Betaine Surfactant Research Articles

Synthesis of three gemini betaine surfactants and their surface active properties

Abstract Three Gemini betaine surfactants bis [N-methylene-N-dimethyl (1-alkyl-1-sodium formate) methine] ammonium bromides (n = 10, 12, 14) were synthesized by substitution reaction, quaternization and neutralization reaction with tetramethylethylenediamine, bromine (Br2), sodium hydroxide (NaOH) and long chain alkyl acid as main raw materials. The chemical structures of the prepared compounds were confirmed by FTIR, 1H NMR, MS spectroscopy and element analysis. With the increasing length of the carbon chain, the values of their CMC (critical micellar concentration) initially decreased. These compounds were superior in surface active properties to single chain betaine surfactant such as decyl dimethyl betaine surfactant. The efficiency of adsorption at the water/air interface (pC20) of these surfactants was very high. The shorter the hydrocarbon chain length of Gemini betaine surfactants, the faster the rate of reduction of surface tension, and smaller the aggregation number of Gemini betaine surfactants. Micelle diameter and maximum wetting angle of pure water drop/air increased, but maximum wetting angle of water phase/n-decane decreased with the increase of the hydrophobic chain length. Their foaming properties toward a felt chip and lime-soap dispersing ability were investigated.

Synthesis and performance of a series of dual hydroxyl sulfobetaine surfactants

ABSTRACTFive kinds of dual hydroxyl sulfobetaines with different carbon atom numbers in hydrophobic chain were synthesized by using linear saturated alcohol, epichlorohydrin and dimethylamine, and then their structures were characterized by FTIR and 1H NMR. The stability of all synthesized betaine surfactants in hard water was at level 4, which indicated they had high tolerance on hard water. Their CMC and γcmc were lower than the conventional cationic surfactant dodecyltrimethylammonium bromide and anionic surfactant sodium dodecyl, so they had more excellent surface activities. With the chain length increasing from C8 to C14, the surface activities, emulsifying properties and foaming properties of these betaine surfactants improved because surfactant molecules tightly arranged in the oil-water interface, but there was abnormal phenomenon of surface activity and foam property from C14 to C16 due to overlong hydrophobic chain. According to the results of the experiment, C14SB was the most practical in the five kinds of surfactants, which was potential candidate to enhance oil recovery in oil field. The performances of C14SB were as follows: CMC = 2.2 × 10−4 mol/L, γcmc = 30.9 mN/m and the time of bleeding 10 mL water t = 375 s at 2 g/L the optimum emulsification concentration.

PH-Responsive Pickering Emulsions Stabilized by Silica Nanoparticles in Combination with a Conventional Zwitterionic Surfactant.

pH-responsive oil-in-water Pickering emulsions were prepared simply by using negatively charged silica nanoparticles in combination with a trace amount of a zwitterionic carboxyl betaine surfactant as stabilizer. Emulsions are stable to coalescence at pH ≤ 5 but phase separate completely at pH > 8.5. In acidic solution, the carboxyl betaine molecules become cationic, allowing them to adsorb on silica nanoparticles via electrostatic interactions, thus hydrophobizing and flocculating them and enhancing their surface activity. Upon increasing the pH, surfactant molecules are converted to zwitterionic form and significantly desorb from particles' surfaces, triggering dehydrophobization and coalescence of oil droplets within the emulsion. The pH-responsive emulsion can be cycled between stable and unstable many times upon alternating the pH of the aqueous phase. The average droplet size in restabilized emulsions at low pH, however, increases gradually after four cycles due to the accumulation of NaCl. Experimental evidence including adsorption isotherms, zeta potentials, microscopy, and three-phase contact angles is given to support the postulated mechanisms.

Effect of inorganic alkalis on interfacial tensions of novel betaine solutions against crude oil

The effects of inorganic alkalis on the dynamic interfacial tensions (IFTs) of three betaine surfactants with different structures against daqing crude oil and model oils containing crude oil fractions, such as saturate, aromatic, resin, asphaltene and acidic fractions, have been studied by spinning drop tensiometer. The influences of pH value (alkali concentration and types) have been investigated. On the basis of the experimental results, one can find that it is difficult to reach the ultralow IFT value for all betaine solutions because of the mismatching of the hydrophilic head and hydrophobic tail. The unsaturated and branched alkyl chain can enlarge the size of hydrophobic part and reduce the equilibrium IFTs. By adding alkali, the IFTs are controlled by the mixed adsorptions of the petroleum acids, produced soaps and betaine molecules. For betaines with small hydrophobic part, 18C and 22C, the mixed adsorption films are compact than those of pure betaine films, which results in the decrease of IFT. On the other hand, the petroleum acids and soaps adsorb competitively with betaine molecules, due to the tighter packing of 26C molecules at the interface, the equilibrium IFT values of 26C increase with an increase in pH value. The stronger the alkali is, the better the synergism or antagonism is. The effects of pH on the IFTs of betaine solutions against model oils containing crude oil fractions agree with those against crude oil. For all betaines, the order of the ability of affecting IFT is acidic fractions > resin > asphaltene > aromatic > saturate in general.

The Effect of Betaine Surfactant on Carbonate Reservoir Wettability in Self-Diverting Acidizing Stimulation

Contact angle alterations of carbonate cores after immersing in spent acid with oleyl amido propyl betaine surfactant were measured to clarify the effect of viscoelastic surfactant on the wettability of carbonate reservoir during self-diverting acidizing. The results showed that spent acid solutions with hydrochloric acid and betaine surfactant induced core wettability to water-wetting for initially oil-wet rocks, and oil-wetting for initially water-wet rocks. Longer immersion time and higher concentration of surfactant enhanced the effects. The adverse wettability reversal for water-wet reservoir was eliminated by mutual solvent or brine postflush. Chemical mechanisms of the wettability alteration were interpreted.

Zwitterionic betaine transition from micelles to vesicles induced by cholesterol

Vesicle formation by self-assembly in an aqueous mixture of zwitterionic carboxylate betaine surfactant and cholesterol was studied as a potential drug delivery nanocarrier. In this study, pyrene and 1,6-Diphenyle1-1,3,5-hexatrine (DPH) were applied as fluorescence probes that provides information on polarity and fluidity of the microenvironment, and used to monitor the transition of zwitterionic betaine from monomers to micelles, and to vesicles promoted by addition of cholesterol to micellar solutions through the variation of vibronic peak intensity ratio I1/I3 of the pyrene and solubilization with intensity quenching I428 of (DPH). In addition, the steady-state and time-resolved fluorescence anisotropy measurements of the (DPH) probe provides information on the effect of cholesterol on the dynamic properties vesicle membrane and vesicular distribution accompanied by dynamic light scattering (DLS), transmission electron microscopy (TEM), and turbidity measurements. Our results show an abrupt change of the ratio I1/I3 of pyrene and fluorescence intensity I428 of (DPH) in the transition from monomer to micelle with increasing betaine concentration, as well as fluorescence anisotropy results thought the transition from micelle to vesicle promoted by cholesterol and confirmed by TEM result. Furthermore, the fluorescence anisotropy measurements shows that addition of small amount of cholesterol to zwitterionic betaine micelle have a significant influence on the molecular packing leading to vesicle formation and increasing bilayer rigidity with increasing cholesterol concentration up to χchol=0.25.

Redox-Controllable Interfacial Properties of Zwitterionic Surfactant Featuring Selenium Atoms.

Control of interfacial properties (foaming and emulsification) plays an important role in industry. Here we developed a novel redox-responsive surfactant, 3-(11-benzylselanyl-undecyl)-dimethylammonium acetate (BSeUCB), using selenium atoms as an environmentally sensitive group. In a reduced state, BSeUCB aqueous solution showed good foaming and emulsification abilities as well as conventional betaine surfactants. After oxidization, BSeUCB transformed into a bola-type structure because of the presence of a new hydrophilic group (selenoxide), and thus the critical micellar concentration, equilibrium surface/interfacial tension, and molecular area at the interface correspondingly increase from 0.32 mM, 46.43 mN·m(-1), 5.30 mN·m(-1), and 0.61 nm(2) to 4.98 mM, 59.15 mN·m(-1), 18.29 mN·m(-1), and 1.22 nm(2), respectively, resulting in a greater amount of energy input required to produce foam or emulsion, and a less dense adsorption layer, i.e., poor foaming and emulsification ability. Such a conversion was reversibly controlled by simply adding a trace amount (<0.06 wt % of the dispersion) of oxidant (H2O2) and reductant (Na2SO3). The products of the redox reaction did not interfere in the switchability except at the first cycle. The oxidization was generally time-consuming, whereas the reduction was very fast.

An experimental investigation of nanoparticle-stabilized CO2 foam used in enhanced oil recovery

Stability of nanoparticle (NP) stabilized CO2 foam using silica and nanoclay, and the resulting improvement in oil recovery are investigated using modified bulk foam tests and flow experiments using a microfluidic device. The size and uniformity of the dispersion of NPs are characterized via Dynamic Light Scattering. The NP-assisted foam properties are evaluated by: (1) modified bulk foam tests where bulk foam is generated using CO2 under approximately 20psi of pressure and its formability and decay (dynamic stability) are recorded as functions of time and (2) foam stability and oil recovery are investigated using a quasi-2D porous medium (microfluidic chip), fabricated based on a 2D representation of a sample of sandstone. The effects of type of NP, particle size, surfactant type and pressure on CO2 foam stability and viscosity and the resulting incremental oil recovery are investigated and discussed. The results show that nanoclay and silica NPs with an Alpha-Olefin Sulfonate (AOS)-Lauramidopropyl Betaine (LAPB) surfactant mixture provide excellent formability and stability (half-life time around four hours) and increased viscosity. The stability and impact of NPs-stabilized foam on recovery in a microfluidic device is explored and reported. Data is collected using an ultra-high resolution full frame image sensor, which allows the entire surface of the model to be unobstructed for observation; images of the entire porous medium are captured while preserving the resolution required to discern features as small as 10μm. The porous medium is approximately 1.4in. in width and 1.6in. in length and the channels are 20μm deep. Results suggest that foam with highest stability (Si-LAPB-AOS) does not provide the best oil recovery performance (a high oil recovery and a low pore volume injected). The novelty of this work lies in its thorough characterization of NPs in stabilizing CO2 foams, investigation of their stability using a modified bulk foam test and examination of their stability and incremental recovery resulting from their use compared to systems without NPs in quasi-2D porous media fabricated based on a two-dimensional representation of a Berea sandstone.

Synthesis of oligomer betaine surfactant (DDTPA) and rheological properties of wormlike micellar solution system

Novel oligomer betaine surfactant penta sodium N, N′, N″- dodecyl diethylene triamine pentaacetic acid (DDTPA) with three dodecyls, five carboxylic acid groups and three quaternary ammonium were synthesized through two steps in this paper. Rheological properties of mixed oligomer betaine surfactant DDTPA/anionic surfactant sodium dodecylsulfonate (SDS) solution systems were studied as functions of SDS concentration, inorganic salt KCl dosage and temperature. Stable and dynamic viscoelastic measurements were carried out to investigate the characters of wormlike micelles formed in certain condition. In the 2.5wt% DDTPA, 4wt% KCl and SDS system, the optimal SDS concentration is 1.2wt%, at which the viscosity reaches a maximum. Interestingly, with adding inorganic salt KCl to mixed surfactant solution(2.5wt% DDTPA, 1.5wt% SDS), the water-like fluid turns into gel-like viscoelastic wormlike micellar solution immediately owing to the screening electrostatic repulsion among the surfactant charged groups by counterions. When KCl concentration is 3wt%, the micellar solution obtains a peak value in viscosity. For the system with 2.5wt% DDTPA, 1.5wt% SDS, 4wt% KCl, the micellar contour length decreases with increasing temperature, leading to an exponential decrease in the values of η0 and τR. This work provides a clear understanding of the profound relationship between surfactant wormlike micellar characteristic and the rheological properties. The dynamic viscoelastic behavior of wormlike micelles usually fits for the Maxwell mode in low oscillation frequency region, but in medium and high frequency region it fits for t the modified Maxwell model.

Synthesis and Surface Active Properties of Novel Oligomer Betaine Surfactants

AbstractA new type of oligomer betaine surfactants pentasodium N,N′,N″-alkyl diethylene triamine pentaacetic acid containing five carboxylate groups, three quaternary ammonium groups and three hydrophobic groups was synthesized by alkaline neutralization reaction and quaternization with diethylene triamine pentaacetic acid, sodium hydroxide and long chain alkyl bromide as main raw materials. The chemical structures of the prepared compounds were confirmed by FTIR, 1H NMR, MS spectroscopy and elementary analysis. With the increasing length of the carbon chain, the CMC of the synthesized compounds initially decreased. The surface active properties of these compounds were superior to that of the single chain betaine surfactants rich as decyl dimethyl betaine. The efficiency of adsorption at the water/air interface (pC20) of these surfactants was very high. It is found that the shorter hydrocarbon chain length of oligomer betaine surfactants, the faster the rate of reduction of surface tension, and the bigger the aggregation number of oligomer betaine surfactants are. Their foaming properties and wetting ability toward a felt chip, and lime-soap dispersing ability were investigated.

BASF and Solazyme launch first commercial microalgae-derived betaine surfactant

BASF and Solazyme launch first commercial microalgae-derived betaine surfactant

Studies on foam flooding for saline reservoirs after polymer flooding

Abstract Multiple betaine surfactant PSDA (penta sodium N, N′, N′′-dodecyl diethylene triamine pentaacetic acid) is a kind of Zwitterionic Gemini surfactants with three dodecyls, five carboxylic acid groups and three quaternary ammonium. It has higher surface activities such lower cmc, lower γ cmc , lower IFT and better foaming properties than single chain surfactants, so, as foaming agent, it is used in foam flooding to displace oil in harsh reservoirs. Systematic experiments of foam flooding after water flooding had been performed for saline reservoirs. The foaming ability, stability and FCI (foam composite index) were the key factors to ensure high performance of oil recovery. The foam flooding formula was optimized by good performance of foaming ability, stability and FCI . The co-injection of foam was the most effective mode and the alternative injection of gas and solution was the poorest. The gas liquid ratio could also affect the flooding efficiencies greatly. The optimized gas liquid ratio was proposed as 4:1 for co-injection mode at the reservoirs condition. Results of single cores flooding experiments indicated that the resistance coefficient of the foam flooding was very high and the residual resistance coefficient was very low. Results of dual cores flooding experiments indicated that foam flooding with polymer could contribute 11–20% OOIP (original oil in place) recovery and had excellent profile control ability. Results of pilot test showed recovery oil of foam flooding was very considerable.

Viscosity and stability of ultra-high internal phase CO2-in-water foams stabilized with surfactants and nanoparticles with or without polyelectrolytes

To date, relatively few examples of ultra-high internal phase supercritical CO2-in-water foams (also referred to as macroemulsions) have been observed, despite interest in applications including “waterless” hydraulic fracturing in energy production. The viscosities and stabilities of foams up to 0.98 CO2 volume fraction were investigated in terms of foam bubble size, interfacial tension, and bulk and surface viscosity. The foams were stabilized with laurylamidopropyl betaine (LAPB) surfactant and silica nanoparticles (NPs), with and without partially hydrolyzed polyacrylamide (HPAM). For foams stabilized with mixture of LAPB and NPs, fine ∼70μm bubbles and high viscosities on the order of 100 cP at>0.90 internal phase fraction were stabilized for hours to days. The surfactant reduces interfacial tension, and thus facilitates bubble generation and decreases the capillary pressure to reduce the drainage rate of the lamella. The LAPB, which is in the cationic protonated form, also attracts anionic NPs (and anionic HPAM in systems containing polymer) to the interface. The adsorbed NPs at the interface are shown to slow down Ostwald ripening (with or without polymer added) and increase foam stability. In systems with added HPAM, the increase in the bulk and surface viscosity of the aqueous phase further decreases the lamella drainage rate and inhibits coalescence of foams. Thus, the added polymer increases the foam viscosity by threefold. Scaling law analysis shows the viscosity of 0.90 volume fraction foams is inversely proportional to the bubble size.

Synthesis and Surface Active Properties of tri[(N‐alkyl‐N‐ethyl‐N‐Sodium carboxymethyl)‐2‐Ammonium bromide ethylene] Amines

AbstractTrimeric betaine surfactants tri[(N‐alkyl‐N‐ethyl‐N‐sodium carboxymethyl)‐2‐ammonium bromide ethylene] amines were prepared with raw materials containing tris(2‐aminoethyl) amine, alkyloyl chloride, lithium aluminium hydride, sodium chloroacetate, and bromoethane by alkylation, Hoffman degradation reaction, carboxymethylation and quaternary amination reaction. The chemical structures of the prepared compounds were confirmed by FTIR, 1H NMR, MS and elemental analysis. With the increasing length of the carbon chain, the values of their critical micelle concentration initially decreased. Surface active properties of these compounds were superior to general carboxylate surfactants C10H21CHN+(CH3)2COONa. The minimum cross‐sectional area per surfactant molecule (Amin), standard Gibbs free energy adsorption (ΔGads) and standard Gibbs free energy micellization (ΔGmic) are notably influenced by the chain length n, and the trimeric betaine surfactants have greater ability to adsorb at the air/water interface than form micelles in solution. The efficiency of adsorption at the water/air interface (pC20) of these surfactants increased with the increasing length of the alkyl chain. Their foaming properties, wetting ability of a felt chip, and lime‐soap dispersing ability were also investigated.

Surfactant Treatment and Leaching Combination Process for Preparation of Deproteinized Natural Rubber Latex

This study aimed to improve the efficacy of protein removal from fresh natural rubber latex (NRL) and to decrease the production cost by using surfactant treatment and leaching combination processes. The 0.5-3% anionic surfactants, i.e. sodium dodecyl sulfate or sodium lauryl ether sulfate, nonionic tween80 surfactant, or an amphoteric cocamidopropyl betaine surfactant was used in surfactant treatment process. Moreover, water, aqueous surfactant solutions, and/or 1-5% organic solvents (i.e. ethanol, isopropanol and/or acetone) was then used in leaching process. The fresh NRL was preserved by paraben compounds in the presence of surfactant at ambient temperature for 20-120 minutes, and then centrifuged. This might prevent the skin irritation of deproteinized NRL (DNRL) caused by ammonium stabilizer that normally uses in latex industry. The upper rubber mass was then leached for upto three cycles with leaching solvents, and then finally redispersed in distilled water. The milky-like DNRLs were obtained by these processes. Their dry rubber contents were 41-47% that could be adjusted. Their viscosities were 9-13 centipoises with the pH of 6.04-6.61. The protein residues in these DNRLs were 0.0000-0.3244% which were lower than that of fresh NRL (1.2428%). These indicated the efficacy of studied deproteinization process for 73.90-100.0%. Types and concentrations of surfactant, incubation times, leaching solvents, and cycles of leaching process affected the efficacy of deproteinization process. Moreover, the properties of these dried films were not different from that of fresh NR film. This DNRL could be further used for several applications including medical skin products.

Controlled hydrothermal synthesis of ball-flower Ni(OH)2/NiOOH composites assisted by rosin-based betaine zwitterionic surfactant

The ball-flower Ni(OH)2/NiOOH composites were successfully synthesized via a facile hydrothermal method, using nickel sulfate as precursor and urea as precipitant, and the rosin-based betaine zwitterionic surfactant as annexing agent. The optimum condition of preparing ball-flower Ni(OH)2/NiOOH composites was 10 g/L rosin-based betaine zwitterionic surfactant, at 180 °C for 8 h. The ball-flower Ni(OH)2/NiOOH composites were consisted of nanosheets. X-ray diffraction, Fourier transform infrared spectroscopy, nuclear magnetic resonance, scanning electron microscopy, and surface tension were used to characterize the as-prepared samples. The effect of rosin-based betaine zwitterionic surfactant on the morphology and size of ball-flower Ni(OH)2/NiOOH composites were investigated in details. Moreover, a possible formation mechanism was proposed based on the effect of the rosin-based betaine surfactant. The result revealed that the crystallinity of the ball-flower Ni(OH)2/NiOOH composites were improved by the rosin-based betaine surfactant, and the morphology and size of Ni(OH)2/NiOOH composites could be well controlled in the presence of the rosin-based betaine zwitterionic surfactant.

Effect of Branched Cationic and Betaine Surfactants on the Wettability of a Poly(tetrafluoroethylene) Surface

Effect of Branched Cationic and Betaine Surfactants on the Wettability of a Poly(tetrafluoroethylene) Surface

Synthesis of didodecylmethyl hydroxyl sulfobetaine and its evaluation for alkali-free flooding

In this paper, didodecylmethyl hydroxyl sulfobetaine was synthesized by reaction of didodecylmethyl amine with sodium 2-hydroxy-3-chloro propanesulfate. The interfacial tensions between Dagang crude oil and solution of the surfactants, solution of surfactant–polymer mixtures were measured. The effects of surfactant concentration and aging time on the interfacial tension were investigated. It is found that the synthesized betaine surfactant could reduce the interfacial tension to ultra-low without alkali, alcohol and the other additives in the absence of or presence of polymer. The surfactant–polymer system could lower the interfacial tension to ultra-low, even was aged for more than 2 weeks. The sand-pack flooding tests indicated that, with 0.2 wt% of the betaine and with 1,500 mg/L of polymer, 16.89 % of an additional OOIP (original oil in place) was recovered from a sand pack. This result suggested that the didodecylmethyl hydroxyl sulfobetaine might be a good surfactant candidate for enhanced oil recovery.

Desorption of decane molecules from a graphite surface produced by sodium alpha olefin sulphate/betaine surfactant mixtures: A computer simulation study

Molecular dynamics simulations of decane molecules adsorbed on a graphite substrate were carried out to study removal of alkanes from the solid surface by using two surfactants. Three different systems were prepared to understand, from the molecular point of view, the removal process. The first system was constructed with sodium alpha olefin sulphate surfactants (AOS), the second system with betaine surfactants and the third system with a mixture of both surfactants. In each case different features were observed. Studies of density profiles show how the decane molecules were adsorbed on the solid surface in a layer structure. Although both surfactants promoted the formation of an additional decane layer, indicating separation or removal from the graphite surface, it was observed that the AOS surfactant had less influence than betaine. Studies of adsorption and orientation of decane molecules were also analysed on the graphite surface, with the different surfactants and the mixture, and it was observed that those molecules present more structure on the surface with the AOS surfactant than with the betaine surfactant. However, the best removal of decane molecules was obtained with the surfactant mixture. In this case it was observed that the first layer close to the surface was modified while an extra layer of decane molecules emerged suggesting decane separation from the surface. Moreover, the maximum removal was found at AOS/betaine ratio concentration of 0.24/0.76.

Progress on Synthesis and Application of Betaine Surfactants

The preparation and properties of alkyl betaine, alkyl amido betaine, α-long chain alkyl betaine, alkoxy betaine, ethoxylated betaine, and some betaine with special structures were summarized. The synthesis routes and properties of several betaines were compared. The application of betaine surfactants in chemical flooding was also reported.