Under‐Oil Superhydrophilic Poly(vinyl alcohol)/Silica Hybrid Nanofibrous Aerogel for Gravity‐Driven Separation of Surfactant‐Stabilized Water‐in‐Oil Emulsions

For efficient and green separation of surfactant‐stabilized water‐in‐oil (W/O) emulsions, under‐oil superhydrophilic poly(vinyl alcohol) (PVA)/silica hybrid nanofibrous aerogel is fabricated by freeze‐drying the dispersion of shortened PVA/tetraethyl orthosilicate composite electrospun nanofibers in t‐butanol, followed by heat‐treatment. Its hierarchical porous structure, observed by scanning electron microscope, consists of major and minor pores with an average diameter of 15.9 and 1.0 µm, respectively. The silica‐based crosslinking structure inside the nanofibers and the chemical linkage between them, evidenced by infrared spectroscopy, endows the nanofibrous aerogel with desirable stability in water and compression recoverability. When it is used for gravity‐driven separation of Span80 stabilized water‐in‐n‐hexane emulsion, the flux is 2083 L m^?2 h^?1 and the purity of the separated n‐hexane reaches 99.997%, corresponding to the separation efficiency of 99.79%. The nanofibrous aerogel after use is readily recycled by rinsing and freeze‐drying, without using any organic solvent, as it possesses under‐oil superhydrophilicity and prominent oil antifouling property. Differing from the previously reported separation materials, PVA/silica hybrid nanofibrous aerogel simultaneously acts as gravity‐driven filtration material and adsorption material to both absorb their coalesced water droplets and allow the separated oil to penetrate in the separation process.     

Predicting the Viscosity of Non‐Newtonian Water‐in‐Oil Emulsions Based on the Lederer Model

The accurate prediction of the viscosity of emulsions is highly important for oil well exploitation. Commonly used models for predicting the viscosity of water‐in‐oil (W/O) emulsions composed by two or three factors cannot always fit well the viscosity of W/O emulsions, especially in the case of non‐Newtonian W/O emulsions. An innovative and comprehensive method for predicting the viscosity of such emulsions was developed based on the Lederer, Arrhenius, and Einstein models, using experimental data. Compared with the commonly applied W/O emulsion viscosity models, the proposed method considers more factors, including temperature, volume fraction of water, shear rate, and viscosity of the continuous (oil) and dispersed phase (water). Numerous published data points were collected from the literature to verify the accuracy and reliability of the method. The calculation results prove the high accuracy of the model.     

一种新型高分子表面活性剂的破乳作用

探讨了合成的SDE系列共聚物乳液对原油乳状液的破乳作用。通过考察破乳剂用量和破乳温度等对该系列共聚物乳液的破乳作用的影响 ,发现该共聚物乳液对锦州采油厂老三联及锦一联集输站的原油具有良好的破乳效果 ,对孤岛采油厂等地的原油也有一定的破乳效果     

Thixotropic Behavior of Oil‐in‐Water Emulsions Stabilized with Ethoxylated Amines at Low Shear Rates

Oil‐in‐water (O/W) emulsification is a lubricating pipeline method based on the reduction of the energy frictional loss produced during viscous flow. The flow behavior of heavy O/W emulsions formulated with nonionic surfactants is described. The effects of pH and salinity of the aqueous phase on droplet diameter, stability, and apparent viscosity of O/W emulsions were evaluated. The low‐shear Couette flow of O/W emulsions displayed intense shear‐thinning and thixotropic behavior. Thixotropy was associated to the droplet deformation energy caused by shear rate changes. The droplet deformation and alignment led to the apparent viscosity reduction compared to the fluid at rest. Thixotropic behavior is supposed to balance between the breakdown and recovery of droplet ordered structures. Emulsion formulation parameters were influenced by the aqueous phase pH, enabling to manage the emulsion properties. The droplet mean diameter of < 18 µm resulted in very stable emulsions.     

Surfactant Concentration,Antioxidants, and Chelators Influencing Oxidative Stability of Water‐in‐Walnut Oil Emulsions

Effects of surfactant concentration, antioxidants with different polarities, and chelator type on the oxidative stability of water‐in‐stripped walnut oil (W/O) emulsions stabilized by polyglycerol polyricinoleate (PGPR) were evaluated. The formation of primary oxidation products (lipid hydroperoxides) and secondary oxidation products (hexanal) decreased with increasing PGPR concentrations (0.3–1.0 wt% of emulsions). Excess surfactant might solubilize lipid hydroperoxides out of the oil–water interface, resulting in the decreased lipid oxidation rates in W/O emulsions. At concentrations of 10–1000 μM, the polar Trolox demonstrated concentration‐dependent antioxidant activity according to both hydroperoxide and hexanal formation. The antioxidant efficiency of the non‐polar α‐tocopherol was slightly reduced at the higher range of 500–1000 μM based on hydroperoxide formation. Both ethylenediaminetetraacetic acid (EDTA) and deferoxamine (DFO) at concentrations of 5–100 μM reduced the rates of lipid oxidation at varying degrees, indicating that endogenous transition metals may promote lipid oxidation in W/O emulsions. EDTA was a stronger inhibitor of lipid oxidation than DFO. These results suggest that the oxidative stability of W/O emulsions could be improved by the appropriate choice of surfactant concentration, antioxidants, and chelators.     

Effect of emulsifiers on the preparation of food‐grade oil‐in‐water emulsions using a straight‐through extrusion filter

This paper describes the preparation characteristics of food‐grade soybean oil‐in‐water (O/W) emulsions using a novel straight‐through extrusion filter, named a silicon straight‐through microchannel (MC). Polyglycerol fatty acid ester (PGFE), polyoxyethelene sorbitan monolaurate (Tween 20), and sucrose fatty acid ester were tested as emulsifiers. Optical observations of the emulsification process exhibited that monodisperse oil droplets were stably formed from an oblong straight‐through MC for PGFE and Tween 20. The effect of the emulsifier on the straight‐through MC emulsification behavior is discussed. The selected PGFE‐ and Tween 20‐containing systems enabled us to prepare monodisperse O/W emulsions with droplet diameters of 38—39 μm and coefficients of variation below 3% using an oblong straight‐through MC with a 16 μm‐equivalent channel diameter.     

Antioxidant Activity of Seaweed Extracts: In Vitro Assays,Evaluation in 5 % Fish Oil‐in‐Water Emulsions and Characterization

In this study the antioxidant activity of absolute ethanol, 50 % ethanol and water extracts of two species of seaweeds, namely Fucus serratus and Polysiphonia fucoides, were evaluated both in in vitro assays and in 5 % fish oil‐in‐water (o/w) emulsions. The 50 % ethanolic extracts of P. fucoides showed higher antioxidant activity both in in vitro assays and in 5 % oil‐in‐water emulsion in the presence or absence of iron. In spite of the higher phenolic content and very good antioxidant activity in some of the in vitro assays, the absolute ethanol extracts of both the species showed a pro‐oxidative tendency in 5 % fish oil‐in‐water emulsion in the presence or absence of iron. In order to investigate the reason for the higher antioxidant activity of 50 % ethanolic extracts of P. fucoides, these extracts were further fractionated into polyphenol‐rich, protein‐rich, polysaccharide‐rich and low‐molecular‐weight fractions. These fractions were tested both in in vitro and in 5 % oil‐in‐water emulsions. The results of the present study showed that the main effect was due to the phenolic compounds. In conclusion, the 50 % ethanolic extracts of P. fucoides can be a potential source of natural antioxidants as these extracts have antioxidant activities similar to those of synthetic antioxidants such as BHT.     

Preparation and characterization of highly stable monodisperse argan oil‐in‐water emulsions using microchannel emulsification

Argan oil is well known for its nutraceutical properties. Its specific fatty acid composition and antioxidant content contribute to the stability of the oil and to its dietetic and culinary values. There is an increasing interest to use argan oil in cosmetics, pharmaceutics, and food products. However, the formulation of highly stable emulsions with prolonged shelf life is needed. In this study, argan oil‐in‐water (O/W) emulsions were prepared using microchannel (MC) emulsification process, stabilized by different non‐ionic emulsifiers. The effects of processing temperature on droplet size and size distribution were studied. Physical stability of argan O/W emulsions was also investigated by accelerated stability testing and during storage at room temperature (25 ± 2°C). Highly monodisperse argan O/W emulsions were produced at temperatures up to 70°C. The obtained emulsions were physically stable for several months at room temperature. Furthermore, emulsifier type, concentration, and temperature were the major determinants influencing the droplet size and size distribution. The results indicated that a suitable emulsifier should be selected by experimentation, since the interfacial tension and hydrophilic–lipophilic balance values were not suitable to predict the emulsifying efficiency. Practical applications: MC emulsification produces efficiently monodisperse droplets at wide range of temperatures. The findings of this work may be of great interest for both scientific and industrial purposes since highly stable and monodisperse argan oil‐in‐water emulsions were produced which can be incorporated into food, cosmetic, or pharmaceutical formulations.     

Water‐Based Bitumen Recovery from Diluent‐Conditioned Oil Sands

Important process development aspects leading to more efficient bitumen recovery from diluent‐conditioned oil sands by water‐based methods are discussed. Bitumen viscosity of 0.5–2 Pa·s is required at the processing temperature and can be reduced to this level by bitumen dilution with an organic solvent. Oil sand porosity, however, poses a restriction on the amount of diluent that can be accepted by the oil sand. Also oil sand‐diluent conditioning time is an important process parameter and can vary from a few minutes for oil sands with low‐viscosity bitumen to several hours if viscosity of the bitumen is high. Additionally, the bitumen separation efficiency during digestion and flotation can be enhanced by reducing the bitumen/water interfacial tension through addition, for example, of tripolyphosphate to the aqueous phase.     

Comparison of Storage Methods for Microfluidically Produced Water‐in‐Oil Droplets

Microfluidically produced water‐in‐oil droplets are an important platform for biochemical research. To investigate the structural integrity of droplets during transfer and storage processes, different methods were compared. Storage as isolated droplets inside plastic tubing or a designed microfluidic chamber led to moderate decreases in droplet volume but only slight changes in monodispersity, whereas bulk storage in an Eppendorf cup led to the complete loss of monodispersity. It is further demonstrated that on‐chip storage of the droplets in a fluidic microcavity array avoids coalescence and enables a reduction in volume with the concurrent increase in the concentration of entrapped proteins, which is relevant for applications in life science.     

微乳液型反相破乳剂的研制及应用

研制了对反相原油乳状液兼有良好清水和快速脱水作用的微乳液型破乳剂,并将其应用于大庆油田喇Ⅱ-1联合站的原油脱水和采出水处理中。在喇Ⅱ-1联合站原有的一段游离水脱除加二段电脱水原油脱水工艺和一级沉降加一级纤维球过滤采出水处理工艺不变的情况下,在采出液中投加15mg/L研制的反相原油乳状液破乳剂后,游离水脱除器放水的平均含油量由投加微乳液型破乳剂前的2004·5mg/L降低到442·8mg/L,处理后采出水的平均含油量由投加微乳液型破乳剂前的31·2mg/L降低到4·1mg/L,药剂费用为0·14元/m3。     

新型原油破乳剂DCN-1的合成及应用

介绍了破乳剂DCN - 1的研制、性能和现场试验结果。它是针对河南油田的高含水稠油研制的一种水溶性高分子破乳剂 ,对该区稠油具有脱水速度快、出水量大、油水界面齐、污水含油率低的特点。     

The Stability of Water‐in‐Crude and Model Oil Emulsions

The critical electric field (cef) technique has been utilized to measure the stabilities of a variety of water‐in‐model oil and petroleum emulsions. The cef method allows for a fast, reproducible, and quantitative gauge of emulsion stability. Here, we have used cef to measure the stability of water‐in‐heptane‐toluene‐asphaltene emulsions and confirmed the importance of solvation of asphaltenes and the state of asphaltene aggregation to emulsion stability. Emulsion stability increased with the concentration of soluble asphaltenes near the point of precipitation. Droplet sizes were measured with optical microscopy in order to calculate interfacial areas and film thicknesses. It was found that film thickness increased with asphaltene concentration up to the solubility limit, above which increased concentration had little effect, and cef increased with interfacial film thickness up to a monolayer coverage of asphaltene aggregates, above which film thickness had a much smaller effect. These findings were applied to a cef investigation of water‐in‐ppetroleum emulsions to develop correlations of the stability of water‐in‐ccrude oil emulsions. A strong correlation (coefficient = 0.95) was found for cef with the product of asphaltene concentration and the difference in hydrogen to carbon atomic ratios of the asphaltenes and petroleum solvent. The development of a kinetic model and its fit to experimental data revealed the effects of asphaltene chemistry, solvency, and resin concentration on the adsorption and consolidation of emulsion stabilizing interfacial films.     

Healthier lipid combination oil‐in‐water emulsions prepared with various protein systems: an approach for development of functional meat products

Five protein‐stabilized oil‐in‐water emulsions were prepared using sodium caseinate (O/SC), soy protein isolate (O/SPI), sodium caseinate and microbial transglutaminase (O/SC + MTG), sodium caseinate, microbial transglutaminase and meat slurry (O/SC + MTG + MS) and SPI, sodium caseinate and microbial transglutaminase (O/IPS + SC + MTG); their composition (proximate analysis and fatty acid profile) and physicochemical characteristics were examined. The lipid phase was a combination of healthy fatty acids from olive, linseed and fish oils, containing low proportions (15%) of saturated fatty acids (SFA) and high proportions of monounsaturated fatty acids (MUFA, 47%) and polyunsaturated fatty acids (PUFA, 36%), with a PUFA/SFA ratio >2, and a n‐6/n‐3 PUFA ratio of 0.4. All the oil‐in‐water emulsions showed high thermal and creamy stability. Results of penetration test and dynamic rheological properties showed la existencia de different types of oil‐in‐water emulsion structures according to stabilizing system of emulsion. Those structures ranged from concentrate solution‐like (stabilized only with SC) (gel strength 0.06 mJ) to gel‐like (samples containing MTG) behaviours (gel strength ranged between 3.4 and 6.2 mJ). Morphological differences in the organization of the network structure were observed (by scanning electron microscopy) as functions of the protein system used to stabilize the oil‐in‐water emulsions.     

Water‐Borne Polymer/Graphene Nanocomposites

The potential of polymerization in a dispersed system as an attractive technique for polymer/graphene composite synthesis is discussed. This overview is focused on the preparation of graphene/polymer composite materials by two methods: (i) emulsion mixing or blending of polymer and graphene aqueous dispersions, and (ii) in situ polymerization in a dispersed system (emulsion, miniemulsion, microemulsion, and Pickering‐stabilized emulsion). Various methods for the stabilization of graphene nanoplatelets (GNPs) prior to composite preparation are presented, and the established specific interactions between the filler and the matrix are discussed. The determination of the electrical conductivity and the opportunity offered by polymerization in a dispersed system for the formation of a segregated network of graphene filler in the frame of a polymer matrix are presented. The mechanical and thermal properties of the composites are also discussed. A short summary of the open questions regarding the synthesis of water‐borne polymer/graphene composites is presented.

     

Water‐Soluble Nitric‐Oxide‐Releasing Acetylsalicylic Acid (ASA) Prodrugs

A series of water‐soluble (benzoyloxy)methyl esters of acetylsalicylic acid (ASA), commonly known as aspirin, are described. The new derivatives each have alkyl chains containing a nitric oxide (NO)‐releasing nitrooxy group and a solubilizing moiety bonded to the benzoyl ring. The compounds were synthesized and evaluated as ASA prodrugs. After conversion to the appropriate salt, most of the derivatives are solid at room temperature and all possess good water solubility. They are quite stable in acid solution (pH 1) and less stable at physiological pH. In human serum, these compounds are immediately metabolized by esterases, producing a mixture of ASA, salicylic acid (SA), and of the related NO‐donor benzoic acids, along with other minor products. Due to ASA release, the prodrugs are capable of inhibiting collagen‐induced platelet aggregation of human platelet‐rich plasma. Simple NO‐donor benzoic acids 3‐hydroxy‐4‐(3‐nitrooxypropoxy)benzoic acid ( 28 ) and 3‐(morpholin‐4‐ylmethyl)‐4‐[3‐(nitrooxy)propoxy]benzoic acid ( 48 ) were also studied as representative models of the whole class of benzoic acids formed following metabolism of the prodrugs in serum. These simplified derivatives did not trigger antiaggregatory activity when tested at 300 μM . Only 28 displays quite potent NO‐dependent vasodilatatory action. Further in vivo evaluation of two selected prodrugs, {[2‐(acetyloxy)benzoyl]oxy}methyl‐3‐[(3‐[aminopropanoyl)oxy]‐4‐[3‐(nitrooxy)propoxy]benzoate?HCl ( 38 ) and {[2‐(acetyloxy)benzoyl]oxy}methyl 3‐(morpholin‐4‐ylmethyl)‐4‐[3‐(nitrooxy)propoxy]benzoate oxalate ( 49 ), revealed that their anti‐inflammatory activities are similar to that of ASA when tested in the carrageenan‐induced paw edema assay in rats. The gastrotoxicity of the two prodrugs was also determined to be lower than that of ASA in a lesion model in rats. Taken together, these results indicated that these NO‐donor ASA prodrugs warrant further investigation for clinical application.     

Interfacial Crystallization of Diacylglycerols Rich in Medium‐ and Long‐Chain Fatty Acids in Water‐in‐Oil Emulsions

The effects of diacylglycerols rich in medium‐ and long‐chain fatty acids (MLCD) on the crystallization of hydrogenated palm oil (HPO) and formation of 10% water‐in‐oil (W/O) emulsion are studied, and compared with the common surfactants monostearoylglycerol (MSG) and polyglycerol polyricinoleate (PGPR). Polarized light microscopy reveals that emulsions made with MLCD form crystals around dispersed water droplets and promotes HPO crystallization at the oil‐water interface. Similar behavior is also observed in MSG‐stabilized emulsions, but is absent from emulsions made with PGPR. The large deformation yield value of the test W/O emulsion is increased four‐fold versus those stabilized via PGPR due to interfacial crystallization of HPO. However, there are no large differences in droplet size, solid fat content (SFC), thermal behavior or polymorphism to account for these substantial changes, implying that the spatial distribution of the HPO crystals within the crystal network is the driving factor responsible for the observed textural differences. MLCD‐covered water droplets act as active fillers and interact with surrounding fat crystals to enhance the rigidity of emulsion. This study provides new insights regarding the use of MLCD in W/O emulsions as template for interfacial crystallization and the possibility of tailoring their large deformation behavior. Practical Applications: MLCD is applied in preparing W/O emulsion. It is found that MLCD forms unique interfacial Pickering crystals around water droplets, which promote the surface‐inactive HPO nucleation at the oil‐water interface. Thus MLCD‐covered water droplets act as active fillers and interact with surrounding fat crystals, which can greatly enhance the rigidity of emulsion. This observation would provide a theoretical reference and practical basis for the application of the MLCD with appreciable nutritional properties in lipid‐rich products such as whipped cream, shortenings margarine, butter and ice cream, so as to substitute hydrogenated oil. MLCD‐stabilized emulsions can also be explored for the development of novel confectionery products, lipsticks, or controlled release matrices.