Removal of Oil Spills from Salty Waters by Commercial Organoclays

In this study two commercial organoclays, Cloisite 15A and Cloisite 30B, were used to investigate their potential for removing of light and heavy crude oils from salty waters. The results of batch kinetic studies indicated that the equilibrium time can be reached within 25–30 minutes of contact time. In addition experiments were performed to determine the effect of salinity, temperature, pH and mixing time on the adsorption process. The adsorption isotherms were obtained for the crude oils at equilibrium, at an optimum pH value of 11.73 and temperature of 19°C for which the initial oil contents varied in the range of 100 to 2000 ppm. Experimental results showed that oil sorption onto these organoclays can be described by Freundlich isotherm. Further, it was found that the oil removal efficiency for Cloisite 30B is higher than that of Cloisite 15A and the greater sorption was observed for Gachsaran crude oil onto the organoclays over Soroosh crude oil.     

Effect of surface modification of montmorillonite on the properties of rigid polyurethane foam composites

<正>This study investigated the influence of various organically modified montmorillonites(organoclays) on the structure and properties of rigid polyurethane foam(RPUF) nanocomposites.The organoclays were modified with cetyltrimethyl ammonium bromide(CTAB),methyl tallow bis(2-hydroxyethyl) quaternary ammonium chloride (MT2ETOH) and tris(hydroxymethyl)aminomethane(THMA) and denoted as CMMT,Cloisite 30B and OMMT, respectively.MT2ETOH and THMA contain hydroxyl groups,while THMA does not have long aliphatic tail in its molecule. X-ray diffraction and transmission electron microscopy show that OMMT and Cloisite 30B can be partially exfoliated in the RPUF nanocomposites because their intercalating agents MT2ETOH and THMA can react with isocyanate.However, CMMT modified with nonreactive CTAB is mainly intercalated in the RPUF matrices.At a relatively low filler content,the RPUF/CMMT composite foam has a higher specific compressive strength(the ratio of compressive strength against the apparent density of the foams),while at relatively high filler contents,RPUF/Cloisite 30B and RPUF/OMMT composites have higher specific compressive strengths,higher modulus and more uniform pore size than the RPUF/CMMT composite.     

Comparative analysis of nanocomposites based on polypropylene and different montmorillonites

Nanocomposites of polypropylene (PP) were prepared by melt mixing using maleic anhydride modified polypropylene (PPg) and different organophilic montmorillonites (OMMT). The selected organo-modified clays differ in their initial particle size, amount and type of surfactant and/or their cation-exchange capacity. All composites have 80, 15 and 5 wt% of PP, PPg and OMMT, respectively. The materials were characterized using TGA, XRD, SEM and rotational rheometry. Cloisite 15A, Cloisite 93A, Nanomer I44 and a bentonite modified with octadecylammonium (B18) display intercalation and exfoliation after mixing and annealing and produce nanocomposites with different degrees of ‘solid-like’ rheological behavior. The composites based in Cloisite 15A and Nanomer I44, which use the same intercalant, show very similar phase structure and rheological response, regardless of the origin and initial characteristics of the clays. These nanocomposites are the most affected by the thermal history during rheological characterization in the molten state. On the other hand, Cloisite 10A and Cloisite 30B display collapse of the silicate layers after compounding with no evidence of exfoliation.     

Studies on removal of cobalt from an alkaline waste using synthetic calcium hydroxyapatite

The removal of cobalt from an alkaline waste solutions containing sodium was carried out using a radiotracer in a batch method using synthetic calcium hydroxyapatite (HAP). The influence of different parameters such as solution pH, contact time, cobalt concentration, and presence of other ions like sodium on cobalt removal was studied. The sorption process followed pseudo-second-order kinetics with necessary time of around 23–25 h to reach equilibrium and the cobalt uptake was quantitatively evaluated using the Freundlich model. The results indicated that the mechanism of cobalt removal by HAP was mainly due to chemisorption on a heterogeneous surface. In the presence of sodium, the sorption of cobalt on HAP was not affected. The sorption of cobalt on HAP was pH independent in the range from 4 to 8, because of its buffering properties. The adsorption of cobalt on HAP was fast and the percentage of cobalt sorption was >97 % during the first 30–40 min of the contact time.     

A novel comparative study of different layered silicate clay types on exfoliation process and final nanostructure of trifunctional epoxy nanocomposites

The effect of three different organically modified layered silicate clays (Nanomer I.30E, Cloisite 30B and Nanofil SE 3000) on the exfoliation process and on the thermal properties and nanostructure of cured trifunctional epoxy resin based nanocomposites was studied. Optical microscopy showed that the best and poorest qualities of clay distribution in the epoxy matrix were obtained with Nanofil SE 3000 and Nanomer I.30E, respectively. However, the isothermal differential scanning calorimetry scans show that, of the three systems, it is only the Nanomer clay that promotes intra-gallery reaction due to homopolymerisation, appearing as an initial rapid peak prior to the cross-linking reaction. This rapid intra-gallery reaction is not present in the curing curve for the Cloisite and Nanofil systems. This fact implies that the fully cured nanostructure of the Cloisite and Nanofil system is poorly exfoliated, which is confirmed by small angle X-ray scattering which shows a scattering peak for these systems at around 2.53°, corresponding to about 3.5 nm d-spacing.     

Influence of Surfactants Synergism on the Adsorption Behavior at Air/Water and Solid/Water Interfaces

The influence of synergistic interaction between sodium dodecylsulfate (SDS) and N,N-dimethyldodecan-1-amine oxide (DDAO) on their adsorption at air/water and solid/water interfaces at 20°C is investigated. The critical micelle concentration values obtained from surface tension measurements indicated strong synergism between SDS and DDAO, according to regular solution model. The excess surface concentration (Γ) and the minimum occupied area by single and mixed surfactant monomers (A_min) at liquid/air interface were also calculated. The adsorption onto the activated charcoal and silica was then measured to find out the correlation between surfactant synergism and their adsorption at solid/water interface. The amounts of surfactant adsorbed onto 1 wt% activated charcoal follow the trend: SDS/DDAO > DDAO > SDS. SDS molecules do not adsorb onto 5 wt% silica substrate, while SDS/DDAO mixed system was found to have the highest adsorption behavior. The obtained indicate that SDS can be removed from water by mixing it with amphoteric surfactant.     

Wettability Alteration with Silica Aerogel Nanodispersion

This work studies the wettability alteration using nanoporous silica aerogels for enhanced oil recovery. Water wet flat glass and outcrop sandstone are used for this aim. Modified silica aerogels are synthesized with cheap water glass as the precursor, and ambient pressure drying method. Sessile drop method was used to measure the contact angles. Sandstones with 0° contact angle changed to mixed wet with 88° contact angle, and flat glasses with a 30° contact angle change to 70° contact angle. Results show that silica aerogels have a great potential in wettability alteration of reservoir rocks by adsorption and deposition mechanisms.     

Adsorption of Fe(III) from Aqueous Medium onto Glycine-Modified Chitosan Resin: Equilibrium and Kinetic Studies

The adsorption of Fe(III) onto glycine-modified chitosan (G@Chs) resin has been investigated. The parameters studied include the effects of pH, contact time, and initial metal ion concentrations by batch method. The optimal pH for the adsorption of Fe(III) was found to be 2.5. The results obtained from equilibrium adsorption studies are fitted in various adsorption models such as Langmuir and Freundlich, and each model parameter were evaluated. Kinetics and thermodynamic parameters of the adsorption process were also investigated. The maximum uptake was found to be 0.9 mmol g^?1 at 25°C.     

Adsorption of nickel on synthetic hydroxyapatite from aqueous solutions

The sorption of nickel on synthetic hydroxyapatite was investigated using a batch method and radiotracer technique. The hydroxyapatite samples used in experiments were a commercial hydroxyapatite and hydroxyapatite of high crystallinity with Ca/P ratio of 1.563 and 1.688, respectively, prepared by a wet precipitation process. The sorption of nickel on hydroxyapatite was pH independent ranging from 4.5 to 6.5 as a result of buffering properties of hydroxyapatite. The adsorption of nickel was rapid and the percentage of Ni sorption on both samples of hydroxyapatite was >98 % during the first 15–30 min of the contact time for initial Ni²⁺ concentration of 1 × 10^?4 mol dm^?3. The experimental data for sorption of nickel have been interpreted in the term of Langmuir isotherm and the value of maximum sorption capacity of nickel on a commercial hydroxyapatite and hydroxyapatite prepared by wet precipitation process was calculated to be 0.184 and 0.247 mmol g^?1, respectively. The sorption of Ni²⁺ ions was performed by ion-exchange with Ca²⁺ cations on the crystal surface of hydroxyapatite under experimental conditions. The competition effect of Co²⁺ and Fe²⁺ towards Ni²⁺ sorption was stronger than that of Ca²⁺ ions. NH₄ ⁺ ions have no apparent effect on nickel sorption.     

Sorption of nonionic organic solutes from water to tetraalkylammonium bentonites: Mechanistic considerations and application of the Polanyi-Manes potential theory

This work describes the role of quaternary alkylammonium amendment length on sorption mechanisms of modified bentonites for four nonionic organic compounds; benzene, carbon tetrachloride, TCE, and 1,2-DCB. Tetramethyl to tetrabutyl alkyl amendments were studied and an important mechanistic shift occurred at the propyl chain length for all four solutes studied. Three- and four-carbon-chain functional groups on the ammonium cation resulted in a linear, rather than a curvilinear isotherm. The uptake on tetrapropyl and tetrabutylammonium clays was noncompetitive in binary systems and showed negligible sensitivity to temperature variations, indicating the linear isotherms describe a partitioning uptake mechanism for these organoclays. The adsorptive organoclays (tetramethyl and tetraethylammonium clays) were fit with the Dubinin-Radushkevich equation to investigate the application of the Polanyi-Manes potential theory to organoclay adsorption. It was found that TCE and carbon tetrachloride, with similar physical and chemical characteristics, behaved according to the Polanyi-Manes theory. Benzene showed an anomalously high adsorption volume limit, possibly due to dense packing in the adsorption space or chemisorption to the short chain alkyl groups.     

Separation of Pt(IV) from Industrial Wastewater Using Rice Husk Adsorbent and Its Derivatives

Some novel adsorbents were prepared by rice husk (RH). The esterified rice husk (RHS) was prepared by treating RH with anhydride of succinic acid to introduce carboxylic function to rice husk. This RHS was used to anchor various polyamines, viz., ethylenediamine (ED) and diethylenetriamine (DT) to prepare new adsorbents. These adsorbents were used to separate Pt(IV) from synthetic as well as industrial wastewaters. Adsorbents were characterized by Fourier transform infrared spectra, elemental analysis, scanning electron microscopy, and energy dispersive x-ray spectrometry. The selectivity order for Pt(IV) removal found was: RHS-DT > RHS-ED > RH > RHS. The Freundlich isotherm provided the high correlation (0.9750–0.9938) for the adsorption with low SSE (0.00215–0.00785) value of Pt(IV) for all the adsorbents. Among the kinetic models, pseudo-second order kinetic model was found to best fit with high correlation for all the adsorbents. The results of thermodynamic parameters suggest that the Pt(IV) adsorption was spontaneous and endothermic in nature. The maximum percentage of desorption of Pt(IV) metal ion was obtained when the reagent HCl–thiourea mixture was used as desorbing agent.     

Effects of Salts Containing Mono-, Di-, and Trivalent Ions on Electrical and Rheological Properties of Oil-Water Interface in Presence of Cationic Surfactant: Importance in the Stability of Oil-in-Water Emulsions

Many industrial applications of oil-in-water emulsions involve salts containing ions of different valence. The properties of the oil-water interface (e.g., interfacial tension, zeta potential and interfacial shear viscosity) are strongly influenced by the presence of these salts. This work investigates the role of NaCl, CaCl₂ and AlCl₃ on these properties of the hexane-water interface in presence of a cationic surfactant, viz., hexadecyltrimethylammonium bromide. Addition of salt enhanced the adsorption of surfactant molecules at the hexane-water interface, which increased the interfacial charge density, and consequently, the zeta potential. Interfacial shear viscosity significantly decreased in the presence of salt. The effectiveness of salt at a given concentration was in the sequence: AlCl₃ > CaCl₂ > NaCl. The hexane-in-water emulsions coarsened with time due to the coalescence of hexane droplets. The increase in droplet size with time was analyzed by a model based on the frequency of rupture of the thin aqueous film. The rate constants for coalescence were determined. The rate of coalescence increased in presence of salt.      

Sorption of Bisphenol A as Model for Sorption Ability of Organoclays

The arrangement of bisphenol A molecules into organoclays and their interactions with the intercalated surfactant were studied. The organoclays were prepared via solid-state intercalation of four cationic surfactants, such as dodecyltrimethyl-, tetradecyltrimethyl-, hexadecyltrimethyl-, and didodecyldimethyl-ammonium, as bromide salts, at different loading levels into the interlayers of two natural clays. The natural clays, the prepared organoclays, and the spent organoclays were characterized by X-ray powder diffraction, infrared spectroscopy, and scanning electron microscopy. X-ray powder diffraction measurements showed successive interlayer expansions of the d₀₀₁ basal spacing due to the intercalation of the cationic surfactants and the bisphenol A sorption. The increased d₀₀₁ basal spacing of the organoclays after bisphenol A sorption indicates that the molecules are integrated between the alkyl chains of the surfactant in the organoclays interlayers. Infrared spectroscopy was employed to probe the intercalation of the cationic surfactants and the sorbed bisphenol A. New characteristic bands attributed to the bisphenol A phenol rings appear in the range 1518–1613 cm⁻¹ on the infrared spectra of the spent organoclays, proving the presence of bisphenol A in the hydrophobic interlayers. Scanning electron microscopy of the organoclays before and after BPA sorption shows that their morphology becomes fluffy and that the presence of the organic molecules expands the clay structure.     

Insertion of fluorophore dyes between Cloisite Na+ layered for preparation of novel organoclays

The aim of this study was to obtain novel photo-functional organomontmorillonites from the intercalation reaction of Cloisite Na⁺ and fluorescent dyes of auramine O, and safranin T in an aqueous solution. The insertion of surfactants in the interlamellar space of nanoclay was followed by Fourier transform infrared spectroscopy and X-ray measurements. An X-ray diffraction analysis established that incorporation of the organic dye cations into the Cloisite Na⁺ expands remarkably the mineral interplanar distances from 1.17 to 1.83–1.97 nm. Field emission scanning electron microscopy was used to study the morphology of the synthesized organoclays. The thermal behavior of the novel hybrid materials was investigated by thermogravimetric analysis and the results show that the organo modified clays verify stepwise decomposition corresponding to initial weight loss from residual water desorption, followed by decomposition of the fluorescent dyes and the dehydroxylation of structural water of the clay layers. Fluorescence properties of the cationic dyes, auramine O, and safranin T incorporated in the clay have significant differences from their behavior in organic solvents and water and the results show that both dyes exhibit a significant fluorescence emission at room temperature when adsorbed in clay.     

Demulsification of Gas Oil/Water Emulsion via High-Intensity Ultrasonic Standing Wave

High-intensity ultrasonic standing wave field was established in a horizontal direction and its effect on “gas oil” in “water” emulsion separation rate was studied. Also, effects of four parameters on emulsion instability behavior were investigated: ultrasound irradiation time (5–30 min), emulsion position in ultrasound field (17–37 cm), ultrasound input intensity (20, 45, and 75%) and dispersed phase concentration (0.5, 2, and 10%). Emulsion light absorbance, droplet diameter and distribution were measured to analyze separation efficiency. The optimum states were 10% oil in water emulsion treated at 17 cm distance from ultrasound source under 30 minutes irradiation time and 20% sound intensity.     

Organically modified montmorillonite and chitosan–phosphotungstic acid complex nanocomposites as high performance membranes for fuel cell applications

Nanocomposite membranes based on polyelectrolyte complex (PEC) of chitosan/phosphotungstic acid (PWA) and different types of montmorillonite (MMT) were prepared as alternative membranes to Nafion for direct methanol fuel cell (DMFC) applications. Fourier transform infrared spectroscopy (FTIR) revealed an electrostatically fixed PWA within the PEC membranes, which avoids a decrease in proton conductivity at practical condition. Various amounts of pristine as well as organically modified MMT (OMMT) (MMT: Cloisite Na, OMMT: Cloisite 15A, and Cloisite 30B) were introduced to the PEC membranes to decrease in methanol permeability and, thus, enhance efficiency and power density of the cells. X-ray diffraction patterns of the nanocomposite membranes proved that MMT (or OMMT) layers were exfoliated in the membranes at loading weights of lower than 3 wt.%. Moreover, the proton conductivity and the methanol permeability as well as the water uptake behavior of the manufactured nanocomposite membranes were studied. According to the selectivity parameter, ratio of proton conductivity to methanol permeability, the PEC/2 wt.% MMT 30B was identified as the optimum composition. The DMFC performance tests were carried out at 70 °C and 5 M methanol feed and the optimum membrane showed higher maximum power density as well as acceptable durability compared to Nafion 117. The obtained results indicated that owing to the relatively high selectivity and power density, the optimum nanocomposite membrane could be considered as a promising polyelectrolyte membrane (PEM) for DMFC applications.     

Improvement in Uranium Adsorption Properties of Amidoxime-Based Adsorbent Through Cografting of Amine Group

Amidoxime (AO)/amine co-functionalized polypropylene fiber adsorbents were prepared. The all-polymeric structures were characterized by using Fourier transform infrared spectroscopy (FTIR), optical microscope, contact angle meter and electron spin resonance (ESR) analysis methods, confirming the grafting, modification, and amidoximation stages gravimetrically, spectroscopically, and visually. The properties for the removal of uranyl(VI) from aqueous solutions were investigated. For amidoxime (AO) fiber, high adsorption rate was observed within the first 30 minutes and the plateau value of 40.6% uranium loading (0.0812 mg/g) was reached at around 30 minutes. The adsorption equilibrium for AO/amine fiber was attained within 20 minutes, resulting in the adsorption of 92.6% uranium loading (0.185 mg/g). The percentage of adsorption increases with increasing pH value (2–6), reaches a maximum at pH 6.0 and then remains almost constant for AO/amine fiber, whereas reduces slightly for AO fiber.     

Effect of acid and alkali treatments of a forest waste,Pinus brutia cones,on adsorption efficiency of methyl green

The removal of methyl green (MG) dye from aqueous solutions using acid- or alkali-treated Pinus brutia cones (PBH and PBN) waste was investigated in this work. Adsorption removal of MG was conducted at natural pH, namely, 4.5 ± 0.10 for PBH and near 4.8 ± 0.10 for PBN. The pseudo-second-order model appeared to be the most appropriate to describe the adsorption process of MG on both PBN and PBH with a correlation coefficient R² > 0.999. Among the tested isotherm models, the Langmuir isotherm was found to be the most relevant to describe MG sorption onto modified P. brutia cones with a correlation factor R² > 0.999. The ionic strength (presence of other ions: Cl^?, Na⁺, and SO₄^2?) also influences the adsorption due to the change in the surface properties; it had a negative impact on the adsorption of MG on these two supports. A reduction of 68.5% of the adsorption capacity for an equilibrium dye concentration Ce of 30 mg/L was found for the PBH; while with PBN no significant influence of the ionic strength on adsorption was observed, especially in the presence of NaCl for dye concentrations superior to 120 mg L^?1.     

Adsorption of cadmium ions from aqueous solutions using nano-montmorillonite: kinetics,isotherm and mechanism evaluations

With increasing industrial development, heavy metal pollution, e.g., cadmium (Cd) pollution, is increasingly serious in soil and water environments. This study investigated the sorption performance of nano-montmorillonite (NMMT) for Cd ions. Adsorption experiments were carried out to examine the effects of the initial metal ion concentration (22.4–224 mg/L), pH (2.5–7.5), contact time (2–180 min) and temperature (15–40 °C). A simulated acid rain solution was prepared to study the desorption of Cd adsorbed on NMMT. After the adsorption or desorption process, the supernatant was analyzed using a flame atomic absorption spectrometry method. The Cd removal rate increased as the pH and contact time increased but decreased as the initial metal ion concentration increased. The maximum adsorption capacity was estimated to be 17.61 mg/g at a Cd²⁺ concentration of 22.4 mg/L. The sorption process can be described by both the Langmuir and Freundlich models, and the kinetic studies revealed that the pseudo-second-order model fit the experimental data. The Cd desorption rate when exposed to simulated acid rain was less than 1%. NMMT possesses a good adsorption capacity for Cd ions. Additionally, ion exchange was the main adsorption mechanism, but some precipitation or surface adsorption also occurred.     

Sorption of nickel on chitosan

The sorption of nickel on chitosan was studied using batch method. As a tracer was used radioisotope ⁶³Ni. The effect of pH and contact time to reach sorption equilibrium was investigated. During the sorption of Ni²⁺ ions occur mostly to ion-exchange reactions on the surface of sorbent. The time to reach the sorption equilibrium of nickel on chitosan was 14 h. The percentage of sorption after 14 h achieved the value of 84 %. On the sorption of nickel used solutions with initial pH in the range from 3.9 to 8.1. In the monitored range of pH after 24 h of contact was the sorption of nickel on chitosan >97 %. The sorption of nickel was reduced by increasing concentrations of Ni²⁺ ions in the solution. The experimental data for sorption of nickel have been interpreted in the term of Langmuir isotherm and the value of maximum sorption capacity of nickel on chitosan was 2.71 × 10^?3 mol g^?1.