Stabilization of liquid water-in-oil emulsions by modifying the interfacial interaction of glycerol monooleate with aqueous phase ingredients

Glycerol monooleate (GMO)-stabilized liquid water-in-vegetable oil emulsions are difficult to stabilize due to the desorption of GMO from the water-vegetable oil interface toward the oil phase. This work improved the stability of GMO-stabilized liquid 20 wt% water-in-canola oil (W/CO) emulsion by modifying the dispersed aqueous phase composition with hydrogen bond-forming agents. As a control, 20 wt% water-in-mineral oil (W/MO) emulsion was also utilized. Different concentrations of hydrogen bond-forming agents (citric acid (CA), ascorbic acid (AA), low methoxyl pectin (LMP)) with and without salts (sodium chloride (S) or calcium chloride (Ca)) were added to the aqueous phase before emulsification, which enhanced emulsifier binding to the water–oil interface. W/CO emulsion without any aqueous phase additive destabilized instantly, whereas W/MO emulsion stayed stable during the week-long observation. The addition of hydrogen bond-forming agents and salts significantly improved emulsion stability. LMP, with many hydrogen bond-forming groups, was able to provide the highest emulsion stability after 7 days in both oils compared to AA, CA and their mixtures with S. Emulsions with both oils formed weak gels due to the formation of an extensive network of water droplet aggregates. Overall, the hydrogen bond-forming agents interacted with GMO at the interface, thereby favoring their presence at the water droplet surface and significantly improving the stability of liquid W/CO emulsions. The knowledge developed in this research can be useful in utilizing GMO to stabilize liquid water-in-oil emulsions without using any fat crystal network.     

乳状液膜法提取红土矿浸出液中镍

采用Span-80-TBP-NH3×H2O体系乳状液膜法提取红土矿浸出液中的Ni(II),研究了膜相组成、内水相试剂浓度、膜相与内水相体积比(油内比)、乳水体积比对镍离子提取效果的影响. 采用微分法测定并比较了反应的浓度级数nC和时间级数nt. 结果表明,膜相组成为Span-80:TBP:石蜡:煤油(体积比)=5:4:2:89、内水相氨水浓度为2 mol/L、油内比为1:1、乳水体积比为1:3、外水相硫酸浓度为0.3 mol/L的条件下,经过二级提取后,红土矿浸出液中Ni(II)去除率可达80%;由浓度级数(nC=1)小于时间级数(nt=2.8)可知,该过程为化学反应控制过程.     

新型聚胺基微球制备及其吸附蛋白质性质

以反相乳液为模板,通过在聚乙烯亚胺（PEI）水溶液/液体石蜡的W/O乳状液中连续滴加戊二醛的方式,在液滴间聚并过程中,交联剂和PEI在油水界面发生交联反应,制备得到新型的聚胺基交联微球。所得微球表面光滑,球形对称,粒径分布范围0.37～4.29 ?m,平均粒径为 1.44 ?m。微球表面Zeta电位的等电点为10.6,热重分析结果表明交联反应提高了PEI的分解温度。吸附蛋白质的实验结果证明,微球能自脂肪酶、纤维素酶、?-淀粉酶、果胶酶的混合蛋白质溶液中选择性吸附脂肪酶,微球对所检测脂肪酶的最大吸附量为127.8 mg/g。     

Characterization of a double emulsion system (oil-in-water-in-oil emulsion) with low solid fats: Microstructure

A double emulsion system [oil-in-water-in-oil (O/W/O)] with 16.3% (w/w) water and 83% (w/w) oil was prepared and stabilized using a novel method of mixing two oil-in-water (O/W) emulsions together. The first emulsion consisted of 85% (w/w) liquid canola oil, 14.4%(w/w) water, 0.5% (w/w) sodium caseinate, and 0.1% (w/w) lecithin and the second emulsion contained 73% (w/w) canola oil, 8% (w/w) palm-cotton stearin (50∶50), 0.2% (w/w) lecithin, 18.2% (w/w) water, and 0.6% (w/w) sodium caseinate. Mixing the two emulsions (50∶50) by weight produced a product with 79% (w/w) liquid canola oil and 4% (w/w) palm-cotton stearin. The two O/W emulsions were prepared separately at 50°C, mixed together at 45°C for 2–5 min, and then supercooled in a −5°C ice/salt bath while mixing at low shear rates (2,000–3,000 rpm). Under supercooling conditions the fat globules in the second emulsion (containing liquid oil and stearin) began to break down as a result of fat crystal growth and shearing action and release plastic fat. During this stage, the continuous aqueous phase underwent a phase transition and the emulsion viscosity dropped from 37,000–50,000 to 250 cP. The released plastic fat continued to harden as the temperature dropped and stabilized the first O/W emulsion (containing only liquid oil). The low shear rate mixing was stopped when the temperature dropped below 15°C and before the O/W/O emulsion hardens. Microstructural analysis of the first emulsion before and after supercooling showed essentially intact fat globules. The microstructure of the second emulsion before supercooling showed the same intact globules as the first emulsion, but after supercooling, an amorphous mass with only a few intact globules was seen. By mixing the two emulsions together and supercooling, a stable O/W/O emulsion was formed with plastic fat as the continuous phase and the first O/W emulsion as the dispersed phase.     

乳化液膜法脱除废水中酚的正交实验研究

化工过程排放的部分废水中酚类的质量分数比较高,含酚废水是水体的重要污染物之一,对含酚废水进行脱酚处理,有利于保护环境和回收酚类物质。在模拟含酚废水情况下,对乳化液膜法脱酚进行了正交实验研究,乳化液膜体系为水/油/水型,内水相为氢氧化钠溶液,外水相为含酚水溶液,膜相为煤油。在最优实验条件下,苯酚的脱除率达到99.8%。     

Effects of NOx-inhibitor agent on fuel properties of three-phase biodiesel emulsions

Biodiesel is one of the more promising alternative clean fuels to fossil fuel, which can reduce the emissions of fossil fuel burning, and possibly resolve the energy crisis caused by the exhaustion of petroleum resources in the near future. The burning of biodiesel emits much less gaseous emissions and particulate matter primarily because of its dominant combustion efficiency. However, the high oxygen content in biodiesel not only promotes the burning process but also enhances NO_x formation when biodiesel is used as fuel. Biodiesel emulsion and the additive of NO_x-inhibitor agent are considered to reduce levels of NO_x emissions in this experimental study. The biodiesel was produced by transesterification reaction accompanied with peroxidation process. A three-phase biodiesel emulsion of oil-in water drops-in oil (O/W/O) and an O/W/O biodiesel emulsion containing aqueous ammonia were prepared afterwards. The effect of the existence of NO_x-inhibitor agent on the fuel properties and the emulsion characteristics of the O/W/O biodiesel emulsions were investigated. The experimental results show that the burning of the O/W/O biodiesel emulsion and the O/W/O biodiesel emulsion containing aqueous ammonia had larger fraction of fuel burnt and thus larger heat release than the neat biodiesel if water content is not considered for the calculation of heating value. The addition of aqueous ammonia within the dispersed phase of the O/W/O biodiesel emulsion appeared to deteriorate the emulsification characteristics. A smaller quantity of emulsion and greater kinematic viscosity were formed while a larger carbon residue and actual reaction-heat release also appeared for this O/W/O biodiesel emulsion. Aqueous ammonia in the O/W/O biodiesel emulsion produces a higher pH value as well. In addition, the number as well as the volumetric fraction of the dispersed water droplets is reduced for the O/W/O biodiesel emulsion that contains aqueous ammonia.     

三元复合驱中原油乳化作用研究

通过乳状液稳定实验考察了大庆油田碱-表面活性剂-聚合物三元复合驱过程乳状液的形成机理、乳状液类型及稳定性。结果表明,大庆原油与碱反应1d时,测得其浓相体积分数为25%,所形成的乳状液为O/W型乳状液,而随着原油与碱作用时间的增加,其浓相体积分数达到40%以上,形成W/O型乳状液,且乳状液稳定性随作用时间增加而增强。大庆原油与水溶性表面活性剂ORS-41溶液作用时,所形成的乳状液为O/W型,且乳状液的稳定性与原油和ORS-41作用时间的长短关系较小。原油与NaOH和ORS-41混合溶液作用时,形成上层为W/O型乳状液,下层为O/W型乳状液的混合体系。     

Efficient recovery of phenol from phenolic wastewater by emulsion liquid membrane

The recovery of phenol from phenolic wastewater by emulsion liquid membrane (ELM) was investigated. The W/O emulsion was prepared with kerosene, Span−80, carrier, liquid paraffin, and NaOH solution. The effects of NaOH concentration, oil–internal solution ratio, shearing speed, Span−80 concentration, and carrier type and concentration on emulsion breakage were studied. In the single factor experiments of stability of W/O emulsion, the lowest percentages of emulsion breakage were achieved at a NaOH concentration of 0.03 g/ml, an oil–internal solution ratio of 2:1, a shearing speed of 1500 r/min, a Span−80 concentration of 8%, a tributyl phosphate (TBP) concentration of 0.8%, and an ethyl acetate concentration of 0.8%, respectively. Then, the effects of nine factors on extraction efficiencies of phenol were investigated. This indicated that the effects of shearing speed, oil-internal solution ratio, emulsion-external solution ratio, liquid paraffin concentration, and mixing speed on extraction efficiencies of phenol were limited. However, the carrier concentration, NaOH concentration, Span−80 concentration, and phenol concentration had important impacts on the extraction efficiency of phenol. The extraction efficiency of phenol could reach 99.7%. Besides, the results of orthogonal experiments indicated that during the extraction of phenol by ELM, the order of importance of factors was NaOH concentration > emulsion-external solution ratio > volume fraction of Span−80 > volume fraction of TBP. After extraction, the recycled emulsion with Span−80 could not easily be effectively demulsified through heating, which only provided the highest demulsification efficiency of 18.2%. However, the recycled emulsion could be effectively demulsified through centrifugation, which could get the highest demulsification efficiency of 86% at a centrifugal rotational speed of 2000 r/min and a centrifugal time of 25 min.     

溶致液晶模板法制备CuO纳米粒子

利用溶致液晶的有序结构特性,在不同的介观空间内组装不同性质的纳米粒子,从而获得具有特定功能的纳米材料。本文研究内容主要包括：利用非离子表面活性剂Brij58制备反六角相溶致液晶,以该反六角液晶为模板,以Cu（NO3）2水溶液代替体系中的水相制备铜纳米粒子。利用偏光显微镜、X射线衍射和粒度分析仪对样品进行表征。实验表明,不同浓度下形成不同相的液晶,在400℃下煅烧可得到CuO纳米材料。     

以D2EHPA-TOPO为载体的乳化液膜体系萃取磷酸中La（Ⅲ）的工艺及传质机理研究

通过以二（2-乙基己基）磷酸酯／氧化三辛基膦（D2EHPA／TOPO）为流动载体,磺化聚丁二烯（LYF）为表面活性剂,液体石蜡为膜增溶剂,煤油为稀释剂,盐酸为内水相的W／O型乳液,与含La（Ⅲ）的磷酸的外水相进行萃取的过程,制备了W／O／W的双重乳化液膜体系,用单因素法考察了载体浓度,表面活性剂浓度,内相酸度,水乳比等对液膜提取率的影响,确定了最佳工艺条件,迁移率达94．21％以上。并以单浓度递变斜率法研究了载体浓度,表面活性剂浓度,磷酸浓度,H2PO4^-浓度,水相平衡H^＋浓度对分配比的影响,推导出了该乳化液膜的传质机理所经历的步骤。传质机理中包括萃取-反萃表达式,和协萃物组成La（H2PO4）L2（HL）2·（H3PO4）·2TOPO。     

乳状液膜分离提取荷叶中3种生物碱

建立了用W/O型乳状液膜分离提取荷叶中3种生物碱——N-去甲基荷叶碱、O-去甲基荷叶碱和荷叶碱的方法。通过对迁移时间、表面活性剂Span 80用量、载体D2EHPA浓度、油内比、乳水比和内水相盐酸浓度的优化,获得了高效的液膜体系,为:迁移时间2.5 min,表面活性剂Span 80的质量分数为3.0%,载体D2EHPA的浓度为0.01 mol/L,油内比为10∶6,乳水比为10∶60,内水相盐酸浓度为0.2 mol/L。在优化的实验条件下,对荷叶中3种生物碱N-去甲基荷叶碱、O-去甲基荷叶碱和荷叶碱的萃取率分别达到了95.6%、100%和97.9%,相应的富集因子依次为8.73、8.50和8.04。说明该乳状液膜体系能够很好地分离提取荷叶中的N-去甲基荷叶碱、O-去甲基荷叶碱和荷叶碱。     

Modeling of the Permeation of Thorium through Liquid Emulsion Membrane

Abstract

A general permeation model for the separation of thorium by liquid emulsion membrane (LEM), using theonyletrichloroacetone HTTA as a carrier is presented. The internal mass transfer in the W/O emulsion drop, the external mass transfer around the drop, the rates of formation, and the decomposition of the complex at the external aqueous‐organic interface were considered. Further, the leakage of the internal aqueous phase to the external phase due to the membrane break‐up is also taken into account. The batch extraction of thorium using HTTA as a carrier was carried out under various experimental conditions. It is found that the extraction rates can be satisfactorily simulated by the proposed model.     

低过冷度石蜡Pickering乳液的制备和表征

石蜡乳液是集储热与传热于一体的新型功能流体,具有广阔的应用前景。但是石蜡乳液在降温时会出现明显的过冷现象,降低了其储热与传热的性能。针对这个问题,用镁-铝层状双金属氢氧化物（Mg-Al LDHs）代替化学表面活性剂,采用高速剪切乳化法,制备了石蜡含量为30%（质量）的O/W型Pickering乳液;分别采用扫描电子显微镜、激光粒度分析仪、流变仪、全能稳定性分析仪和差示扫描量热仪对所制得的石蜡Pickering乳液的微观形貌、粒度分布、黏度、稳定性和热力学性质进行了表征。结果表明,当Mg-Al LDHs的含量从1%（质量）增加到5%（质量）时,石蜡Pickering乳液的粒度减小,黏度升高,稳定性得到改善;在石蜡Pickering乳液中,Mg-Al LDHs纳米颗粒吸附在石蜡液滴表面,诱导石蜡在降温时异相成核结晶,从而抑制了其过冷现象;所制备的石蜡Pickering乳液的相变焓值约为56.6 J·g^-1,在测试的温度范围内（30~70℃）的平均表观比热容为6.08 J·g^-1·K^-1,是纯水的1.45倍,具有良好的储热性能。     

Double-stimuli responsive O/W emulsion gel based on a novel amidoamine surfactant

A heat-induced O/W emulsion gel that undergoes a phase transition from sol to gel on heating was formed from the addition of aqueous HCl to a toluene solution of a long-chain amidoamine derivative (C18AA). The heat induced O/W emulsions are highly sensitive to temperature, and the sol-gel transition temperature could be simply controlled by adjusting the C18AA concentration. Interestingly, the sol-gel transition of the O/W emulsions was also very sensitive to pH. Thus, we have successfully prepared a novel double-stimuli responsive gel based on O/W emulsions consisting of C18AA and HCl.     

用于稳定化妆品中维生素C的油包多元醇体系的研究

通过将维生素C配制成溶液及水包油和油包多元醇的乳化体系,进行高温加速试验,重点研究了油包多元醇体系对维生素C的稳定性影响.研究结果表明,维生素C即使在少量水存在的情况下也很难稳定,只有在非水的油包多元醇乳化体系中具有较高的保持率.     

Emulsification, drying and film formation of alkyd emulsions

A method was developed and optimised for the emulsification of a conventional short oil alkyd resin which was solid at room temperature. The method was based on the emulsion inversion point (EIP) method whereby hot water (90°C) was added to molten alkyd resin (90°C) containing the emulsifier. Under slow mixing and addition of water, a point was reached where the emulsion instantaneously phase inverted from a water in oil emulsion (W/O) to an oil in water emulsion (O/W). Using optimum conditions, emulsions with droplet of diameters less than 0.8 μm were obtained. The drying and film formation of long oil alkyd emulsions were investigated with emphasis on loss of dry upon storage. The main reason for loss of dry was adsorption of the cobalt (drier) on pigment surfaces as a precipitated hydroxide. Titanium dioxides with alumina surface treatment and organic pigments were most detrimental to drying. Acrylate- and phosphate-based dispersants also deactivated cobalt presumably due to complexation and precipitation of cobalt. Emulsions prepared with an emulsifiable cobalt drier containing 2,2′-bipyridyl (complexing agent for cobalt) showed the best resistance to loss of dry. Films formed from the emulsions showed that surfactant migrated to the film surface which when washed with water leaves holes or pits in film. The pits were arranged in a hexagonal pattern, characteristic of Bénard cells which form due to interfacial tension gradients generated in the film during evaporation of water.     

冷冻解冻法破除液体石蜡W/O乳状液

冷冻解冻法是一种新型的破除W/O乳状液的物理破乳方法.为了揭示冷冻解冻破乳作用机制,本文以稳定性好的液体石蜡W/O乳状液为研究对象,采用差热扫描量热仪（DSC）与显微镜,研究了高黏度连续相液体石蜡体系的W/O乳状液的冷冻解冻破乳过程.结果表明：该破乳过程是一个渐进过程.当乳珠粒径均匀细小,小于5.5 μm时,乳珠在冷冻解冻循环中逐渐长大,经多次冷冻解冻后完成破乳;然而当乳珠粒径较大时,如51 μm,乳状液体系仅需单次冷冻解冻循环就可破乳较完全,破乳率超过90%.此外,乳状液含水量的增加有利于提高破乳效率.乳状液水相的凝固点受乳珠尺度的影响,但受含水量的影响不显著.当乳珠粒径较大时,水相凝固点随乳珠粒径的减小而降低;但是当乳珠粒径降至5.5 μm时,乳珠粒径的改变对其影响已不明显.     

Extraction of formic acid with G/O/W microdispersion system

The enrichment of formic acid in dilute solution was achieved by complex extraction method. An extraction system with high partition coefficient was determined. The continuum model was then applied for describing mass transfer process and predicting the mass transfer characteristics in O/W system. The rate-limiting step was determined to be mass transfer of formic acid in aqueous phase, by comparison of mass transfer rates between extractant in organic phase and solute in aqueous phase. The effect of dispersion size of organic droplets on mass transfer characteristics in O/W systems was determined, indicating inefficient extraction process with low mass transfer coefficients and surficial area in O/W systems. Inert gas was introduced into extraction system and a G/O/W system was developed. The calculation of mass transfer performance in G/O/W system indicates the addition of microbubbles effectively enhances the mass transfer process. Also, suitable volumetric fraction of inert gas was optimized. According to the calculation, a double-membrane-dispersion-device was designed, with which G/O/W double emulsion was prepared and effective enrichment of formic acid from its dilute solution was realized.     

G/O/W微分散体系实现甲酸/三辛胺-正辛醇体系萃取分离

以络合萃取法实现了稀溶液中甲酸的富集。确定了高分配系数的萃取体系。根据传质基本方程建立了传质模型,计算并分析了油/水体系中的传质过程,确定传质控制步骤为甲酸自水相至水/油界面的传质。计算了分散尺寸对体系传质性能的影响,结果表明,由于水/油相比高,体系的传质系数低,界面积小,以油/水微分散乳液实现萃取过程,传质效率仍不高。引入惰性气体,并构建气/油/水体系,计算并分析了气/油/水体系中的传质过程并优化了气相加入量,结果表明,气相的加入可以有效促进传质过程。设计了双重膜分散设备,制备了微米尺度的气/油/水双重乳液,并以此实现了稀溶液中甲酸的高效富集。     

Unsteady-State Absorption of Co 2 Into W/O Type Emulsion with Aqueous Amine Liquid Droplets

Unsteady-state absorption of CO 2 into W/O type emulsion was studied by both experimental measurements and prediction from mathematical modeling. Absorption experiments were carried out using a stirred vessel with a flat gas-liquid interface under 0.101 MPa and 25°C. Continuous phase was benzene, which has larger solubility than water. Dispersed phase was an aqueous solution of MEA, DEA, TEA, and AMP. The effects of reactant concentration, size of aqueous droplets, volume fraction of continuous phase, and stirring speed on the absorption rate of CO 2 were investigated. In the mathematical model, the mechanism of CO 2 absorption into the continuous phase through a gas-liquid interface was described on the basis of the penetration model, while the subsequent absorption/reaction in dispersed droplets was modeled on the basis of the film model.