercalated surfactant.

Topics: Adsorption; Aluminum Silicates; Clay; Nitrophenols; Silicon Dioxide; Spectrophotometry, Infrared; Surface-Active Agents; Vibration

Water purification is of extreme importance worldwide. p-Nitrophenol was used as a test chemical to design and test an organoclay for the removal of p-nitrophenol from an aqueous solution. Synthesis of the organoclay with methyltrioctadecylammonium bromide [CH(3)(CH(2))(17)](3)NBr(CH(3)) labeled as MTOAB results in multiple expansions of the montmorillonite clay from 1.24 nm to a maximum of 5.20 nm as is evidenced by the XRD patterns. Thermal analysis shows strong bonding of the surfactant to the clay siloxane layers and the interaction of the p-nitrophenol with the clay surfaces. It is proposed that the p-nitrophenol penetrates the siloxane layer of the clay and bonds through the ditrigonal space of the siloxane hexagonal units to the inner OH units. Such a concept is supported by the observation of an additional infrared band at 3652 cm(-1) for the organoclay. Shifts in the p-nitrophenol OH stretching vibrations mean a strong interaction of the p-nitrophenol molecule. Significant changes in the siloxane stretching bands are also observed.

Topics: Adsorption; Aluminum Silicates; Bentonite; Bromides; Chemistry, Physical; Clay; Nitrophenols; Quaternary Ammonium Compounds; Sodium; Spectrophotometry, Infrared; Surface Properties; Temperature; Thermogravimetry; X-Ray Diffraction