Microwave-Assisted Ionic Liquid Extraction of n-Alkanes and Isoprenoid Hydrocarbons from Petroleum Source Rock

Microwave-assisted ionic liquid extraction (MAILE) has been investigated for the extraction of n-alkanes and isoprenoid hydrocarbons from petroleum source rock and the conditions for maximum yield of the analytes were determined. An aqueous solution of an ionic liquid, 1-butyl-3-methylimidazolium bromide (BmimBr), was employed as the extracting medium. The results showed that the concentration of ionic liquid, extraction time and extraction temperatures have effects on extraction yields of aliphatic hydrocarbons with optimal conditions at: 3.0 mol L⁻¹ ionic liquid solution, 30 min and 120 °C, respectively. The extraction yields of all the n-alkanes and acyclic isoprenoid hydrocarbons were much higher using microwave-assisted ionic liquid extraction than with Soxhlet extraction and accelerated solvent extraction. There were good correlations of the diagnostic geochemical ratios calculated from the gas chromatographic (GC) data of MAILE, Soxhlet extraction and accelerated solvent extraction. The results of this study show that MAILE is an efficient and green analytical preparatory technique for geochemical evaluation of petroleum source rock.

     

A new and fast extraction method for the determination of priority phenols from marine sediments by liquid chromatography

A new and fast method for the determination of priority phenols in marine sediment samples by high-performance liquid chromatography using microwave-assisted micellar extraction is optimized. This study is carried out using the nonionic surfactants polyoxyethylene 9 lauryl ether (polidocanol) and genapol X-080 as extractants. Parameters studied include surfactant concentration, solution pH, extraction time, and power. Once the method is optimized, it is applied to different spiked marine sediments from of the Canary Islands coastlines (Spain). The results obtained indicate that a power irradiation of 500 W for 2 min achieved the best extraction efficiency (approximately 100% recovery) and less than 10% relative standard deviation. Detection limits are obtained in the 2-20 microg/g range for the phenols studied. Finally, the proposed method provides a simple, fast, and organic solvent-free procedure to analyze phenols from marine sediment samples.     

Effect of Surfactants on the Formation,Morphology, and Surface Property of Synthesized SiO2 Nanoparticles

Abstract

This study investigated the effect of cationic, anionic (saturated and unsaturated), and nonionic surfactants on the formation, morphology, and surface properties of silica nanoparticles synthesized by the ammonium‐catalyzed hydrolysis of tetraethoxysilane in alcoholic media. Results indicate that at a relatively low surfactant concentration (1 × 10^?3–1 × 10^?6 M), cationic surfactants significantly affected the growth of silica particles as measured by dynamic light scattering and transmission electron microscopic analyses. In contrast, the anionic and nonionic surfactants showed relatively minor effects in the low concentration range. The magnitude of negative zeta potential was reduced for silica colloids that were synthesized in the presence of cationic surfactant because of charge neutralization. The presence of anionic surfactants only slightly increased the negative zeta potential while the nonionic surfactant showed no obvious effects. At high surfactant concentrations (>1 × 10^?3 M), cationic and anionic surfactants both induced colloid aggregation, while the nonionic surfactant showed no effect on particle size. Raman spectroscopic analysis suggests that molecules of cationic surfactants adsorb on silica surfaces via head groups, aided by favorable electrostatic attraction, while molecules of anionic and nonionic surfactants adsorb via their hydrophobic tails.     

Equilibrium partition of polycyclic aromatic hydrocarbons in cloud point extraction with a silicone surfactant

In the cloud point extraction (CPE) process with PEG/PPG-18/18 dimethicone, the flexible chain structure of the silicone surfactant efficiently decreased the water content remaining in the surfactant-rich phase, compared with conventional nonionic surfactants, represented by Triton X-114. Meanwhile, the phase volume ratio of surfactant-rich phase to aqueous phase obtained in the silicone surfactant CPE system was found to be maintained at a low value with increasing surfactant concentration; whereas a rapid increase tendency was commonly observed in that of other nonionic surfactants. Based on these advantages, the equilibrium partition of three polycyclic aromatic hydrocarbons (PAHs), anthracene, phenanthrene and pyrene, was studied in the CPE process with PEG/PPG-18/18 dimethicone. Equilibrium parameters, including preconcentration factor, distribution coefficient and recovery, were determined, and the performance was compared with that of another related CPE research, where Tergitol 15-S-7 was used. Due to the low surfactant-rich phase volume, higher concentrations of the three PAHs in the surfactant-rich phase, and the resulting higher preconcentration factors and distribution coefficients were able to be achieved at the same time. Moreover, the great performance was able to be maintained even at a high surfactant concentration or PAHs initial concentration.     

Micellar-enhanced ultrafiltration of cadmium ions with anionic–nonionic surfactants

Micellar-enhanced ultrafiltration (MEUF), a surfactant-based separation process, is promising in removing multivalent metal ions from aqueous solutions. The micellar-enhanced ultrafiltration of cadmium from aqueous solution was studied in systems of anionic surfactant and mixed anionic/nonionic surfactants. The micelle sizes and zeta potentials were investigated by dynamic light scattering measurements. The effects of feed surfactant concentration, cadmium concentration and the molar ratio of nonionic surfactants to sodium dodecyl sulfate (SDS) on the cadmium removal efficiency, the rejection of SDS and nonionic surfactants and the permeate flux were investigated. The rejection efficiencies of cadmium in the MEUF operation were enhanced with higher SDS concentration and moderate Cd concentration. When SDS concentration was fixed at 3 mM, the optimal ranges of the molar ratios of nonionic surfactants to SDS for the removal of cadmium were 0.4–0.7 for Brij 35 and 0.5–0.7 for Triton X-100, respectively. With the addition of nonionic surfactants, the SDS dosage and the SDS concentration in the permeate were reduced efficiently.     

Determination of cationic surfactants in pharmaceutical disinfectants using a new sensitive potentiometric sensor

A new sensitive potentiometric surfactant sensor was prepared based on a highly lipophilic 1,3-didecyl-2-methyl-imidazolium cation and a tetraphenylborate antagonist ion. This sensor was used as a sensing material and incorporated into the plasticized PVC-membrane. The sensor responded fast and showed a Nernstian response for investigated surfactant cations: cetylpyridinium chloride (CPC), hexadecyltrimethylammonium bromide (CTAB) and Hyamine with slope 59.8, 58.6 and 56.8 mV/decade, respectively. The sensor served as an end-point detector in ion-pair surfactant potentiometric titrations using sodium tetraphenylborate as titrant. Several technical grade cationic surfactants and a few commercial disinfectant products were also titrated, and the results were compared with those obtained from a two-phase standard titration method. The sensor showed satisfactory analytical performances within a pH range of 2-11, and exhibited excellent selectivity performance for CPC compared to all of the organic and inorganic cations investigated. The influence of the nonionic surfactants on the shape of titration curves was negligible if the mass ratio of ethoxylated nonionic surfactants and cationic surfactants (EONS:CS) was not greater than 5.     

Sensitivity Enhancement of the Fluorometric Determination of Aluminum by the Use of Surfactant

Abstract

The effects of surfactants on fluorescence analysis were studied. The addition of surfactants to a metal complex solution causes a remarkable enhancement of fluorescence. By means of such phenomenon the sensitivity of the fluorometric determination of aluminum was increased about six-fold over conventional methods. From the stability of the chelate complex in the presence of surfactant and the degree of enhancement of fluorescence, the nonionic surfactant was judged to be the most useful of the types of surfactants: cationic, anionic and nonionic. An ultramicro amount of aluminum, 5 × 10^?10 g Al/ml, could be determined by the proposed method.     

High Temperature Steam Extraction for the Determination of Aliphatic Hydrocarbons in Petroleum Source Rock

A simple method for the extraction of hydrocarbons from petroleum source rock by high temperature steam was investigated and the conditions for maximum yield were determined. The results showed that the temperature and kinetic rates have significant effects. The optimum temperature for the extraction of n-alkanes and isoprenoid hydrocarbons from sedimentary organic rocks was 250 °C. The optimum extraction time for lower and medium molecular weight n-alkanes was 20 min, while the higher molecular weight alkanes were exhaustively extracted after 50 min. The yields of the analytes were much higher with using the high temperature steam extraction than Soxhlet extraction. The recoveries of the n-alkanes for GC–MS analysis from the extractant water by SPME with a PDMS fibre ranged from 90 to 100% and most of the compounds were above 93%.

     

Experimental study on methane solubilization by organic surfactant aggregates

Seeking to enhance coal mine safety, an experimental study of a kind of water-based explosion suppression medium for the absorption of mine gas was carried out. Using methane as the model gas, solubilizing experiments with different concentrations of anionic and nonionic surfactants were carried out using headspace gas chromatography for surfactants consisting of sodium fatty alcohol polyoxyethylene ether carboxylate (AEC), fatty acid methyl ester sulfonate (MES), fatty methyl ester ethoxylate (FMEE), hexyl d-glucoside (APG06), octyl beta-d-glucopyranoside (APG08) and n-decyl glucoside (APG10). By selecting individual surfactants, the study investigated the methane solubilization performance of water mist with binary anionic–nonionic surfactants. Furthermore, the release of methane in solution was also examined. The results show that the apparent solubility of methane in solution is linearly and positively correlated with the surfactant concentration. The methane solubilization is significantly improved by the addition of anionic–nonionic surfactants. The optimal solubilizing ratio of the anionic–nonionic surfactant varies with the solution compositions. For a fixed ratio, surfactant compositions exhibit the most distinct synergistic effect and the best performance for methane solubilization. The release of methane from mixed micelles composed of the compound solution is superior to that of a single surfactant. Through the analysis of the solubilization effect and the stability of different absorbents, it is concluded that the anionic–nonionic surfactant system shows much better capability than the other selected surfactants.     

Synergism and Physicochemical Properties of Anionic/Amphoteric Surfactant Mixtures with Nonionic Surfactant of Amine Oxide Type

The physicochemical properties of initial formulation, that is anionic/amphoteric surfactants mixture SLES/AOS/CAB (sodium lauryl ether sulfate (SLES), α-olefin sulfonates (AOS) and cocamidopropyl betaine (CAB) at ratio 80 : 15 : 5) with nonionic surfactant of amine oxide type (lauramine oxide (AO)) in various concentration (1–5%) were studied. To characterize the surfactants mixture, the critical micelle concentration (CMC), surface tension (γ), foam volume, biodegradability and irritability were determined. This study showed that adding of AO in those mixtures lowered both γ and CMC as well as enhanced SLES/AOS/CAB foaming properties, but did not significantly affect biodegradability and irritability of initial formulation. Moreover, an increase in AO concentration has a meaningful synergistic effect on the initial formulation properties. All those results indicates that a nonionic surfactant of amine oxide type significantly improves the performance of anionic/amphoteric mixed micelle systems, and because of that anionic/amphoteric/nonionic mixture can be used in considerably lower concentrations as a cleaning formulation.

     

Mixed micelle formation and solubilization behavior toward polycyclic aromatic hydrocarbons of binary and ternary cationic-nonionic surfactant mixtures

Water solubility enhancements of polycyclic aromatic hydrocarbons (PAHs), viz., naphthalene, anthracene and pyrene, by micellar solutions at 25 degrees C using two series of surfactants, each involving two cationic and one nonionic surfactant in their single as well as equimolar binary and ternary mixed states, were measured and compared. The first series was composed of three surfactants, benzylhexadecyldimethylammonium chloride (C16BzCl), hexadecyltrimethylammonium bromide (C16Br), and polyoxyethylene(20)mono-n-hexadecyl ether (Brij-58) with a 16-carbon (C16) hydrophobic chain; the second series consisted of dodecyltrimethylammonium bromide (C12Br), dodecylethyldimethylammonium bromide (C12EBr), and polyoxyethylene(4)mono-n-dodecyl ether (Brij-30) with a 12-carbon (C12) chain. Solubilization capacity has been quantified in terms of the molar solubilization ratio, the micelle-water partition coefficient, the first stepwise association constant between solubilizate monomer and vacant micelle, and the average number of solubilizate molecules per micelle, determined employing spectrophoto-, tensio-, and flourimetric techniques. Cationic surfactants exhibited lesser solubilization capacity than nonionics in each series of surfactants with higher efficiency in the C16 series compared to the C12 series. Increase in hydrophobicity of head groups of cationics by incorporation of ethyl or benzyl groups enhanced their solubilization capacity. The mixing effect of surfactants on mixed micelle formation and solubilization efficiency has been discussed in light of the regular solution approximation (RSA). Cationic-nonionic binary combinations showed better solubilization capacity than pure cationics, nonionics, or cationic-cationic mixtures, which, in general, showed increase with increased hydrophobicity of PAHs. Equimolar cationic-cationic-nonionic ternary surfactant systems showed lower solubilization efficiency than their binary cationic-nonionic counterparts but higher than cationic-cationic ones. In addition, use of RSA has been extended, with fair success, to predict partition coefficients of ternary surfactant systems using data of binary surfactants systems. Mixed surfactants may improve the performance of surfactant-enhanced remediation of soils and sediments by decreasing the applied surfactant level and thus remediation cost.     

Extraction of polycyclic aromatic hydrocarbons and organochlorine pesticides from soils: a comparison between Soxhlet extraction, microwave-assisted extraction and accelerated solvent extraction techniques

The methods of simultaneous extraction of polycyclic aromatic hydrocarbons (PAHs) and organochlorine pesticides (OCPs) from soils using Soxhlet extraction, microwave-assisted extraction (MAE) and accelerated solvent extraction (ASE) were established, and the extraction efficiencies using the three methods were systemically compared from procedural blank, limits of detection and quantification, method recovery and reproducibility, method chromatogram and other factors. In addition, soils with different total organic carbon contents were used to test the extraction efficiencies of the three methods. The results showed that the values obtained in this study were comparable with the values reported by other studies. In some respects such as method recovery and reproducibility, there were no significant differences among the three methods for the extraction of PAHs and OCPs. In some respects such as procedural blank and limits of detection and quantification, there were significant differences among the three methods. Overall, ASE had the best extraction efficiency compared to MAE and Soxhlet extraction, and the extraction efficiencies of MAE and Soxhlet extraction were comparable to each other depending on the property such as TOC content of the studied soil. Considering other factors such as solvent consumption and extraction time, ASE and MAE are preferable to Soxhlet extraction.     

Oleate Ester-Derived Nonionic Surfactants: Synthesis and Cloud Point Behavior Studies

The synthesis and cloud point behavior of high oleate ester-derived nonionic surfactants are now reported. The effect of various polyethoxylate chain lengths (polyethylene glycol with 7, 11, and 16 units of ethylene oxide (EO) monomer) as the surfactant's hydrophilic head on the cloud point was investigated. The effect of varying amounts of sodium chloride and five different ionic surfactants on the cloud points of the synthesized nonionic surfactants were also presented. When the chain length of polyethoxylate increased, the cloud point of the synthesized nonionic surfactant also increased, ranging from 16°C, 43°C, and 64°C for 7, 11, and 16 EO units, respectively. Increments in sodium chloride concentration depressed the cloud point values of the synthesized nonionic surfactants linearly. The addition of ionic surfactants elevated the cloud points of the synthesized nonionic surfactant. However, in the presence of sodium chloride, the cloud point of the mixed ionic-nonionic solution was suppressed and anincrease in ionic surfactant concentration was required to elevate the cloud point. It was also found that the cloud points of synthesized surfactants can be raised up to 95°C in the presence of 4wt% NaCl solution.     

阳离子与非离子混合表面活性剂模板合成介孔SiO2

利用各种两亲分子有序组合体构成超分子模板,合成从介观到宏观尺度不同形态的无机材料成为材料科学新崛起的研究方向[1].介孔SiO2在催化、吸附、分离介质及化学传感器等方面有广阔的应用前景.     

Indirect AAS Determination of Cationic Surfactants in Waste Effluents and Shampoos

Abstract

An indirect atomic absorption spectro-metric (AAS) method using electrothermal atomization (ETAAS) for the determination of cationic surfactants has been proposed. The method involves ion-pair formation between cationic surfactant and sodium hexanitro-cobaltate(III), extraction of the ion-pair into 1, 2-dichloroethane and determination of cobalt con centration in organic phase by ETAAS and hence indirectly relating to the cationic surfactant concentrations. Surfactants of the anionic and nonionic group do not interfere to a great extent, and matrix inter ferences from many other cations, anions and organics are also not observed. The method has been success fully applied to cationic surfactant determination in waste water and hair rinsers. Relative standard deviation values (RSD) of 3.2% for waste water samples and 4.3% for shampoo were observed in these analyses.     

Effect of Surfactants and Ionic Strength on Dissociation of Hydrochlorides of Phenothiazine Derivatives

Abstract

A study of the effect of the anionic surfactant dodecyl sulfate, the cationic surfactant carbethoxypentadecyl trimethyl ammonium bromide (Septonex), nonionic surfactant p-octyl phenyl polyoxyethylene (Triton X-100), and a strong electrolyte (KBr) on the dissociation of the hydrochlorides of two derivatives of phenothiazine (diethazine and fluphenazine) was made. It was found that sodium dodecyl sulfate increases the pKa value, whereas Septonex and Triton X-100 decrease this value. The presence of KBr suppresses the effect of the surfactants. A new method for the potentiometric determination of fluphenazine in an aqueous medium was proposed.     

Separation of phenols from aqueous micellar solutions by cloud point extraction

The cloud point technique was used to recover phenol, 4-methylphenol, and 4-nitrophenol from aqueous solutions using oxyethylated methyl dodecanoates as nonionic surfactants. Oxyethylated methyl dodecanoates are convenient nonionic surfactants for such separations. Their cloud points can be easily modified by a change in surfactant hydrophilicity or by the addition of a second nonionic surfactant and/or an electrolyte. The use of the hydrophile lipophile balance is preferred to model the cloud point of oxyethylated methyl dodecanoates and their mixtures with other surfactants. The composition of the surfactant-rich phase depends on electrolyte type and the overheating. The phase can contain only 5-15% of water. Recovery of phenols changes in the order 4-nitrophenol >4-methylphenol > phenol and is increased in the presence of sodium chloride. The presence of salting-out electrolytes is preferred both to decrease the cloud point and to increase the efficiency of extraction.     

Removal of cadmium ions using micellar-enhanced ultrafiltration with mixed anionic-nonionic surfactants

Micellar-enhanced ultrafiltration (MEUF) was used to remove cadmium ions from wastewater efficiently. In this study the nonionic surfactants polyoxyethyleneglycol dodecyl ether (Brij35) and polyoxyethylene octyl phenyl ether (TritonX-100) were for micellar-enhanced ultrafiltration to lower the dosage of the anionic surfactant sodium dodecyl sulfate (SDS). The surfactant critical micelle concentration (CMC) and the degree of micelle counterion binding were investigated. The effects of nonionic surfactant addition on the efficiency of cadmium removal, the residual quantities of surfactant, the permeate flux and the secondary membrane resistance were investigated. A comparison between MEUF with SDS and MEUF with mixed anionic–nonionic surfactants was undertaken. The results show that the addition of Brij35 or TritonX-100 reduced the CMC of SDS and the degree of counterion binding for the micelles. Due to these variations the Cd²⁺ rejection efficiency was at a maximum when the Brij35:SDS and the TritonX-100:SDS molar ratio was 0.5. The Cd²⁺ rejection efficiency in MEUF with SDS is higher than for MEUF with mixed surfactants when the total dose of surfactant is constant. The permeate flux of MEUF with SDS is higher than that for MEUF with mixed surfactants while the secondary resistance of MEUF with SDS is less than that of MEUF with mixed surfactants.     

Demulsification of Crude Oil Emulsions Using Some New Water-Soluble Schiff Base Surfactant Blends

Six new surfactant blends were prepared by mixing one Schiff base non ionic surfactant prepared by etherification of Schiff base monomer with β, ^` β-dichlorodiethylether and PEG 400 in presence of NaOH with six water-soluble Schiff base nonionic surfactants prepared in the same way but etherified with PEG 2000. The mixing process was based on the high dehydration rates given by the PEG 400 Schiff base surfactant compared to the other PEG 2000 surfactants. The experimental results of this study indicate that the demulsification rates of these blends are higher than those of the PEG 400 surfactant. Demulsification process was carried out on an emulsion of w/o ratio 50:50 and studied at 60°C at two different concentrations of the demulsifiers (200 and 240 ppm). The dehydration rates of the six prepared blends reached 100%. The total dehydration time varied from 50 minutes up to 2 hours.     

Determination of the alkyl- and methoxy-phenolic content in wood extractives by micellar solid-phase microextraction and gas chromatography-mass spectrometry

This work combines the utilization of the micellar media during the extraction step and the focused microwave-assisted extraction followed by the solid-phase microextraction-gas chromatography/mass spectrometry (SPME-GC/MS) to determine the alkyl- and methoxy-phenolic content in wood extractives. The proposed environmental-friendly method is mainly characterized by short analysis times (5 min for the microwaves extraction step) and for avoiding the use of organic solvents. Different surfactants were tried for the extraction process: the cationic surfactant CTAB and the non-ionic surfactants Triton X-100 and POLE, with similar extraction efficiencies (85.5-99.7%). The overall method presents limits of detection in the ng g⁻¹ region for the alkylphenols (from 7 to 150 ng g⁻¹) and in the μg g⁻¹ region for the methoxyphenols (from 0.80 to 22.9 μg g⁻¹). The vanillin was the compound most abundant in the wood extractives studied, with concentrations up to 116.2 mg kg⁻¹.