Quaternary Ammonium Gemini Surfactants Research Articles

Study on the synthesis of nanosheets petal-shaped ZSM-5 Zeolites

In this work, a novel strategy for hydrothermal synthesis of nanosheets petal-shaped ZSM-5 zeolites was introduced. The experimental results indicated that the nanosheets petal-shaped ZSM-5 zeolites exhibited a higher specific surface area and more abundant acid sites. Under the synergistic crystallization effect of ethanol and seeds, the addition of CTAB promoted the growth of the layered structure, and the introduction of trace amounts of seeds effectively inhibited the growth of mordenite in a high alkalinity environment, reducing the crystallization time to 48 hours. More importantly, the petal-shaped ZSM-5 zeolites exhibited excellent MTP (Methanol-to-Propylene) catalytic performance, with methanol conversion maintained above 97.8 % for 80 hours and a maximum propylene selectivity of 49.1 %. This paper proposes an Ethanol-Seed-CTAB synthesis method for producing petal-shaped ZSM-5 zeolite with a unique morphology. This approach does not require the use of complex gemini quaternary ammonium surfactants in the synthesis process, greatly promoting the application and dissemination of nanosheets zeolites.

Surface activity, aggregation behaviour and wettability of mixtures of perfluorobranched short-chain gemini quaternary ammonium surfactant and hydrocarbon anionic surfactants in dilute solution

The hydrophobic and oleophobic properties of perfluorobranched short chains are similar to those long chain fluorocarbons (fluorocarbon chain length ≥ 7), and their environmentally friendly properties make them good alternatives to traditional perfluorooctyl derivatives. For this purpose, a novel perfluorinated branched short chain quaternary ammonium gemini surfactant (PBFS) with high surface activity was synthesized, and the surface properties, aggregation behavior, wetting performance and adsorption performance of the complex system of PBFS and sodium octyl sulfate (SOS) were systematically studied. PBFS exhibited superior surface activity in aqueous solution with the critical micelle concentration (CMC) of 0.1667 mmol/L and the corresponding surface tension (γCMC) of 20.17 mN/m. Moreover, despite the fact that the mixing of PBFS and SOS was not ideal, the two still had the good synergistic effect: the CMC of the compounding solution was reduced to 0.0072 mmol/L and γCMC was 16.01 mN/m when the compounding ratio (CF: CH) was 1:8. And the composite solution could completely wet low surface energy polytetrafluoroethylene (PTFE) plates at 1 mmol/L, and could also wet PTFE plates at extremely low concentrations (0.0625 mmol/L), showing good wetting performance.

Rheology of high-temperature resistant fracturing fluids formed by VES, acids and oxidants for enhancing CO2 injection in deep coal seams

To address the low efficiency of CO2 injection into deep coal seams due to coal adsorption-induced swelling and low permeability, this study proposes the use of a CO2 injection enhancement fracturing fluid (IEFF) to increase injection efficiency, which is composed of viscoelastic surfactant (quaternary ammonium Gemini surfactant, 18-3-18), organic acids (acetic acid, C2H4O2) and oxidants (hydrogen peroxide, H2O2). The rheology and micelle morphology of the IEFF were investigated in terms of temperature and substance ratios. In addition, comparative study was conducted with monomeric surfactants (STAB). The results demonstrated that compared to STAB, 18-3-18 exhibited a two orders of magnitude lower critical micelle concentration (CMC), a lower surface tension (γCMC), and formed a system with favorable rheology at lower concentrations. Moreover, the viscosity of the IEFFs increased as the substance ratio of C2H4O2 to H2O2 decreased. Inflection points in the IEFFs were observed at 313.15 K, 323.15 K, and 333.15 K, where the viscosity exceeded 25 mPa·s. At 323.15 K, a shear rate of 170 s−1, and a substance ratio of 1:1.5, the IEFF reached its maximum viscosity of 40.390 mPa·s, with a micelle size of 109.56 nm, and the intertwined wormlike micelles formed a robust network structure. The results can provide a reference for optimizing fracturing fluid and promoting the efficiency of CO2 injection into deep coal seams.

Gemini Quaternary Ammonium Surfactants with Different Counterions-modified Montmorillonite for Efficient Removal of Methyl Orange.

Organic Na-montmorillonite (OMt-12-2-12·2Y - , Y=CH 3 CO 3 - , C 6 H 5 COO - and Br - ) modified by a series of Gemini quaternary ammonium surfactants with different counterions was prepared for enhancing the adsorption capacity of methyl orange. Compared with the initial adsorption capacity of 5.251 mg/g of Na-Mt, the adsorption effect of OMts under the optimal conditions increased by about 31~34 times. The adsorption isotherms and kinetics of all adsorption processes were respectively described by Langmuir and pseudo-second-order models. The structure, hydrophobicity and hydration of the counterions, as well as the affinity of the counterions with the long aliphatic chains, had a certain influence on the adsorption performance of OMts for methyl orange.

Effect of Quaternary Ammonium Gemini Surfactant Solution on the Rate Constant of the Ninhydrin–Lysine Reaction

Effect of Quaternary Ammonium Gemini Surfactant Solution on the Rate Constant of the Ninhydrin–Lysine Reaction

O/D emulsions stabilized by quaternary ammonium gemini surfactants together with alumina nanoparticles

AbstractOil‐in‐dispersion (O/D) emulsions are the focus in many fields due to their new microstructures and new functions. Herein, O/D emulsions were successfully prepared using series of cationic gemini surfactants 12‐s‐12 (s = 2, 3, and 6) and alumina nanoparticles. The microstructures and type of emulsions were identified using optical microscopy, zeta potential and contact angle methods. Gemini surfactants with two head groups carry more charges than that of conventional surfactants when adsorbed at the oil–water interface. The O/D emulsions can be stabilized at lower surfactant concentrations compared with the conventional single‐headed surfactants. In the presence of 0.1 wt% alumina nanoparticles, gemini surfactants 12‐s‐12 (s = 2, 3, and 6) can stabilize emulsions at the concentration of 3 × 10−4 mM (1.84 × 10−5 wt%), 6 × 10−4 mM (3.76 × 10−5 wt%) and 1 × 10−3 mM (6.68 × 10−5 wt%), respectively. Addition of excessive organic salts such as sodium salicylate and sodium p‐methylbenzenesulfonate shielded the head group charges of gemini surfactants, leading to gemini surfactants to behave as nonionic surfactants Adsorption of surfactants at the alumina nanoparticles occurred, resulting in the transformation from the O/D emulsions to Pickering emulsions. This work shows the advantages of preparing O/D emulsions using gemini surfactants and also provides a new methods of emulsion type transformations by adding excessive oppositely charged organic salts.

Organo-Montmorillonite Modified by Gemini Quaternary Ammonium Surfactants with Different Counterions for Adsorption toward Phenol

The discharge of industrial phenol pollutants causes great harm to the natural environment and human health. In this study, phenol removal from water was studied via the adsorption of Na-montmorillonite (Na-Mt) modified by a series of Gemini quaternary ammonium surfactants with different counterions [(C11H23CONH(CH2)2N+ (CH3)2(CH2)2 N+(CH3)2 (CH2)2NHCOC11H23·2Y-, Y = CH3CO3-, C6H5COO- and Br-, 12-2-12·2Y-]. The results of the phenol adsorption indicated that MMt-12-2-12·2Br-, MMt-12-2-12·2CH3CO3- and MMt-12-2-12·2C6H5COO- reached the optimum adsorption capacity, which was 115.110 mg/g, 100.834 mg/g and 99.985 mg/g, respectively, under the conditions of the saturated intercalation concentration at 2.0 times that of the cation exchange capacity (CEC) of the original Na-Mt, 0.04 g of adsorbent and a pH = 10. The adsorption kinetics of all adsorption processes were in good agreement with the pseudo-second-order kinetics model, and the adsorption isotherm was better modeled by Freundlich isotherm. Thermodynamic parameters revealed that the adsorption of phenol was a physical, spontaneous and exothermic process. The results also showed that the counterions of the surfactant had a certain influence on the adsorption performance of MMt for phenol, especially the rigid structure, hydrophobicity, and hydration of the counterions.

Preparation of Quaternary Ammonium Gemini Surfactant and Its Application in Insulator Cleaning

In this paper, quaternary ammonium salt type Gemini surfactant G12 was designed and synthesized, and its structure was characterized by infrared and nuclear magnetic resonance. The surface tension, permeability, emulsification ability and cleaning of insulator surface contamination in the composite system were tested, and the test results showed that it had low critical micelle concentration (cmc) and good emulsification performance. Due to the presence of rigid groups, the permeability is average. When quaternary ammonium Gemini surfactant G12 is mixed with permeant JFC-E, and is combined with auxiliary and organic solvent, the cleaning rate of insulators can reach more than 90%.

Excellent foaming properties of anionic-zwitterionic-Gemini cationic compound surfactants for gas well deliquification: Experimental and computational investigations

Foams are often employed as an efficient and cleaner method to remove the liquid accumulated at the bottom of the gas wells and promote the production of natural gas. However, the extreme conditions (e.g., high content of condensate, high salinity, high temperature, etc.) in the wells would retard the performance of the foaming agents. Usually, mixtures of different foaming surfactants were used to achieve high performances under those extreme conditions. In this paper, foams stabilized by surfactant mixtures containing alpha-olefin sulfonate (AOS), synthesized green cocamidopropyl betaine (CAPB) and modified quaternary ammonium Gemini surfactant (CAGB) in a proportion of 0.2:0.2:0.2 (wt%/wt%/wt%) were developed to evaluate their industrial application potential in gas well deliquification. The ternary surfactant (CAPB-CAGB-AOS) foam exhibited higher stability than the other dual surfactant foams and singular surfactant foams. Additionally, the foaming efficiency (defined as the ratio of the mass of water converted into foam to the mass of the initial liquid) and liquid unloading efficiency of the CAPB-CAGB-AOS mixture could be improved with the presence of condensate. Salts and methanol had a weak influence on the performance of the CAPB-CAGB-AOS foam. The introduction of ethylenediamine tetraacetic acid disodium (EDTA‧2Na) can enhance the performance of the CAPB-CAGB-AOS foam against salts. The temperature (> 60 °C) favored the foaming efficiency and liquid unloading efficiency of the CAPB-CAGB-AOS mixture, which reached up to 100% and 88.5% at 90 °C. These results indicated that the synergy effect of these three surfactants on the stability and liquid unloading efficiency of the foam can be confirmed. Moreover, the synergy effect can also be confirmed by the surface tension test, the foam's microstructure observation and the computational studies on calculated binding energies and electrostatic interactions.

Quantitative structure–activity relationship study to predict the antibacterial activity of gemini quaternary ammonium surfactants against Escherichia coli

QSAR modeling for predicting the antifungal activities of gemini imidazolium surfactants against Candida albicans using GA-MLR methodsEly Setiawan, Karna Wijaya, Mudasir Mudasir

Mixtures of anionic surfactants with single/triple polyoxyethylene chains and Gemini quaternary ammonium surfactant: interaction and surface activity studies

The combination of anionic and cationic surfactants can obtain high surface activity so that it has been widely used in many fields. However, the problem of ease to precipitate in the isoelectric mole ratio limits its further application. The introduction of polyoxyethylene chain into anionic surfactant and the use of Gemini quaternary ammonium surfactant can solve this problem origin from excessively strong interaction to a great extent while maintaining the best surface activity of the mixed system. Single polyoxyethylene chain carboxylate and triple polyoxyethylene chains sulfonate surfactants are mixed with Gemini quaternary ammonium surfactant respectively and their interactions are explored. The experimental results show that the complex of anionic surfactants with single or triple polyoxyethylene chains and Gemini quaternary ammonium surfactant can obtain high surface activity. And the polyoxyethylene group weakens the charge density of hydrophilic head groups of anionic surfactants. The branched polyoxyethylene chains will weaken this weakening effect. Excessively large steric hindrance of surfactant may reduce the stability and surface activity of mixed system. For anionic nonionic surfactants, the single chain structure and the appropriate numbers of polyoxyethylene groups are more conducive to compounding with Gemini quaternary ammonium surfactants to obtain the best surface activity and the most stable solution.

Synthesis and Surface Properties of Novel Quaternary Ammonium Gemini Surfactants with Polar Head Groups Containing 2‐Hydroxypropyl Moieties

AbstractThe purpose of this paper is to comprehend in‐depth the effect of the surfactant structure on its and physicochemical properties such as surface/interfacial properties, foam stability, wettability, and biodegradability. To this end, quaternary ammonium Gemini surfactants, alkanediyl‐α,ω‐bis[(2‐hydroxypropyl)dodecylammonium] dibromide (abbreviated as Cm‐n‐Cm[iso‐Pr(OH)]2 with m = 12, 14 and n = 2, 3, 4) were synthesized via substitution and quaternization reactions, and their chemical structures were characterized by Fourier transform infrared (FT‐IR) and nuclear magnetic resonance (1HNMR) spectroscopies. The results showed that with the decrease of the spacer length, the surface tension was reduced more strongly, and with the increase of the alkyl tail length, micelles were more easily formed. Besides, the highest surface activity of C14‐2‐C14[iso‐Pr(OH)]2 was observed by increasing NaCl concentration to 200 g L−1. The temperature had a great influence on thermodynamic parameters of the adsorption and micellization. The interfacial tension between 0.26 g L−1 C14‐2‐C14[iso‐Pr(OH)]2 solution and oil could reach 0.022 mN m−1. An elongation of the spacer chain in C14‐n‐C14[iso‐Pr(OH)]2 was unfavorable to foam stability. Besides, the oil‐wetted core, which was aged in 0.6 g L−1 C14‐2‐C14[iso‐Pr(OH)]2 solution, exhibited more hydrophilicity. Cm‐n‐Cm[iso‐Pr(OH)]2 surfactants produced higher biodegradable rates in river water (≥ 90% after 28 days) than the biodegradable surfactant of international recommendation (71% after 28 days) at 30 °C.

Spacer length effect on the aggregation behaviours of gemini surfactants in EAN

As the symbol of gemini surfactants, the spacer group connects two surfactant monomers and plays an important role in the self-assembling of gemini surfactants. Recent attention has been paid to the effects of spacer nature and length in aqueous systems. In this study, the aggregation behaviours of quaternary ammonium gemini surfactants 12-s-12 with different spacer length (s = 2, 3, 4, 5, 6, 8, 10, 12) have been investigated in the protic ionic liquid EAN. The micellization behaviour was characterized by surface tension measurement. With the help of small-angle X-ray scattering (SAXS), the size and shape of aggregates were verified. The spacer length effect could be reflected by the changes in the micellization and phase behaviours of 12-s-12/EAN systems. The critical packing parameter of gemini molecules would decrease monotonically with the spacer length, which is supported by SAXS results. Due to the charge screening effect of EAN, the aggregation behaviours of 12-s-12 would be mainly influenced by spacer length. Our results would be the important supplement to the spacer length effect of gemini surfactants in the nonaqueous systems. With the increase of spacer chain length, the reverse hexagonal lyotropic liquid crystal phase would transform into the micellar phase.

Synthesis and characterization of cationic quaternary ammonium geminis (16–s–16) and their role in ninhydrin–[Cu(II)–His]+ reaction

Cationic quaternary ammonium gemini surfactants were synthesized by mixing N,N-dimethylcetylamine and α,ω-dibromoalkane. The synthesized products were characterized by C, H, N elemental and 1H NMR analyses. The critical micelle concentration (CMC) of these surfactants with and without additives was calculated by means of the conductivity technique. The role of the synthesized quaternary ammonium geminis in the reaction was investigated by a UV–vis spectroscopy. The rate constant (kψ ) was determined at different gemini concentrations and plotted graphically as kψ vs. [16–s–16]. Additionally, the influence of other reaction parameters (viz., reactants, pH, and temperature) was investigated. The binding constants were also determined (K A for [Cu(II)–His]+ and K B for ninhydrin). The resulting kψ –[16–s–16] plot can be understood in terms of a pseudo-phase model of micelles.

Polyoxyethylene Quaternary Ammonium Gemini Surfactants as a Completion Fluid Additive to Mitigate Formation Damage

Summary During well completion operations, the wells are killed with specific fluids to control the well. These fluids can invade and damage the formation because of fluid/rock interactions. Fluids such as fresh water, brines, and weighted fluids (e.g., barite weighted, calcite weighted, and bentonite weighted) are used to control the formations during completion operations. These fluids can invade and interact with clays and damage the formation. In addition, these fluids may alter the near-wellbore wettability and make them more oil-wet, thereby affecting the production from these formations. In this work, polyoxyethylene quaternary ammonium gemini surfactants with different types of spacers are proposed as clay swelling additives in completion fluids to mitigate the formation damage in unconventional reservoirs. Adding the new surfactants will maintain the in-situ permeability and avoid the formation damage. The novel gemini surfactants are tested on unconventional tight sandstone formation enriched with high clay content to mitigate the formation damage during well completion. The process involved a complete stabilization of clays using gemini surfactants added in deionized water (DW). Coreflooding experiments were carried out on Scioto sandstone rock samples with an average porosity of 15.6% and average absolute permeability of 0.25 md. Several coreflooding experiments were carried out with different fluids, such as potassium chloride (KCl), sodium chloride (NaCl), and different classes of gemini surfactants. Coreflooding experiments were designed in a way that the cores were preflushed with the subjected fluid and then post-flooded with DW. Results showed that the cores saturated with KCl and NaCl solutions lost permeability significantly when flooded with water while gemini surfactant solutions maintained the same permeability even after being treated with DW. Conditioning with the KCl solution resulted in a 38% reduction of permeability and that with NaCl solution resulted in an 80% reduction of permeability when treated with DW. No significant change of permeability was found for the case of gemini surfactants. This indicates that the synthesized surfactants can be used for well completion operation without any side effects.

Quaternary ammonium gemini surfactants having different spacer length as clay swelling inhibitors: Mechanism and performance evaluation

Abstract The swelling of shale formation upon exposure to water-based drilling fluids leads to several problems. Common shale (clay) inhibitors used in the industry have several shortcomings which adversely affect the drilling mud properties. This study involves the development, application, and mechanism of new quaternary ammonium gemini cationic surfactants as clay swelling inhibitors. These gemini surfactants are structurally similar but different in terms of the spacer lengths. The inhibition characteristics of gemini surfactants were evaluated using a linear swell tester, capillary suction timer, scanning electron microscope (SEM), rheology, filtration, wettability, and zeta potential analysis. It was observed that the new gemini cationic surfactants with various lengths of spacers reduced the clay swelling. The GS12 surfactant, containing flexible large spacer C12 proved to be a beneficial swelling inhibitor as compared to GS8 and GS10 due to increased hydrophobicity. It also showed acceptable performance compared to the common shale inhibitor used in the industry. SEM images revealed that water caused significant damage to clay structures showing irregular and sharp edges. However, the surfactant-treated clay showed a fine, dense, and smooth surface. An inhibition mechanism using synthesized surfactants was also proposed. Experimental tests showed the synthesized surfactants adsorb and intercalate between layers of clay through hydrogen bonding and attractive electrostatic forces. The orientation of lipophilic tails inhibits the water adsorption in the clay which results in reduced clay swelling. The synthesized surfactants reduced the clay swelling without affecting the other mud properties such as rheology, stability, and filtration properties.

Surface Activities, Antibacterial Activity and Corrosion Inhibition Properties of Gemini Quaternary Ammonium Surfactants with Amido Group and Carboxylic Counterions.

A series of gemini quaternary ammonium surfactants containing carboxylate counterion with the formula C17H35CONH(CH2)2N+(CH3)2(CH2)2N+(CH3)2(CH2)2 NHCO C17H35·2Y (Y=HCOO-, CH3COO-, CH3CHOHCOO-) have been synthesized by a counterion conversion process and characterized by Fourier transform infrared spectroscopy and mass spectroscopy. It is found that these surfactants reduce the surface tension of water to a minimum value of 26.78 mN·m-1 at a concentration of 1.21 ×10-5 mol·L-1. TEM images reveal that aggregates with vesicles or tubular structure are spontaneously formed in these surfactants aqueous solution with the concentration of 1×10-3 mol·L-1. It is also found that they are effective corrosion inhibitors for A3 steel in acid solution and have superior antibacterial activity at a concentration of 0.1g·L-1.

A mesoscopic DPD simulation study on long chain quaternary ammonium gemini surfactant solution

Dissipative particle dynamics (DPD) simulation method is applied to study the aggregation process of quaternary ammonium gemini surfactants in three systems including pure water, water-ethanol and water-oil mixture solution. The results show that DPD simulation can directly observe the formation and evolution of spherical surfactant clusters. In pure water system, higher surfactant concentration leads to form large spherical cluster. In water-ethanol system, additional ethanol molecules can destroy the stable structure of the hydrophobic radical and inhibit the aggregation of surfactant. In water-oil mixture, we find that gemini surfactants distribute in the oil-water interface, and the interfacial tension reduces as surfactant concentration increases. We studied the effect of temperature on critical micelle concentration (CMC) as well as the distribution of surfactants micelle at water-oil interface.

The surface adsorption, aggregate structure and antibacterial activity of Gemini quaternary ammonium surfactants with carboxylic counterions.

A group of Gemini quaternary ammonium surfactants with the formula CnH2n+1CONH(CH2)2N+(CH3)2(CH2)2N+(CH3)2(CH2)2 NHCOCnH2n+1 · 2Y (n = 11, 13 and 15, Y = HCOO−, CH3COO− and CH3CHOHCOO−) have been synthesized by a counterion conversion process and characterized by Fourier transform infrared spectroscopy and mass spectroscopy. Their adsorption and self-aggregation properties are investigated by surface tension, conductivity, dynamic light scattering and transmission electron microscopy (TEM) measurements. The results show that these surfactants reduce the surface tension of water to a minimum value of 26.51 mN m−1 at a concentration of 5.72 × 10−2 mmol l−1. Furthermore, the increased alkyl chain length of the carboxylic counterions leads to the increased critical micelle concentration, the decreased degree of counterion binding (β) and the decreased self-assembly tendency, but the minimum area per surfactant molecule (Amin) adsorbed at the air–aqueous solution are similar. TEM images reveal that these surfactants self-assemble spontaneously into aggregates with vesicle or bilayer structures. It is also found that they have superior antibacterial activity at a concentration of 0.1 g l−1. The high surface activity and high antibacterial activity of the Gemini quaternary ammonium salt surfactants containing different carboxylic counterions bring more possibilities for the application in the field of biomedicine.

Synthesis of Novel Ethoxylated Quaternary Ammonium Gemini Surfactants for Enhanced Oil Recovery Application

Two aspects are always considered in the design and development of new surfactants for oilfield application. One of them is that surfactant must be sufficiently stable at reservoir temperature and the other is the solubility of the surfactant in the injection water (usually seawater) and the formation brine. Most industrially applied surfactants undergo hydrolysis at elevated temperature and the presence of reservoir ions causes surfactant precipitation. In relevance to this, a novel series of quaternary ammonium gemini surfactants with different length of spacer group (C8, C10, and C12) was synthesized and characterized using FT-IR, 13C NMR, 1H NMR, and MALDI-TOF MS. The gemini surfactants were prepared by solvent-free amidation of glycolic acid ethoxylate lauryl ether with 3-(dimethylamino)-1-propylamine followed by reaction with dibromoalkane to obtain quaternary ammonium gemini surfactants. The gemini surfactants were examined by means of surface properties and thermal stabilities. The synthesized gemini surfactants showed excellent solubility in the formation brine, seawater, and deionized water without any precipitation for up to three months at 90 °C. Thermal gravimetric data revealed that all the gemini surfactants were decomposed above 227 °C, which is higher than the oilfield temperature (≥90 °C). The decrease in critical micelle concentration (CMC) and surface tension at CMC (γcmc) was detected by enhancing spacer length in the order C8 ˃ C10 ˃ C12 which suggested that the larger the spacer, the better the surface properties. Moreover, a further decrease in CMC and γcmc was noticed by enhancing temperature (30 °C ˃ 60 °C) and salinity (deionized water ˃ seawater). The current study provides a comprehensive investigation of quaternary ammonium gemini surfactants that can be further extended potentially to use as a suitable material for oilfield application.