Use of Foam Flotation to Remove tert-Butylphenol from Water

Abstract

The surfactants cetyl pyridinium chloride (CPC) and sodium dodecyl sulfate (SDS) were used in a study of an adsorptive bubble flotation process in batch mode to remove tert-butylphenol (TBP) from water. The TBP removal is maximized when the surfactant concentration is around the critical micelle concentration (CMC). Since micelles form above the CMC, this indicate that the higher the surfactant monomer concentration, the better the removal, but the micelles compete with the air/water interface for the TBP, resulting in micelles reducing removal efficiency. The addition of NaCl to the feed solution results in a significant reduction of the ability of CPC to remove TBP, while it improves the ability of SDS to remove TBP.     

The effect of micellar lifetime on the rate of solubilization and detergency in sodium dodecyl sulfate solutions

The slow relaxation time (τ₂) of sodium dodecyl sulfate (SDS) micelles, measured by the pressure-jump technique, was maximum at 200 mM concentration at 25°C, indicating that the most stable micelles are formed at this concentration. This is presumably related to the optimum molecular packing in the micelle. The rate of solubilization of benzene and Orange OT dye into SDS solutions was also maximum at 200 mM concentration. The results are explained as follows: The distance between micelles (i.e., intermicellar distance) decreases as the surfactant concentration (or the number of micelles) increases, resulting in a stronger electric repulsion between micelles. Therefore, the micelles become more rigid, due to the compressive force of intermicellar repulsion, as the concentration increases up to 200 mM SDS. With further increase in the SDS concentration, the micellar shape changes from spherical to cylindrical to accommodate more surfactant molecules in the solution and to minimize the free energy of the system. The interior of the tightly packed micelles is more hydrophobic than that of loosely packed micelles and, therefore, the tightly packed micelles induce rapid solubilization of nonpolar molecules (e.g., benzene, Orange OT) into these micelles.     

The Interaction between some Acid Dyes and Nonylphenol—Ethylene Oxide Derivatives III-A Discussion of Possible Modes of Interaction

Measurements of cloud points and critical micelle concentrations of nonylphenol-ethylene oxide derivatives in aqueous solutions containing acid dyes lend further support to the suggestion that interaction between the dye and surfactant molecules involves the non-polar groups. These and additional diffusion measurements indicate that mixed micelles are formed by interaction of dye with surfactant molecules rather than with surfactant micelles.     

A Systematic Study of Mixed Surfactant Solutions of a Cationic Ester-Bonded Dimeric Surfactant with Cationic, Anionic and Nonionic Monomeric Surfactants in Aqueous Media

A novel cationic biodegradable dimeric (gemini) surfactant, ethane-1,2-diyl bis(N,N-dimethyl-N-hexadecylammoniumacetoxy) dichloride (16-E2-16), containing an ester-linked spacer was synthesized. Its pure and mixed micellization properties with monomeric surfactants cetyl trimethyl ammonium chloride, cetyl pyridinium chloride, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, cetyl alcohol ethoxylate (20EO) and tert-octylphenol ethoxylate (9.5EO) were investigated by surface tension measurements at 30 °C. The critical micelle concentration (CMC) of 16-E2-16 is well below that of cetyl trimethyl ammonium chloride containing the same number of carbon atoms in the hydrophobic tail per polar head. At different mole fractions of the gemini surfactant, the CMCs of the gemini-conventional binary mixtures were determined and were found to be less than the ideal CMC values in all the cases indicating synergistic interactions. Aggregation number and Stern–Volmer constant, obtained by the fluorescence quenching technique, also support the synergistic behavior of the surfactant systems.     

Synergistic solubilization of decafluorobiphenyl by micelles of fluorocarbon surfactants

Solubilization of decafluorobiphenyl (FBIP) by surfactants in aqueous solution was examined to investigate the properties of micelles composed of surfactants having a per-fluorocarbon chain. Fluorocarbon surfactants solubilize FBIP better than hydrocarbon surfactants. Significant solubilization by fluorocarbon surfactants was observed upon addition of salt. Highly synergistic solubilization of FBIP using surfactant mixtures was also observed for fluorocarbon and hydrocarbon surfactants in the presence of salt. The high solubilization ability of surfactants can be attributed to micelle growth. A simple geometrical consideration of molecular packing in micelles revealed that the characteristic micelle is composed of bulky fluorocarbon chains. The solubilization behavior accompanied by micelle growth would be closely associated with a change in interfacial contact area between the micelle core and bulk water. The behavior of fluorescence intensity of micelle-solubilized FBIP also indicated a change in micropolarity of fluorocarbon micelles accompanied by micelle growth.     

Polymer–surfactant interactions in graft copolymer solutions

Graft copolymers composed of water-soluble cellulosic backbones and > 0.4% (by weight) alkyl grafts are insoluble in water but soluble in surfactant solutions. Studies of the bulk viscosity and stability of polymer-surfactant solutions at 49°C indicate that the mechanism for solubilization of the polymer is the incorporation of the alkyl side chains into surfactant micelles. The tendency for side chains to combine with micelles appears to depend at least in part on the geometry of the surfactant tail group such that surfactants containing straight-chain tail groups solubilize alkyl side chains more readily than olefinic surfactants. The presence of small solutes near the surface of the micelle also inhibits incorporation of side chains from the polymer. Unsolubilized side chains remain in the aqueous phase of the solution, where they form thermally unstable intermolecular aggregates.     

Kinetics of precipitation of surfactants. I. Anionic surfactants with calcium and with cationic surfactants

Isoperibol calorimetry was used to measure the rates of precipitation for aqueous solutions of several anionic surfactants with calcium and of anionic and cationic surfactants. A monomer concentration-dependent supersaturation ratio was used to describe the relative rates of precipitation for the surfactant systems studied. This supersaturation ratio allows for the relative rates of precipitation of any surfactant solution to be compared whether micelles are present in solution or not. In general, as the supersaturation ratio increases, the rate of precipitation decreases and the induction time decreases, bot above and below the critical micelle concentration (CMC). The rate of precipitation of sodium dodecyl sulfate (SDS) with dodecyl pyridinium chloride is much slower than the rate of precipitation of the anionic surfactants with calcium for similar supersaturation ratios. The rate of precipitation of SDS with calcium is slightly faster than the rate of precipitation of sodium octyl benzene sulfonate for similar supersaturation ratios. Studies of precipitate crystals, conducted using image analysis, showed that size and shape dependent on the initial supersaturation, the precipitating surfactant molecule, and the extent of aging (until an equilibrium size and shape was reached). Also, differences in the appearance of crystals formed from solutions above and below the CMC were observed. These were most likely due to the difference in supersaturation of these solutions. The crystals formed due to precipitation of SDS with calcium at a concentration above the CMC formed flat trapezoidal, rhombic and hexagonal shapes. These aged into clusters by 1 wk. For a solution that was precipitated at concentrations beginning below the CMC, the crystals began as elongated and rhombic flat plates and aged into trapezoidal, rhombic, and needle-like structures.     

Soil Clean Up by in-situ Surfactant Flushing. III. Laboratory Results

Abstract

Data on the solubilization of p-dichlorobenzene (DCB), naphthalene, and biphenyl in aqueous solutions of sodium dodecylsulfate (SDS) (0-100 mM concentration) indicate increases in effective solubilities of these hydrophobic compounds by factors of roughly 20 to 100. DCB is effectively removed from spiked clay-sand mixtures by leaching with SDS solutions in laboratory columns. Surfactant solutions loaded with DCB are satisfactorily treated by gentle extraction with hexane, and the recovered surfactant solution satisfactorily solubilizes biphenyl. A simple model for predicting the solubilization behavior of surfactants is developed and tested experimentally.     

In vitro solubilization of antibiotic drug sulfamethazine: An investigation on drug–micelle aggregate formation by spectroscopic and scattering techniques

Micellar solubilization has been used extensively for the dissolution of sparingly soluble drugs for effective drug delivery. Apart from improving the solubility and bioavailability, micelles can help reduce toxicity and improve permeability in the system. In this article, solubilization of a well-known antibiotic, sulfamethazine (SMZ) upon micellization, is studied by employing various spectroscopic and scattering techniques like, ultraviolet–visible, fluorescence, small angle neutron scattering (SANS), and zeta potential (ZP) studies. The size(s) and charge(s) of the micelles were monitored by SANS and ZP. A positively charged/cationic surfactant, cetyl trimethyl ammonium bromide (CTAB) and a negatively charged/anionic surfactant, sodium dodecyl sulfate (SDS) are used for micelle formation. Regardless of the surfactant type, the solubility of SMZ increases linearly with the increase in the surfactant concentration, as a result of association between the drug and micelles. However, the solubility of SMZ is found to be better with CTAB than SDS. Upon interaction with SMZ, we observed that the critical micelle concentration of CTAB occurred at a lower concentration than that of SDS surfactant. As fitted in the ellipsoidal core–shell model, SANS results also show the formation of charged micelles. This comparative study can help us to select an appropriate medium for SMZ solubilization to improve selective drug delivery in biomedical applications.     

Use of alizarin red S for determining critical micelle concentration of cationic surfactants

The critical micelle concentrations of cetyl trimethyl ammonium bromide and cetyl pyridinium bromide have been calculated by a spectral-dye method. Alizarin red S at pH 9.12 was found to be suitable for these two cationics. Two shifts in the dye maximum, one due to complex formation (500 mॖ or 525 mॖ) and the other due to the dye-surfactant complex solubilized in the micelles of the cationics were realized. The critical micelle concentration was represented by the point of intersection of two curves at wavelength 500 mॖ and 550 mॖ for cetyl pyridinium bromide and 525 mॖ and 550 mॖ for cetyl trimethyl ammonium bromide.     

Interactions of Polyacrylamide with Cationic Surfactants: Thermodynamic and Surface Parameters

The aggregation behaviour of two cationic surfactants, viz. cetyl trimethyl ammonium bromide (CTAB) and N-cetyl pyridinium chloride (CPC), in different concentrations of water-soluble polyacrylamide has been studied in alkaline medium by electrical conductivity and surface tension measurements. A decrease in the critical micelle concentration (CMC) of the surfactant with an increase in polymer content in the mixture was observed. The thermodynamic and surface parameters have been determined and discussed. The results indicate that micellisation becomes more favourable at higher polymer content.     

Recovery of Co2+ Ions from Aqueous Solutions by Froth Flotation

ABSTRACT

The recovery of Co(II) ions from aqueous solutions under acidic conditions (pH 5) was investigated in flotation columns with inside diameters of 4.0 and 8.0 cm. Three surfactants, dodecylamine, cetyl pyridinium chloride, and sodium dodecyl sulfate, were used as collectors. Sodium dodecyl sulfate was found to be the most efficient; all three, however, produced hydrated froths, leading to rather low recoveries and separation efficiencies. The volumetric gas flow rate was found to affect the process in relation to the amount of surfactant added and the column diameter. The scale-up of the column should be done in terms of the same superficial gas velocity in order to maintain similar levels of metal ion recovery.     

Solubilization Behavior of Phorbol Esters from Jatropha Oil in Surfactant Micellar Solutions

Phorbol esters (PEs) are important toxic compounds found in Jatropha curcas oil and pressed seeds. These compounds are tumor promoters; thus, their removal prior to further utilization of the pressed seed is important. This work aimed to investigate the solubilization behavior of PEs and Jatropha oil in nonionic [effect of the ethylene oxide number (EON), carbon‐chain length and temperature] and anionic (NaCl addition) surfactant systems. The results reveal that an increase in the EON of the nonionic surfactant molecules, rather than an increase in the carbon‐chain length, enhances PE solubilization. The hydrophile‐lipophile balance (HLB) value was correlated with PE solubilization for nonionic surfactant solutions. The solubilization of PEs decreased slightly with increasing temperature, in contrast to solubilization of the oil. Moreover, the mole fraction of PE solubilized in the micelle decreased with increasing electrolyte concentration in anionic surfactant solutions. The solubilization behavior of PEs in both nonionic and anionic solutions indicates that PE acts more like a polar compound than a nonpolar compound. In addition, the PEs in nonionic micelles are likely located in the palisade region (i.e., between the head group and the first few carbon atoms of the tail), whereas those in anionic micelles are likely near the outer core of the head group. This finding suggests that a nonionic surfactant with a higher EON has a greater potential to extract PE from Jatropha seeds. If an anionic surfactant is combined as co‐surfactant, a small amount of electrolyte should be added to increase PE solubilization.     

Synergistic Behavior Between Zwitterionic Surfactant α-Decylbetaine and Anionic Surfactant Sodium Dodecyl Sulfate

Here, we present experimental surface tension isotherms of mixed solutions of a zwitterionic surfactant α-decylbetaine (DB) and an anionic surfactant sodium dodecyl sulfate (SDS) in different molar ratios. These mixed solutions show a composition dependency with respect to both surface tension effectiveness and critical micelle concentration. The pseudo-regular solution theory has been used to evaluate the interaction parameters in the micelle, β ^m and at the surface, β ^s. The results revealed that the mixed solutions of DB/SDS behave synergistically in both surface tension reduction effectiveness and mixed micelle formation at all mole fractions investigated. The values of adsorption area per surfactant molecule at air/solution interface were estimated, which provides some useful information on evaluating the interaction between DB and SDS in mixed adsorbed monolayers. The solubilization behaviors of toluene in DB/SDS mixed solutions were also investigated to help in understanding the structure of mixed micelles of DB and SDS.     

Mixtures of anionic and cationic surfactants with single and twin head groups: Solubilization and adsolubilization of styrene and ethylcyclohexane

Mixtures of anionic and cationic surfactants with single and twin head groups were used to solubilized styrene and ethylcyclohexane into mixed micelles and adsolubilize them into mixed admicelles on silica and alumina surfaces. Two combinations of anionic and cationic surfactants were studied: (i) a single-head anionic surfactant, sodium dodecyl sulfate (SDS), with a twin-head cationic surfactant, pentamethyl-octadecyl-1,3-propane diammonium dichloride (PODD), and (ii) a twin-head anionic surfactant, sodium hexadecyl-diphenyloxide disulfonate (SHDPDS), with a single-head cationic surfactant, dodecylpyridinium chloride (DPCl). Mixtures of SDS/PODD showed solubilization synergism (increased oil solubilization capacity) when mixed at a molar ratio of 1∶3; however, the SHD-PDS/DPCl mixture at a ratio of 3∶1 did not show solubilization enhancement over SHDPDS alone. Adsolubilization studies of SDS/PODD (enriched in PODD) adsorbed on negatively charged silica and SHDPDS/DPCl adsorbed on positively charged alumina showed that while mixtures of anionic and cationic surfactants had little effect on the adsolubilization of styrene, the adsolubilization of ethylcyclohexane was greater in mixed SHPDS/DPCl systems than for SHDPDS alone. Finally, it was concluded that whereas mixing anionic and cationic surfactants with single and double head groups can improve the solubilization capacity of micelles or admicelles, the magnitude of the solubilization enhancement depends on the molecular structure of the surfactant and the ratio of anionic surfactant to cationic surfactant in the micelle or admicelle.     

Extraction of Piperine from Piper Nigrum (Black Pepper) by Aqueous Solutions of Surfactant and Surfactant + Hydrotrope Mixtures

Abstract

The effect of combining butyl benzene sulfonate as hydrotrope with a surfactant in aqueous solutions is investigated for isolation of piperine, an alkaloid, from black pepper. The standard free energy change associated with piperine solubilization in the aqueous solutions of surfactant and hydrotrope individually and in their mixtures is determined from the solubility of piperine in these solutions. A combination of sodium dodecyl sulfate (SDS) and the hydrotrope gives increased percentage extraction of piperine as compared to the hydrotrope alone. The piperine purity recovered from aqueous solutions was higher as compared to the purity of piperine recovered using organic solvents. The piperine crystallized from aqueous solutions of surfactants and hydrotrope also showed cleaner surfaces and uniform structures with sharp edges, unlike the particles crystallized from organic solvents.     

Study of nonionic surfactants on HVOCs removal from coacervate solutions using cocurrent vacuum stripping in a packed column

ABSTRACT

Cloud point extraction has been shown to be an effective technique to remove hydrophobic volatile organic compounds (HVOCs) from aqueous solution using nonionic surfactant. A cocurrent vacuum stripper is used to recover the surfactant in coacervate phase from extraction for economic viability. The solutions containing two series of aromatic and chlorinated HVOCs. Surfactants studied were alkyl phenol ethoxylates, secondary alcohol ethoxylates (AEs), and branched secondary AEs. From equilibrium measurements, the apparent Henry’s law constant (volatility) of the HVOCs in surfactant solution decreased with increasing HVOCs hydrophobicity due to solubilization of the HVOCs in micelles. The results showed that the mass transfer of HVOC decreases due to the solubilization enhancement of the HVOCs.     

一些阴离子／阳离子二元混合体系的增溶行为

研究了十二烷基聚氧乙烯（约含3个EO基团）硫酸三乙醇铵（TADPS）分别与十六烷基三甲基溴化铵（CTABr）、氯化十六烷基毗院（CPCI）以及氯化十二烷基吡啶（DPCI）的二元混合体系对正庚烷、正辛醇以及甲苯的饱和增溶行为。结果表明,混合体系在增溶方面的协同效应取决于增港物的极性或增港物在胶团中的位置．对增溶于胶团内核的非极性正庚烷,TAPDS／CTABr体系显示出较强的实际正协同效应,最大添加浓度（MAC）可用Nishikido的阴离子-阳离子复合物理想增港模型来预测;对既可增溶于胶团的内核,又可增溶于胶团栅栏中的微极性的甲苯,三个混合体系皆表现出实际的正协同效应;但对增溶于胶团栅栏,与表面活性剂形成混合胶团的两亲物质正辛醇,TAD－PA／CTABr体系显示出负协同效应,并且增溶物在胶团相和水相中的分布系数符合Treiner的非理想增溶模型。这些结果表明,阴离子／阳离子混合体系在胶团强化超滤（MEUF）技术中具有潜在的应用前景。     

无机电解质对Pluronic嵌段共聚物胶束化以及增溶萘的影响(II)F108和P94胶束对萘的增溶

无机电解质 K Cl使萘分子和 Pluronic嵌段共聚物 F10 8或 P94空胶束的第一步缔合平衡常数K1值和萘在胶束和水相间的分配系数 KV 值增大 ,即促进了萘的增溶 ,这是由于 KCl使胶束的聚集数增大 ,内核趋向主要由 PO构成所致。KSCN的作用则相反 ,它使胶束的聚集数减小 ,同时降低了内核的 PO含量 ,因而使萘在 F10 8和 P94胶束中的 K1和 KV 值降低     

Molecular Self-Aggregation of Tetradecylbenzene Sodium Sulfonate Isomers

This paper deals with the effect of the surfactant isomeric structure on self-aggregation in aqueous solution. The relationship between the molecular structure of a series of tetradecylbenzene sulfonate isomers (with the benzene ring located at different positions along the alkyl chain) and surface tension was made clear. It is found that the critical micelle concentration increases and the surface tension at critical micellar concentration decreases as the benzene group moves toward the center of the alkyl chain. The structure of micelles was studied by ¹H-NMR relaxation, which indicates that the density of methylene protons in the surface layer of the micellar core decreases as the branching of the hydrophobic group increases. The spontaneous vesicle formation in aqueous solution was investigated by transmission electron microscopy. The results reveal that, as the benzene group moves toward the center of alkyl chain, the assembly structure changes from micelle to vesicle, then to lamellar bilayers, while the critical packing parameter increases.