Linker-modified microemulsions for a variety of oils and surfactants

Previously, we reported on the use of hydrophilic and lipophilic linker molecules to enhance the solubilization capacity of chlorinated hydrocarbons using sodium dihexyl sulfosuccinate (SDHS). In this work we extend the use of linker molecules to a wider range of oils and surfactants. The data show that the linker effect works for all the systems studied and that linker-based systems are even more economical than surfactant-only systems for more hydrophobic oils. Using a more hydrophobic surfactant, such as sodium bis(2-ethyl)dihexyl sulfosuccinate (Aerosol-OT), requires a formulation enriched with a hydrophilic linker, whereas the formulation for the more hydrophilic SDHS requires the use of a more lipophilic linker. By considering the properties and appearance of the formulation before contacting with the oil, and by evaluation the coalescence dynamics, we found that hydrophilic linker-rich formulations were preferred. These formulations were tested as fabric pretreatments for removing motor oil and hexadecane from cotton, and as flushing solutions for glass bead columns contaminated with these oils. The cleaning performance of these linker-based systems was superior to common surfactant and pretreatment formulations in the detergency tests, achieving more than 80% removal of motor oil and hexadecane trapped in the packed-column flushing tests.     

DISPLACEMENT OF A HYDROCARBON OIL FROM A METAL SURFACE USING A SURFACTANT SOLUTION

ABSTRACT

Separation of oils from solid surfaces is important in cleaning and degreasing operations. Water and oils are immiscible requiring the use of an additive which is miscible with water yet has an affinity for oils. Surface active agents, known as surfactants, have this property, being miscible with water while having an affinity for hydrocarbons. In some cases, surfactant solutions displace oils from a solid surface (i.e., remove oil by replacing the oil/solid interfacial area with surfactant solution/solid interfacial area). The presence of alkalinity as well as surfactant concentration is known to affect the ability of a surfactant solution to wet the solid surface and displace the oil. Experiments have been performed to determine quantitatively the effects of surfactant concentration and pH on the displacement of an oil from a metal surface. The displacement is measured in terms of the contact angle formed by the oil on the solid surface in the presence of the surfactant solution, the amount of time needed for the surfactant solution to cause part of the oil to detach from the solid surface, and the volume of the detached oil. Measuring the contact angle of the oil as a function of time shows that surfactant concentration and pH affect the displacement of oil from a metal surface. Increasing the pH of a solution of Triton X-100, a non-ionic surfactant, enhances oil displacement. Increasing the surfactant concentration also enhances oil displacement. The volume of oil which detaches from the solid surface increases with increasing pH and increasing surfactant concentration.

     

Evaluation of plant-based oils for production of offset printing ink

The oils and solvents are the main components of the printing ink, and the chemical composition of the ink could be harmful or toxic to human health and the environment. Therefore, there is an increasing demand to develop inks containing green, biobased, sustainable, and renewable raw materials instead of petrochemical substances. In this study, flaxseed oil (FO), pomegranate seed oil, plum kernel oil (PKO), and grape seed oil (GSO) were selected to produce offset printing inks. Pinus pinaster (P. pinaster) resin was also used in the formulation of inks to examine the effects of natural resin on ink together with vegetable oils. The phenolic content was analyzed for the resin and oils to figure out their potential antioxidant and bioactive characteristics. Optical and rheological tests were applied to evaluate the printability of the inks. L*a*b*, ΔE, density, and gloss tests were performed for optical evaluation. The viscosity, tack, and rub resistance tests were applied to perform rheological analysis. The biobased, environmental friendly, and self-drying (cold set) offset printing inks were obtained using natural pine resin and three different plant-based oils FO, PKO, and GSO. The printability analysis of the inks figured out the potential usage of plant-based oils in the offset printing ink formulation.     

我国洗涤用绿色表面活性剂最新进展

随着石油价格的不断上涨,以油脂和淀粉等生物质资源为原料的表面活性剂越来越受到重视。以脂肪酸甲酯磺酸盐（MES）、脂肪酸甲酯乙氧基化物（FMEE）、烷基葡萄糖苷（APG）、聚甘油脂肪酸酯（PGFE）以及改性油脂和植物油酸等为代表的一系列绿色表面活性剂的生产和应用技术趋于成熟。在各类清洁产品中将逐步取代传统的石油基表面活性剂,如烷基苯磺酸钠和脂肪醇聚氧乙烯醚等。新型绿色表面活性剂的应用将推动我国洗涤剂行业逐步走上可持续发展之路。     

Effect of Ionic Strength on Oil Removal from Stainless Steel in the Presence of Ionic Surfactant

Abstract

Contact angles of oil droplets on solid surfaces provide useful insight into surfactant cleaning behavior. Contact angles of hexadecane and MAR‐TEMP^® 355, an industrial quench oil, on stainless steel were measured for ionic surfactant solutions as a function of ionic strength. The ionic strength of sodium dodecyl sulfate (SDS) and cetyl trimethyl ammonium bromide (CTAB) solutions was modified by the addition of sodium chloride. Increases in the contact angle with additions of 1.0 mM and 2.5 mM NaCl were observed for the two oils in SDS and for hexadecane in CTAB. For the industrial quench oil, detachment occurred in CTAB concentrations above the critical micelle concentration; as a result, the equilibrium contact angle measurements were not measured. The critical concentration of CTAB decreased with increasing NaCl concentration. Oil‐removal studies indicate that increasing ionic strength by as little as 2.5 mM can result in improved cleaning. A theoretical insight previously used to explain contact‐angle behavior for a hexadecane‐gold system is used to describe the results obtained with the current system.     

Cleaning Ability of Mixed Solutions of Sulfonated Fatty Acid Methyl Esters

Here, we present results from a systematic study on cleaning of oily deposits from solid surfaces (porcelain and stainless steel) by solutions of fatty acid sulfonated methyl esters (SME), sodium salts. The zwitterionic dodecyldimethylamine oxide (DDAO) has been used as a cosurfactant. As representatives of the vegetable and mineral oils, sunflower seed oil and light mineral oil have been used. The process of oil drop detachment from the solid substrates (roll-up mechanism) has been monitored. In the case of porcelain, excellent cleaning of oil is achieved by mixed solutions of SME and DDAO. In the case of stainless steel, excellent cleaning (superior than that by linear alkylbenzene sulfonate and sodium lauryl ether sulfate) is provided by binary and ternary mixtures of SME, which may contain also DDAO. For the studied systems, the good cleaning correlates neither with the oil/water interfacial tension, nor with the surfactant chainlength and headgroup type. The data imply that governing factors might be the thickness and morphology of admicelle layers formed on the solid/water interface. The results indicate that the SME mixtures represent a promising system for formulations in house-hold detergency, having in mind also other useful properties of SME, such as biodegradability, skin compatibility, and hard water tolerance.     

Formulation of ultralow interfacial tension systems using extended surfactants

Inspired by the concept of lipophilic and hydrophilic linkers, extended surfactants have been proposed as highly desirable candidates for the formulation of microemulsions with high solubilization capacity and ultralow interfacial tension (IFT), especially for triglyceride oils. The defining characteristic of an extended surfactant is the presence of one or more intermediate-polarity groups between the hydrophilic head and the hydrophobic tail. Currently only limited information exists on extended surfactants; such knowledge is especially relevant for cleaning and separation applications where the cost of the surfactant and environmental regulations prohibit the use of concentrated surfactant solutions. In this work, we examine surfactant formulations for a wide range of oils using dilute solutions of the extended surfactant classes sodium alkyl polypropyleneoxide sulfate (R-(PO) _x −SO₄Na), and sodium alkyl polypropyleneoxide-polyethyleneoxide sulfate (R-(PO) _y -(EO) _z −SO₄Na). The IFT of these systems was measured as a function of electrolyte and surfactant concentration for polar and nonpolar oils. The results show that these extended surfactant systems have low critical micelle concentrations (CMC) and critical microemulsion concentrations (CμC) compared with other surfactants. We also found that the unique structure of these extended surfactants allows them to achieve ultralow IFT with a wide range of oils, including highly hydrophobic oils (e.g., hexadecane), triolein, and vegetable oils, using only ppm levels of these extended surfactants. It was also found that the introduction of additional PO and EO groups in the extended surfactant yielded lower IFT and lower optimum salinity, both of which are desirable in most formulations. Based on the optimum formulation conditions, it was found that the triolein sample used in these experiments behaved as a very polar oil, and all other vegetable oils displayed very hydrophobic behavior. This unexpected triolein behavior is suspected to be due to uncharacterized impurities in the triolein sample, and will be further evaluated in future research.     

Extended Surfactants Including an Alkoxylated Central Part Intermediate Producing a Gradual Polarity Transition—A Review of the Properties Used in Applications Such as Enhanced Oil Recovery and Polar Oil Solubilization in Microemulsions

The research published in the past half century indicates that surfactant interfacial performance in producing low tension or high solubilization with polar oils is not generally attained with pure conventional species exhibiting well-defined polar and nonpolar parts. The improvement trends reached with surfactant mixtures as well as the introduction of additives like cosurfactants and linkers lead to the introduction of the so-called extended surfactants, whose structure includes an intermediate polarity spacer between the hydrophilic head and the lipophilic tail. Recent investigations on different kinds of surfactants in a variety of applications—such as detergency, cosmetics, enhanced oil recovery or crude demulsifying, and vegetable oil extraction—indicate that these extended surfactants are likely to be particularly performing with oils containing polar groups, such as triacylglycerols and asphaltenic crudes. Possible applications of extended surfactants in enhanced oil recovery, crude emulsion breaking, detergency and cleaning, medicine and cosmetics vehicles, and natural oil extraction as well as some other cases are quickly reviewed.     

How to Attain Ultralow Interfacial Tension and Three-Phase Behavior with Surfactant Formulation for Enhanced Oil Recovery: A Review. Part 1. Optimum Formulation for Simple Surfactant–Oil–Water Ternary Systems

Enhanced recovery of crude oil by surfactant flooding requires the attainment of an ultralow interfacial tension. Since Winsor’s work in the 1950s it has been known that a minimum interfacial tension and a concomitant three-phase behavior of a surfactant–oil–water system occurs when the interactions of the surfactant and the oil and water phases are exactly equal. It has been known since the 1970s that these conditions are attained when a linear correlation is satisfied between the formulation variables, which are characteristic parameters of the substances as well as the temperature. This first part of our review on how to attain ultralow interfacial tension for enhanced oil recovery shows how formulation scan techniques using these correlations are used to determine an optimum formulation and to characterize unknown surfactants and oils. The physicochemical significance of the original empirical correlation is reported as the surfactant affinity difference or hydrophilic–lipophilic deviation model. We report the range of accurate validity of, and how to test, this simple model with four variables.     

A review of environmentally friendly rubber production using different vegetable oils

Vegetable oils were investigated as plasticizers to improve the sustainability of rubber compounding. The potential use of different vegetable oils as an alternative to petroleum-based rubber process oils was reviewed. This article presents a literature review on the current understanding of the influence of vegetable oil properties on natural rubber (NR) compounding. Hansen solubility parameters of the vegetable oils were determined to assist with the selection of vegetable oil for NR. We believe that the use of Hansen parameters could make the use of vegetable oils in rubber more convenient and cost-effective.     

Adhesion of edible oils to food contact surfaces

Adhesion of oils and fatty food products to packages is an important storage problem, because it increases product-package interactions that alter quality. Reducing such adhesion would also allow savings in recycling and cleaning processes. The aim of our work was to test if some thermodynamical adhesion models were correlated to edible oils’ bulk adhesion as measured experimentally. Food-contact surfaces were low-density polyethylene, polyethylene teraphthalate, stainless steel, and glass. The Young-Dupré equation and five models of adhesion from the literature were used to calculate solids’ surface tension and the thermodynamical work of adhesion (Wa). The dispersive, polar, acid-base, and hydrogen surface tension components of oils and solids were calculated. The experimental adhesion, or amount of edible oils remaining on solid surfaces after contact, was found to be correlated to Young-Dupré Wa, involving contact angle measured by specially designed image analysis technique. Two models, involving, respectively, surface tension’s hydrogen component and a linear dependence of Wa^p on the liquid polar surface tension component, fitted best with oil bulk adhesion as measured experimentally. Our theoretical approach to fatty food material adhesion seems, so far, consistent to predict global residues of edible oils on solid surfaces.     

Use of ethylcellulose polymers as stabilizer in fat-based food suspensions examined on the example of model reduced-fat chocolate

Surfactants are an important ingredient in the manufacture of chocolate. Their role is to coat the surfaces of the sugar and cocoa particles dispersed in fat, generally cocoa butter, to maintain or enhance the flowability of molten chocolate. Coating the surfaces of the dispersed particles with a surfactant reduces inter-particle interactions responsible for particle aggregation which leads to viscosity reduction of the mixture. Controlled flow behavior of molten chocolate is a requirement for successful processing and for optimal mouthfeel. This becomes in particular crucial in the formulation of fat-reduced chocolate. In fat-reduced chocolate, low molecular weight surfactants such as lecithin and polyglycerol polyricinoleate (PGPR) need to be applied at unacceptably high concentrations to maintain flowability of a chocolate with increased dispersed phase volume. This paper reports on an alternative approach, the use of the polymeric surfactant ethylcellulose. Shear viscosity measurements on model chocolates demonstrated a viscosity reducing effect. The effect of ethylcellulose polymer adsorbed at an oil/water interface was visualized in volume change experiments on macroscopic pendant drops revealing a difference in the nature of the interface compared to an interface covered with a low molecular weight surfactant.     

微乳型厨房除油污气雾剂的研制

本文阐述了厨房油垢的成因以及常用的洗涤方法、将溶剂的渗透、溶解性能和表面活性剂的渗透、润湿、乳化性能结合,研制一种微乳型的弱碱性厨房清洗剂,在弱碱性条件下达到较好的去油污效果,对环境友好,而且具有光亮功能。选用合适的抛射剂和防锈剂制成气雾剂,解决了洗涤剂对马口铁罐的腐蚀问题。     

Effects of Triglyceride Molecular Structure on Optimum Formulation of Surfactant-Oil-Water Systems

The effects of triglyceride molecular structure on the formulation of surfactant-oil-water systems were evaluated by comparing the optimum salinity and the dynamic interfacial tensions. The systems contained an anionic extended surfactant and triglyceride oils with different chain lengths and degrees of unsaturation. The results show that with an increasing degree of oil unsaturation (more double bonds), surfactant interactions with the triglycerides become weaker, thus requiring higher optimum salinity and resulting in higher interfacial tension values. Effects of ester groups and chain length of triglycerides are also discussed and the EACN of the triglycerides and vegetable oils studied are reported.     

Performance of classic oils and lubricating oils in froth flotation of Ukraine coal

In this study, the appropriate collector and collector amount for Ukraine coal in froth flotation was determined. For this purpose, the performance of classic oils (kerosene, diesel-oil and fuel-oil) and lubricating oils (spindle oil, bright stock and heavy neutral) was evaluated by combustible recovery, ash rejection and efficiency index. It was found that the combustible recovery and ash rejection changed, depending on the type and concentration of oil. The maximum combustible recovery was obtained by using bright stock. It was determined that bright stock, fuel-oil and kerosene were suitable for the flotation of Ukraine coal. On considering the flotation efficiency index values, the best results were obtained with bright stock and diesel-oil. Consequently, it was shown that bright stock and spindle oil could be used as alternative oils instead of classic oils for cleaning of Ukraine coal by the froth flotation.     

Insights into the compatibility of vegetable-based plasticizers on the performance of filled rubber vulcanizates

Substitution of petroleum-based processing oils with eco-friendly sustainable plasticizers in rubber compounds has gained much global attention due to their toxicity. In this regard, so far, the major attempts have focused on substituting aromatic oils with fatty acid based vegetable oils. In this work, the chemical and physical effects of canola oil as a model of fatty acid based vegetable oils on the process-ability, vulcanization kinetics, and final properties of carbon-black filled styrene–butadiene rubbers are systematically investigated. In contrast to the previous studies, it was shown that although these types of vegetable oils have a plasticizing impact, they can indeed threaten the requirements of reinforcing criteria in rubber vulcanizates. The final properties of the vulcanizates were found to be deteriorated due to the incompatibility of canola oil fatty acids constituents with rubber matrix and especially as a result of chemical interference of their unsaturated bonds in sulfur vulcanization kinetics.     

稠油油藏深部微乳酸酸化体系研究

油井生产过程中近井地带渗透率逐渐下降,利用酸蚀作用可提高渗透率。微乳酸体系把常规酸与油、表面活性剂以及助表面活性剂混合形成一种均匀、透明的体系,具有很高的稳定性,油/水界面张力超低,利用微乳酸进行稠油油藏深部酸化,对油井和水井解堵具有广泛的应用前景。     

溶解度参数原理在厨房重垢洗涤剂配方中的应用

厨房油烟会产生烦人的油垢,既影响厨房卫生,又不利于身体健康,其清洗难度很大。常用的重油垢清洗剂有强碱型、溶剂型和表面活性剂型。强碱型对重油垢去除能力强,其缺点是腐蚀性较强,对器具表面和使用者有腐蚀性和伤害作用。有机溶剂型对油垢具有良好的溶解作用,但由于有机溶剂易燃、易爆而且有毒,不太适用于厨房环境。表面活性剂型使用方便、作用温和以及成本低,但对重垢的去除效果不太理想。利用溶解度参数原理,结合HLB值,在测定油垢酸值、溶解度参数等的基础上配制溶剂／表面活性剂型厨房重油垢清洗剂,所制得的清洗剂对油垢有较好的溶解和乳化效果。     

微乳液应用于金属表面油污的清洗

以十二烷基苯磺酸钠(SDBS)为表面活性剂配制了微乳液,对金属表面油污清洗进行模拟实验,考察了SDBS、Na2CO3、煤油、正丁醇用量对微乳液清洗率的影响,并从温度稳定区间范围、清洗率随温度及时间变化对不同配方进行考察,最终筛选出一种处理金属表面油污的最佳微乳液配方:SDBS含量为8％(以去离子水的质量计,下同)、Na2CO3含量为1.4％、煤油含量为12.8％、正丁醇含量为6.4％.随后,考察了缓蚀剂的种类及用量对碳钢、黄铜、铝3种金属的防护性能,最终选定以含量0.06％硅酸钠作为微乳液缓蚀剂;对制得的清洗剂进行了性能评价,其清洗率在98％左右,在实验期内碳钢、黄铜、铝表面光洁,没有明显的质量变化和生锈情况,表明该清洗剂具有优良的缓蚀防锈性能.     

Microemulsion-Based Vegetable Oil Detergency Using an Extended Surfactant

This work examined the use of a single extended surfactant in the microemulsion-based detergency of vegetable oils. The results showed that good canola oil detergency (>80%) was achieved at 25 °C using a single extended surfactant (C_14,15–8PO–SO₄Na) at concentrations as low as 125 ppm, i.e., significantly lower than the surfactant concentration range of 500–2,500 ppm reported in other microemulsion-based detergency work. It was found that the maximum detergency (95%) was achieved in the type II microemulsion region. These results demonstrate that the microemulsion-based extended surfactant formulation is a promising approach for vegetable oil detergency at low temperature.