Beneficial effects of wettability altering surfactants in oil-wet fractured reservoirs

In fractured reservoirs, an effective matrix-fracture mass transfer is required for oil recovery. Surfactants have long been considered for oil recovery enhancement, mainly in terms of their ability to reduce oil–water interfacial tension. These surfactants are effective when the fractured formations are water-wet, where capillary imbibition of surfactants from the fracture into the matrix contributes to oil recovery. However, another beneficial aspect of surfactants, namely their ability to alter wettability, remains to be explored and exploited. Surfactants capable of altering wettability can be especially beneficial in oil-wet fractured formations, where the surfactant in the fracture diffuses into the matrix and alters the wettability, enabling imbibition of even more surfactant into the matrix. This sequential process of initial diffusion followed by imbibition continues well into the matrix yielding significant enhancements in oil recovery.In order to test this hypothesis of sequential diffusion–imbibition phenomenon, Dual-Drop Dual-Crystal (DDDC) contact angle experiments have been conducted using fractured Yates dolomite reservoir fluids, two types of surfactants (nonionic and anionic) and dolomite rock substrates. A new experimental procedure was developed in which crude oil equilibrated with reservoir brine has been exposed to surfactant to simulate the matrix-fracture interactions in fractured reservoirs. This procedure enables the measurements of dynamic contact angles and oil–water interfacial tensions, in addition to providing the visual observations of the dynamic behavior of crude oil trapped in the rock matrix as it encounters the diffusing surfactant from the fractures. Both the measurements and visual observations indicate wettability alterations of the matrix surface from oil-wet to less oil-wet or intermediate wet by the surfactants. Thus this study is of practical importance to oil-wet fractured formations where surfactant-induced wettability alterations can result in significant oil recovery enhancements. In addition, this study has also identified the need to include contact angle term in the dimensionless Bond number formulations for better quantitative interpretation of rock–fluids interactions.     

Ozonation Impact on Degradation and Toxicity of Non-Ionic Surfactants

Aqueous solutions of five selected non-ionic surfactants: Triton (i-octylphenolethoxylates), Tergitol (2,6,8-trimethyl-4-nonanoloxethylates), Symperonic (n-nonylphenol-oxethylates) and Brij (fatty alcohol ethoxylates) were investigated in this study. Using the bioluminescent bacteria Vibrio fischeri the toxicity of the surfactants solutions were determined. An attempt was made to relate rather low biodegradability of nonionic surfactant solutions measured by the BOD₅/COD ratio (ranging from 1 to 17%) to their toxicity. The ozonation process was carried out in a 1.5 dm³ stirred cell reactor equipped with two ozone detectors. The following parameters were analyzed: pH, COD, BOD₅, DOC, TOC, polarography as well as UV spectrum. The positive effect of ozonation, represented by decay of UV absorption, was visible in almost complete destruction of the surfactants, with exception of Triton X-705 (only 65% degradation after absorption of 2000 mgO₃/dm³). The most striking results were obtained in toxicity tests for ozonated solutions of the non-ionic surfactants – an increase of the bacterial growth inhibition (1.5 to 4 times increase in toxicity due to ozonation). The obtained results were discussed taking into account the literature and our own experimental data on mechanisms of ozonation and biodegradation of non-ionic surfactants of the Triton-type and similar chemical structures.     

The Interaction of Glymes with Surfactant Micelles

The critical micelle concentrations (CMC) values and counterion dissociation (α values) have been determined for a number of mixed micellar systems consisting of two typical ionic surfactants and glycol ethers (glymes) as cosurfactants, namely diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether. Conductance experiments were used to determine the CMC and α values of the mixed micelles as a function of glyme concentration in the aqueous mixed solvent. Favorable interactions between sodium dodecyl sulfate micelles and glyme cosurfactants were deduced from the decreases in the CMC values and the large increase in the α values of these systems as a function of increasing glyme concentration in the mixed solvents. In contrast to the anionic surfactant/glyme systems, in general, there appeared to be little favorable interactions between the surfactant and glymes when micelles of the cationic surfactant dodecyltrimethylammonium bromide were formed in water/glyme solvent systems containing an increasing amount of the glymes. The interaction of glymes with the surfactant micelles was examined closely via ¹³C nuclear magnetic resonance (NMR) chemical shifts for both surfactant and glyme carbons; these chemical shifts changes were interpreted in terms of the distribution and the localization of the glymes in the aggregates. Finally, partition constants, determined from two-dimensional diffusion-oriented spectroscopy (2D-DOSY) experiments, were used to calculate thermodynamic quantities of transfer of the glymes between the bulk phase and the self-assembled aggregates. All these results are interpreted in terms of the key contributions that both the glyme ethoxylated groups and alkyl endgroups make to the hydrophobic interactions.     

混合指示剂单相滴定法测定烷基磷酸酯钾盐

本研究用混合指示剂单相滴定法测定ISO标准方法所不能测定的磷酸盐阴离子表面活性剂的浓度.测定PK、E502A、昆山PK的常数K分别为355.lg/M、420.7g/M和344.0g/M,变异系数分别为1.45%、0.59%和1.26%,测定实际试样的加标回收率为98.2～103.9%.方法准确、简单、快速,不需用毒性较大的有机溶剂,本法适用于化纤油剂和涤纶短纤维上油率等的测定.     

Thermal analysis of montmorillonites modified with quaternary phosphonium and ammonium surfactants

The thermal stability of seven organically modified montmorillonites (‘organoclays’) has been investigated using differential thermal analysis, differential scanning calorimetry, and thermogravimetry in conjunction with X-ray diffractometry. Six organoclays were synthesised by replacing the interlayer inorganic cations, initially present, with quaternary phosphonium and ammonium surfactant cations. The samples modified with tetrabutylphosphonium (TBP), and butyltriphenylphosphonium (BTPP) ions have an appreciably higher thermal stability than the octadecyltrimethylammonium (ODTMA)-modified clays. Thus, in the case of TBP- and BTPP-modified montmorillonites, the onset temperature of decomposition is close to 300 °C. Samples modified with hexadecyltributylphosphonium (HDTBP) ions have a lower onset temperature of decomposition of 225 °C. In comparison, the onset temperature for ODTMA-montmorillonites (obtained at different concentrations of ODTMA-bromide) ranges from 158 to 222 °C, being highest where the concentration of intercalated surfactant is lowest. The onset temperature for a commercial alkylsilane-treated quaternary ammonium-modified organoclay (S-BEN N-400FP) is 207 °C. The basal spacing of the TBP- and BTPP-modified clays is 1.7–1.8 nm, indicating a monolayer arrangement of quaternary phosphonium ions in the interlayer space, while the value of 2.5 nm for HDTBP-montmorillonite indicates a more open structure. The ODTMA-modified samples have basal spacings ranging from 1.9 to 2.1 nm, indicative of a bilayer to pseudo-trilayer arrangement. The exceptionally high basal spacing of 3.4 nm for the S-BEN N-400FP organoclay might be due to interlayer penetration of organosilane hydrolysis products during synthesis. The thermal properties of organoclays are apparently related to the nature of the surfactants and their arrangement in the interlayer space of montmorillonite.     

聚乙烯亚胺含量对( Ni-P) -纳米Si3 N4复合刷镀层性能的影响

聚乙烯亚胺(PEI)是一种水溶性的高分子阳离子聚合物表面活性剂,可通过吸附在颗粒周围来阻止纳米颗粒相互接近,使得它们不能相互碰撞、吸引,防止纳米颗粒絮凝、团聚.研究了聚乙烯亚胺(PEI)表面活性剂对刷镀(Ni-P)-纳米Si3N4复合镀层性能及结构的影响,并确定了聚乙烯亚胺表面活性剂在复合刷镀液中的最佳含量.结果表明:聚乙烯亚胺表面活性剂能有效阻止复合刷镀液中颗粒的絮凝、团聚,其用量对复合刷镀层中Si3N4含量、刷镀层硬度及摩擦性能有显著的影响.当其含量为0.8 g/L时,获得了分散均匀、稳定悬浮的复合刷镀液,复合刷镀层微观表面结构致密,微粒分布均匀,摩擦因数最小为0.16,显微硬度最大为HV910.     

脂肪酸烷基醇酰胺硫酸酯的合成及性能研究

脂肪酸烷基醇酰胺硫酸酯是一类性能优异的新型阴离子型表面活性剂，尤其具有良好的钙皂分散性及乳化性。本文报道了其合成工艺条件，测定了有关物性     

Surface controlled synthesis of Cu2FeSnS4 particles for enhanced hydrogen evolution reaction

Cu₂FeSnS₄ (CFTS) particles are synthesized using different surfactants such as thioglycolic acid (TGA), polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA) via the solution process. The effect of surfactants on crystal structure, morphology, elemental composition, and electrocatalytic properties of CFTS particles are investigated. CFTS particles with a better crystalline phase are obtained in PVP (surfactant), while impurity phases are observed in TGA and PVA (surfactants). The morphology of CFTS is significantly changed when a different surfactant is used in the synthesis process. The mixture of aggregate and porous (1 μm) particles is observed when PVA is used as a surfactant to synthesize CFTS particles. At the same time, highly porous particles having nanosheets and nanoparticles at the surface are obtained in the case of PVP. In the TGA case, spherical particles with 1 μm size are observed. The electrocatalytic ability of all CFTS particles toward hydrogen evolution reactions (HER) is studied in 0.5 M H₂SO₄ electrolyte. The overpotential of PVP-based CFTS particles is the lowest as ƞ = 421 mV at 10 mA/cm² compared to the other two samples. CFTS particles synthesized using PVP exhibit enhanced electro-catalytic performance due to higher surface area.     

Synthesis of mesoporous ZnS synergistically templated by butylamine and alkanols

Pore size and pore volume adjustable mesoporous ZnS was synthesized through a co-template method, which was achieved by the combined interaction between butylamine and some alkanols with proper lengths of the straight carbon chain. The pore size for mesoporous ZnS templated by butyl amine alone was 4.29 nm, and could be enlarged to 6.96 and 8.33 nm respectively through adding certain amounts of hexanol and octanol. Correspondingly, the pore volume also exhibited an augmentation with increasing carbon chain lengths of alkanols from C₆ to C₈. However, the pore size and pore volume dropped abruptly when decanol was added as the auxiliary agent. The formation of mesopores for ZnS prepared using butylamine molecules as the only templating agent is considered to be attributed to the coordination between N atoms in amines and Zn²⁺ ions at the surfaces of zinc suphide. The templating effect of butylamines might be improved by adding hexanols and octanols to form aggregates through solubilization to tailor the pore size and pore volume of ZnS effectively, while the function of decanols for changing the porous structure is restricted by its low solubility.