Amino-functionalized MCM-41 and MCM-48 for the removal of chromate and arsenate.

The aim of the present work was to investigate the efficiency of three amino-functionalized (hexadecylamine, dodecylamine, and dimethyldodecylamine) mesoporous silicas (MCM-41 and MCM-48) toward the adsorption of arsenate and chromate. Hexadecylamine-functionalized materials were characterized; BET surface areas, pore volumes, and sizes decreased with the functionalization, whereas XRD patterns show that the hexagonal structure of MCM-41 and the cubic structure of MCM-48 were not modified. The zeta potential decreases with pH and the highest arsenate and chromate removal was observed at the lowest pHs. Adsorption of chromium and arsenate was significantly enhanced after functionalization and amino-functionalized MCM-41 adsorb larger amounts of arsenate when compared to expanded MCM-48 materials. Chromate sorption capacities increased with the chain length and the larger capacities were obtained with hexadecylamine-functionalized mesoporous silicas. Mesoporous silicas modified by dimethyldodecylamine exhibited the higher arsenate sorption capacities.

Cloud point extraction of Δ9-tetrahydrocannabinol from cannabis resin.

A cloud point extraction coupled with high performance liquid chromatography (HPLC/UV) method was developed for the determination of Δ(9)-tetrahydrocannabinol (THC) in micellar phase. The nonionic surfactant "Dowfax 20B102" was used to extract and pre-concentrate THC from cannabis resin, prior to its determination with a HPLC-UV system (diode array detector) with isocratic elution. The parameters and variables affecting the extraction were investigated. Under optimum conditions (1 wt.% Dowfax 20B102, 1 wt.% Na2SO4, T = 318 K, t = 30 min), this method yielded a quite satisfactory recovery rate (~81 %). The limit of detection was 0.04 µg mL(-1), and the relative standard deviation was less than 2 %. Compared with conventional solid-liquid extraction, this new method avoids the use of volatile organic solvents, therefore is environmentally safer.

Extraction of humic acid by coacervate: investigation of direct and back processes.

The two aqueous phases extraction process is widely used in environmental clean up of industrial effluents and fine chemical products for their reuse. This process can be made by cloud point of polyethoxylated alcohols and micellar solubilization phenomenon. It is commonly called "coacervate extraction" and is used, in our case, for humic acid extraction from aqueous solution at 100mg/L. The surfactants used are alcohol polyethoxylate and alkylphenol polyethoxylate. Phase diagrams of binary water/surfactant and pseudo-binary are plotted. The extraction results are expressed by the following responses: percentage of solute extracted, E (%), residual concentrations of solute and surfactant in dilute phase (X(s,w), and X(t,w) respectively) and volume fraction of coacervate at equilibrium (ϕ). For each parameter, the experimental results are fitted to empirical equations in three dimensions. The aim of this study is to find out the best compromise between E and ϕC. The comparison between experimental and calculated values allows models validation. Sodium sulfate, cetyltrimethylammonium bromide (CTAB) addition and pH effect are also studied. Finally, the possibility of recycling the surfactant has been proved.

Elimination of fuel spills from effluent using cloud point extraction methods.

Cloud point extraction procedure was used to remove hydrocarbons from aqueous streams coming from fuels storage centre. This real effluent was characterized by a high chemical oxygen demand (COD=7000 mg O(2)/L) due to significant concentration of hydrocarbons as gasoline diesel and kerosene. Two biodegradable non-ionic surfactants (Lutensol AO7 and Triton X-114) were employed to treat this effluent. First, the phase diagrams of the binary systems, water-surfactant and the pseudo-binary system, water-surfactant-hydrocarbons were determined. The effect of sodium sulphate on water-surfactant-hydrocarbons systems was studied. The experimental results, with respect to surfactant wt.% and temperature, were expressed in term of residual (soluble) chemical oxygen demand (COD(S)), residual concentrations of surfactant in the dilute phase (X(t,w)) converted to chemical oxygen demand (COD(TA)) and the volume fraction of coacervate (phi(C)) at the equilibrium. The results obtained for each parameter were represented on three-dimensional diagrams using an empirical fitting method. For instance, COD can be decreased from 7000 mg O(2)/L to 50 mg O(2)/L and 30 mg O(2)/L, using Triton X-114 and Lutensol AO7, respectively at room temperature. However, the extraction extent of such effluent was found to be low at basic pH, which may be useful for surfactant regeneration.

Aqueous heavy metals removal on amine-functionalized Si-MCM-41 and Si-MCM-48.

Ordered mesoporous silica with hexagonal and cubic structure, type MCM-41 and MCM-48 respectively, were synthesized under basic media using pure silica, cetyltrimethylammonium bromide and tetramethylammonium hydroxide, for MCM-41 and tetraethylorthosilica, cetyltrimethylammonium and NaOH for MCM-48. The expanded materials were prepared by post-synthesis method with N-N dimethyldodecylamine (DMDDA) and dodecylamine (DDA). Small angle X-ray diffraction, nitrogen adsorption-desorption measurements, FT-IR and thermogravimetry were used to characterize the samples. The expanded materials were tested for adsorption of Cd(2+), Co(2+), Cu(2+) and Pb(2+) in aqueous solution. Aminated materials were found to be fast adsorbents for metallic ions cation with affinity for Cu(2+), Pb(2+), than for Cd(2+) and Co(2+) from single solution. In mixed metallic ions cation solutions, competition by the adsorption sites is likely to occur, the adsorption preference is for Cu(2+)and Pb(2+). The kinetic of the reaction is very rapid and follow pseudo-second order and clearly indicated that Langmuir model describe better the for metal ions adsorption on aminated mesoporous material than Freundlich model.

Color removal from acid and reactive dye solutions by electrocoagulation and electrocoagulation/adsorption processes.

In this study, electrocoagulation of Marine Blue Erionyl MR (acid dye) and electrocoagulation followed by adsorption of Brilliant Blue Levafix E-BRA (reactive dye) from aqueous solutions were investigated, using aluminum electrodes and granular activated carbon (GAC). In the electrocoagulation and adsorption of dyestuff solutions, the effects of current density, loading charge, pH, conductivity, stirring velocity, contact time, and GAC concentration were examined. The optimum conditions for the electrocoagulation process were identified as loading charges 7.46 and 1.49 F/m3, for a maximum abatement of 200 mg/L reactive and acid dye, respectively. The residual reactive dye concentration was completely removed with 700 mg/L GAC. The results of this investigation provide important data for the development of a combined process to remove significant concentrations of recalcitrant dyes from water, using moderate activated carbon energy and aluminum consumption, and thereby lowering the cost of treatment.

Adsorption of Supranol Yellow 4 GL from aqueous solution by surfactant-treated aluminum/chromium-intercalated bentonite.

The aim of this paper is to study the adsorption of the acid dye Supranol Yellow 4 GL (S.Y. 4 GL) from aqueous solution on an inorgano-organo clay. Bentonite is naturally occurring clay with good exchanging ability. By exchanging its interlamellar cations with cetyltrimethylammonium bromide (CTAB) and hydroxyaluminic or chromium polycations, the properties of natural bentonite can be greatly improved. Batch adsorption tests of Supranol Yellow 4 GL were carried out at 20 degrees C and constant pH 6.5. To investigate the adsorption mechanisms, the simplified kinetic models, such as pseudo-first-order, pseudo-second-order, Elovich equation and intraparticle diffusion are tested. The results show that adsorption follows second-order rate kinetic. The correlation coefficients obtained for second-order kinetics model are greater than 0.998 indicating a better fitting of this equation. The experimental data are analysed by Langmuir, Freundlich and Elovich isotherms. The equilibrium adsorption capacity of anionic dye is determined from the Langmuir equation and found to be 142, 85 and 128, 20mg/g (standard deviation; Deltaq (%)=3.52 and 18.51) for CTAB-Cr-B and CTAB-Al-B, respectively.

Simultaneous elimination of dissolved and dispersed pollutants from cutting oil wastes using two aqueous phase extraction methods.

Oily wastewater experimental study has been accomplished using two aqueous phases extraction methods on the basis of phase separation properties of non-ionic surfactants above the so-called cloud point curve and the solubilization phenomena of coacervate micelles (surfactant rich phase). Two commercial ethoxylate fatty alcohol surfactants (Oxo-C(10)E(3), Oxo-C(15)E(7)) were employed to treat three kinds of cutting oil wastewater, in order to define the conditions promoting cutting oils emulsions destabilization and cloud point extraction possesses simultaneously. Before extraction test, the phase diagrams of binary water/surfactants systems were drawn and the effect of some cutting oil additives on water-surfactant systems was, therefore studied. The results of oily wastewater extraction with respect to wt.% surfactant and temperature were expressed in terms of chemical oxygen demand (COD) of the dilute phase before and after extraction, residual chemical oxygen demand (COD(R)), residual concentrations of surfactant in the dilute phase (X(t,w)) converted to chemical oxygen demand (COD(T)) and the volume fraction of coacervate (phi(c)) at the equilibrium. The results obtained for each parameter which were also represented on three dimensional diagrams using an empirical smoothing method were in agreement with the experimental ones, where the COD(R) was reduced from 55 to 1.1 g O(2)l(-1).

Adsorption of zinc on natural sediment of Tafna River (Algeria).

The environmental impact of metal additions to sediment depends on its sorption ability. The paper presents a study of zinc adsorption using the experiment data on natural sediment of Tafna River in northwest of Algeria. The effect of various operating variables, namely initial concentration, mass of sediment, and contact time, have been studied. The optimum contact time needed to reach equilibrium is of the order of 30 min and is independent of initial concentration and mass of zinc ions. The extent of adsorption increases with increase of concentration, and with decrease of adsorbent mass. The content of carbonate in sediment increases the adsorption indicating the active support material towards zinc ions. A batch sorption model, which assumes the pseudo-second-order mechanism, is developed to predict the rate constant of the sorption, the equilibrium sorption capacity and the initial sorption rate with the effect of initial zinc ion concentration and sediment dose. Various thermodynamic parameters, such as DeltaG degrees , DeltaH degrees and DeltaS degrees , have been calculated. The thermodynamics of zinc ion/sediment system indicates spontaneous, endothermic and randomness nature of the process.

Reduction of clinkerization temperature by using phosphogypsum.

Valorization of phosphogypsum as mineralizer in the burning of Portland cement clinker was studied in our laboratory. X-ray fluorescence, optical microscope technique and powder X-ray diffraction were then used to characterize the synthesized clinker and its raw mixture in terms of chemical composition and clinker mineralogical composition. The effects of phosphogypsum on structural and morphological properties of clinker minerals and on the presence of alite were followed by scanning electron microscopy combined with microprobe analysis. The addition of phosphogypsum to the cement raw mixture shows that the burning temperature decreases and therefore improves the production process of clinker. The addition of 10% phosphogypsum permits a complete clinkerization at low burning temperature (1200 degrees C), instead of 1470 degrees C, which increases the cement factory efficiency by 25% and extends the service life of furnace fire brick. Structural and morphological analysis of clinker produced under the new conditions show that phosphogypsum preserve perfectly the crystalline structure of silicate phases, which leads to the improvement of physical and mechanical properties of cement.

Removal of Supranol Yellow 4GL by adsorption onto Cr-intercalated montmorillonite.

Cr(III)-intercalated montmorillonite was utilized as an adsorbent for the removal of the organic pollutant, Supranol Yellow 4GL, a synthetic dye used for chemical fibres. The material was prepared by the reaction of Na montmorillonite with a base-hydrolyzed solution of Cr nitrate salt (OH(-)/Cr(3+) molar ratios of 2). XRD data showed that the interlayer spacing (d(001)) of montmorillonite was increased from 12.35 to 23.06 Angstroms. The kinetics and mechanism of the adsorption of the acid dye, Supranol Yellow 4GL, on Cr(III)-intercalated montmorillonite was investigated. The equilibrium time was reached within 30 min. The process follows pseudo-second-order rate kinetics. The Langmuir isotherm described the adsorption data over the concentration range (20-160 mg/l). The separator factor R(L) revealed the favourable nature of this adsorption process. Also, the thermodynamic parameters such as DeltaS degrees, DeltaH degrees, DeltaG degrees were determined.

Sorption study of an acid dye from an aqueous solutions using modified clays.

The removal of the pollutant Supranol Yellow 4GL (S.Y.4GL) was studied by using different clays: clay exchanged with sodium (BNa+) and hydroxyaluminic polycation pillared clays in the presence or absence of non-ionic surfactant. While decomposing the surfactant at 500 degrees C, the surface of the clay changed significantly. The study of the behaviour of the three clays with respect to coloring solutions, allowed to determine the equilibrium time and the rate-determining step of the dye S.Y.4GL adsorption. Two simplified kinetic models, were tested to investigate the adsorption mechanisms in terms of pseudo-first order and pseudo-second order equations. Besides, the adsorption capacity data were fitted to Langmuir and Freundlich equations as well. A better fixation was obtained with an acidic pH. The effect of temperature on the adsorption of dye has been also studied and the thermodynamic parameters DeltaG degrees , DeltaH degrees and DeltaS degrees were determined.

Equilibrium and kinetics of color removal from dye solutions with bentonite and polyaluminum hydroxide.

Wastewater from the textile industry contains soluble dyes that are toxic and particularly difficult to remove. A promising low-cost treatment, however, is use of polyaluminum hydroxide associated with bentonite. At suitable conditions, this process is able to efficiently remove color from solutions containing mixtures of soluble acid azo dyes and produce easily settleable sludge. The removal mechanism, which is believed to involve adsorption or precipitation and weak pH variations, is not well understood. With the overall reaction being second order, two elementary first-order reactions could be assumed. The equilibrium removal is a decreasing function of the temperature. However, this effect is weak and decreases when the dye concentration increases. At usual values of concentration in textile wastewater, this effect can be neglected. The resulting solid compound is particularly resistant to mechanical stress. Moreover, color was significantly released at pH greater than 8. Sodium ions have no influence on the compound stability, which reinforces the assumption of the involvement of an adsorption process.