新型生物表面活性剂的分离和鉴定

采用超滤法分离青霉素发酵液中的表面活性物质,并将表面活性物质富集浓缩,再结合冷冻干燥等手段回收,得到了一种生物表面活性剂,同时解决了青霉素溶剂萃取过程中的乳化问题.截留分子质量为10 ku的超滤膜能有效分离料液中起生物表面活性剂作用的表面活性物质,消除了青霉素提炼过程中的乳化现象.这种生物表面活性剂在青霉素发酵液中的含量为2.659 g/L.     

伴随化学反应的液液相间传质现象

液液体系中形成动态相间分散层 (IDZ)的观点合理解释了伴随化学反应的传质动力学特性 .研究表明 ,用 3 - (正十二烷基 )胺萃取HCl时发生的萃取速率突变现象 ,可用由于局部反应平衡常数的变化和浓度梯度增长 ,在有机相边界层内形成W/O型IDZ过程予以解释 .添加少量表面活性剂可以改变IDZ的液滴数量与尺度 ,进而显著地改变通过相界面的扩散系数 .如果表面活性剂能够稳定IDZ和 (或 )促进反应剂在液滴表面上的吸附 ,则呈现正效应 ;如果表面活性剂使IDZ的稳定性降低和 (或 )减弱液滴表面对反应剂的吸附 ,则观察到负效应 .上述现象在 2 -羟基 - 5 -辛基二苯甲酮肟萃取和反萃Cu²⁺的过程中得到了证实 .     

浅析甲醇萃取分离中的"乳化现象"

用丙酮氰醇法生产MMA时,在采用脱盐水对MMA/MET/H2O进行萃取操作的过程中,易出现两相分层困难的问题,其中水相粘性增加,有机相增溶作用增强,两组分互相夹带,在有效的萃取时间内无法达到分离的目的,而发生乳化现象。本文针对乳化现象从装置实际出发,进行对比试验、分析、探讨乳化过程和可能发生乳化的条件,从而为装置生产提供一定的借鉴和预防措施。     

浅析甲醇萃取分离中的“乳化现象”

用丙酮氰醇法生产MMA时,在采用脱盐水对MMA/M ET/H2O进行萃取操作的过程中,易出现两相分层困难的问题,其中水相粘性增加,有机相增溶作用增强,两组分互相夹带,在有效的萃取时间内无法达到分离的目的,而发生"乳化现象"。本文针对"乳化现象"从装置实际出发,进行对比试验、分析、探讨乳化过程和可能发生乳化的条件,从而为装置生产提供一定的借鉴和预防措施。     

乳化萃取在湿法磷酸净化过程中的应用

乳化萃取是一种新型的萃取分离技术。实验选用磷酸三丁酯为萃取剂,煤油为稀释剂,采用乳化萃取技术对湿法磷酸净化进行研究,考察了搅拌时间和搅拌转速对乳状液液滴直径及P2O5萃取率的影响。结果表明:该萃取体系下乳状液的类型为W/O型,当搅拌转速为500r/min,搅拌时间为30s时,萃取达到平衡,一级P2O5萃取率为45%,而常规萃取则要1h才能达到平衡。     

萃取法分离钛白废酸中的铁

首先通过臭氧氧化作用把钛白废酸中的二价铁转化成三价铁,然后采用萃取法去除其中的三价铁。考察了络合剂（盐酸）浓度、萃取剂、萃取相比等对三价铁萃取率的影响,并初步探索了反萃法回收萃取剂及萃取剂的循环利用。结果表明：当盐酸浓度为3.4 mol/L时,几乎可完全络合溶液中的三价铁;在萃取剂磷酸三丁酯中加入苯作为稀释剂,可有效降低磷酸三丁酯的粘度,消除萃取过程中的乳化现象;磷酸三丁酯萃取三价铁的传质过程很快,2-3 min即达平衡;当萃取相比O/W（萃取剂与钛白废酸体积之比）=0.6∶1时,三价铁萃取率可达97%以上。当反萃相比W/O=4∶1时,三价铁反萃率接近100%。磷酸三丁酯经过5次萃取-反萃循环后,三价铁的萃取率没有明显下降。去除三价铁后的钛白废酸,经蒸馏浓缩到质量分数70%左右,再与浓硫酸混合后可用于钛白粉的生产,蒸馏过程中回收的盐酸循环使用。反萃出来的三价铁可作为生产铁红的原料。     

青霉素发酵液中可溶性蛋白质的沉降及其在溶剂萃取中的乳化作用

利用自合成的阴离子型共聚物研究了青霉素发酵液中可溶性蛋白质的沉降行为．同时考察了发酵液中部分蛋白质被除去后,液液萃取过程中乳化程度的变化情况．实验结果表明,含反应性官能团的高分子共聚物能有效地除去青霉素发酵液中的蛋白质,减轻液液萃取过程中的乳化程度,从而提高青霉素的提取率,同时减少废渣的产生．高分子共聚物的组成对发酵液中蛋白质的沉降和有机相破乳有很大的影响．     

青霉素发酵液中生物表面活性剂的提取

采用超滤法分离青霉素发酵液中的表面活性物质,并将表面活性物质富集浓缩,再结合冷冻干燥等手段回收,得到可利用的生物表面活性剂,同时解决了青霉素发酵液乳化的问题。截留分子量为10kDa的超滤膜能有效分离料液中的表面活性物质,每升发酵液中含表面活性剂2.659g。     

W／O／W复乳溶剂蒸发法制备微胶囊的影响因素及研究新进展

重点综述了W/O/W复乳溶剂蒸发法制备微胶囊的过程及影响因素,并结合SPG膜乳化法阐述了其最新研究进展.     

微乳液的特性与应用

O/W,W/O 或油、水双连续结构微乳液,具有很高的稳定性、很大的增溶量,能形成超低界面张力。在工业生产中,微乳液可作为润滑剂、清洗剂、反应介质、萃取介质及化妆品溶液。在三次采油中,微乳液驱油最有应用前景.     

Hydrophobic Modification and Regeneration of Shirasu Porous Glass Membranes on Membrane Emulsification Performance

The effect of hydrophobic modification and regeneration of Shirasu porous glass (SPG) membranes was systematically investigated on the monodispersity of emulsions. The results showed that the hydrophobic modification and regeneration of SPG membranes had little influence on the monodispersity of emulsions, no matter how many modification and regeneration runs were operated. The emulsification runs affected the emulsification performance to a certain extent when hydrophobically‐modified SPG membranes were used for preparing water‐in‐oil (W/O) emulsions repeatedly. However, they almost did not affect the emulsification performance when regenerated hydrophilic SPG membranes were used for preparing oil‐in‐water (O/W) emulsions. The SPG membranes could be used repeatedly after hydrophobic modification or regeneration with almost the same emulsification performance as fresh or freshly‐modified ones. The results provided some valuable guidance for the repetitive use of SPG membranes to prepare monodisperse O/W and W/O emulsions.     

Comparison of fuel properties and emission characteristics of two- and three-phase emulsions prepared by ultrasonically vibrating and mechanically homogenizing emulsification methods

Emulsions have long been considered as an alternative fuel for combustion equipment in order to achieve better fuel economy and pollution reduction. While a mechanical homogenizing method is frequently used to prepare emulsions, the use of an ultrasonic emulsification method to do so is still rather limited, and is mostly applied to two-phase emulsions only. Hence, two-phase W/O and three-phase O/W/O emulsions, prepared by a mechanical homogenizer and an ultrasonic vibrator, respectively, were prepared and used as engine fuel. The emulsion properties, engine performance, and engine emission characteristics between these two emulsification methods were measured and compared. The potential of the ultrasonic emulsification method was also evaluated. The experimental results show that the emulsions prepared by the ultrasonic vibrator appeared to have more favorable emulsification characteristics such as smaller dispersed water droplets that were distributed more uniformly in the continuous oil phase, lower separation rate of water droplets from the continuous phase of diesel fuel and thus a lower separating rate of the dispersed water droplets from the emulsion, larger emulsion stability, and larger emulsion viscosity than the emulsions produced using a mechanical homogenizer. In addition, a larger content of water was emulsified when the emulsion was prepared using the ultrasonic vibrator than the mechanical homogenizer. The emulsions prepared by the ultrasonic vibrator also had a lower fuel consumption rate, lower bsfc, and significantly lower CO emission while at the same time having a larger black smoke opacity. When comparing the two-phase W/O and the three-phase O/W/O emulsions prepared by either the ultrasonic vibrator or the mechanical homogenizer, the two-phase W/O emulsions appeared to have a lower fuel consumption rate, bsfc, CO, and a lower black smoke opacity than the three-phase O/W/O emulsions, regardless of whether they were prepared by ultrasonic vibrator or mechanical homogenizer.     

Preparation of water-in-oil and ethanol-in-oil emulsions by membrane emulsification

In this work, water-in-oil emulsions (W/O) and ethanol-in-oil emulsions (E/O) emulsions were prepared successfully by membrane emulsification. The emulsifiers selected were PGPR and MO-750 for the W/O and E/O emulsions, respectively. For W/O emulsions prepared with an oil pre-filled membrane, the dispersed flux was lower and the droplet size sharper than that obtained with a water pre-filled membrane. On the contrary, for E/O emulsions prepared with the membrane pre-filled with oil, the dispersed phase (ethanol) rapidly pushed out the oil from the membrane pores. Therefore, the pre-treatment of the membrane had almost no effect on the dispersed phase flux and on the droplet size. The droplet size distribution of the E/O emulsion was close to that obtained with a classical homogenizer. The dispersed phase fluxes were high and no fouling was observed for our experimental conditions (1.6 l emulsion, 10 wt% ethanol). These results confirm that membrane emulsification could be an interesting alternative for the preparation of E/O emulsions for the purpose of biodiesel fuels, considering the scale-up ability of membranes and their potentiality for industrial processes.     

制备单分散含单体O/W乳液的SPG膜乳化过程

采用Shirasu多孔玻璃（SPG）膜乳化法制备了单分散含对苯二甲酰氯（TDC）单体的O/W乳液,系统地研究了SPG膜乳化过程的影响因素.实验结果表明,采用SPG膜乳化法制备单分散O/W乳液时,选择阴离子表面活性剂比考虑亲水亲油平衡（HLB）匹配更重要;增大分散相或连续相的黏度,能够改善乳液的单分散性和稳定性;随着单体浓度增加,乳液的单分散性变差,液滴的平均粒径逐渐变小.当SPG膜孔径大于1.0 μm左右时,可得到单分散的含TDC单体乳液;而当孔径小于1.0 μm左右时,水分子更容易扩散并溶解到油水界面甚至油相内部与TDC生成对苯二甲酸（TPA）,TPA积累到一定程度在油水界面上析出将膜孔堵塞,从而无法制得单分散乳液.随着乳化时间增长,乳液的平均直径逐渐变小、单分散性逐渐变差.     

Preparation of monodisperse water-in-oil-in-water emulsions using microfluidization and straight-through microchannel emulsification

Water-in-soybean oil-in-water (W/O/W) emulsions with an internal water phase content of 10–30% (vol/vol) were prepared by a two-step emulsification method using microfluidization and straight-through microchannel (MC) emulsification. A straight-through MC is a silicon array of micrometer-sized through-holes running through the plate. Microfluidization produced water-in-oil (W/O) emulsions with submicron water droplets of 0.15–0.26 μm in average diameter (d _av,w/o) and 42–53% in CV (CV_w/o) using tetraglycerin monolaurate condensed ricinoleic acid esters (TGCR) and polyglycerin polycondensed ricinoleic acid esters (PGPR) as surfactants dissolved in the oil phase. The d _av,w/o and viscosity of the W/O emulsions increased with an increase in internal water phase content. Straight-through MC emulsification was performed using the W/O emulsions as the to-be-dispersed phase and polyoxyethylene (20) sorbitan monooleate (Tween^® 80) as a surfactant dissolved in the external water phase. Monodisperse W/O/W emulsions with d _av,w/o/w of 39.0–41.0 μm and CV_w/o/w below 5% were successfully formed from a straight-through MC with an oblong section (42.8×13.3 μm), using the TGCR-containing systems. The d _av,w/o/w of the monodisperse W/O/W emulsions decreased as the internal water phase content increased because of the increase in viscosity of the to-be-dispersed phase. Little leakage of the internal water droplets and no droplet coalescence or droplet break-down were observed during straight-through MC emulsification.     

Efficient Encapsulation of a Water-Soluble Molecule into Lipid Vesicles Using W/O/W Multiple Emulsions via Solvent Evaporation

We developed a novel method for preparing lipid vesicles with high entrapment efficiency and controlled size using water‐in‐oil‐in‐water (W/O/W) multiple emulsions as vesicle templates. Preparation consists of three steps. First, a water‐in‐oil (W/O) emulsion containing to‐be‐entrapped hydrophilic molecules in the water phase and vesicle‐forming lipids in the oil phase was formulated by sonication. Second, this W/O emulsion was introduced into a microchannel emulsification device to prepare a W/O/W multiple emulsion. In this step, sodium caseinate was used as the external emulsifier. Finally, organic solvent in the oil phase was removed by simple evaporation under ambient conditions to afford lipid vesicles. The diameter of the prepared vesicles reflected the water droplet size of the primary W/O emulsions, indicating that vesicle size could be controlled by the primary W/O emulsification process. Furthermore, high entrapment yields for hydrophilic molecules (exceeding 80 % for calcein) were obtained. The resulting vesicles had a multilamellar vesicular structure, as confirmed by transmission electron microscopy.     

The effect of shear and oil/water ratio on the required hydrophile-lipophile balance for emulsification

Required hydrophile-lipophile balance (HLB) values were examined in terms of the nature of kerosene-water, both oil-in-water (O/W) and water-in-oil (W/O), emulsions formed using Span 80/Tween 80 surfactant blends. Both the nature of the emulsification method and the oil/water ratio were critical in determining the resulting emulsion type. Both high- and low-shear conditions were investigated. Under high shear, low internal phase emulsions formed using the surfactant mixtures that corresponded to the required HLB values for emulsification involving kerosene (6 for W/O and 14 for O/W). However, at low shear, high internal phase (concentrated) emulsions resulted. Furthermore, depending on the oil/water ratio, some of the high internal phase emulsions were opposite to the type expected, given the HLB of the surfactant blend used. From these results, it appears that the emulsification technique (applied shear and oil/water ratio) used can be of greater importance in determining the final emulsion type than the HLB values of the surfactants themselves.     

Effects of emulsification variables on fuel properties of two- and three-phase biodiesel emulsions

Biodiesel has attractive fuel properties such as excellent biodegradability and lubricity, almost no emissions of sulfur oxides, PAH and n-PAH, reduced CO₂, PM and CO emission, superior combustion efficiency, etc. However, burning of biodiesel generally produces higher levels of NO_x emissions, primarily due to its high oxygen content. In this study, the emulsification technology has been considered to reduce the NO_x emission level of fossil fuel. Biodiesel, produced by means of transesterification reaction accompanied with a peroxidation process, was emulsified to form two-phase W/O and three-phase O/W/O emulsions. The effects of the emulsification variables such as hydrophilic lipophilic balance (HLB), and water content on the fuel properties and emulsion characteristics of W/O and O/W/O emulsions were investigated in this study. The experimental results show that the surfactant mixture with HLB = 13 produced the highest emulsification stability while HLB = 6 produced the lowest emulsification stability and the most significant extent of water–oil separation among the various HLB values for O/W/O biodiesel emulsion. The kinematic viscosity, specific gravity and carbon residual of the biodiesel emulsions were larger than those of the neat biodiesel. In addition, the W/O biodiesel emulsion was found to have a smaller mean droplet size, lower volumetric fraction of the dispersed phase than the O/W/O biodiesel emulsion, and the highest heating value among the test fuels, if the water content is deducted from the calculation of the heating value.     

Emulsification characteristics of three- and two-phase emulsions prepared by the ultrasonic emulsification method

Diesel engines exhausting gaseous emission and particulate matter have long been regarded as one of the major air pollution sources, particularly in metropolitan areas, and have been a source of serious public concern for a long time. The emulsification method is one of the potentially effective techniques to reduce emission pollution from diesel engines. Ultrasonic waves are a kind of sound waves with a frequency larger than 20 kHz, and they cannot be detected by the human ear. The phenomena of cavitation and hot spots produced by the rather violent action of ultrasonic waves can cause rapid chemical and physical reactions. This allows immiscible liquids to be well stirred with each other by means of ultrasonics. An ultrasonically vibrating machine that provides ultrasonic waves of a 40-kHz frequency was employed to prepare two- and three- phase emulsions in this experimental study. The fuel properties and the emulsion stability of the diesel emulsions were measured and analyzed. Experimental results show that the ultrasonic emulsification method successfully prepared two- and three-phase emulsions with tiny dispersed-phase droplets that are very evenly distributed in the outer oil or water phase. The ultrasonic processing time, quantity and HLB of the emulsifying agent were noted to have determinative influences on the formation of the emulsion and the fuel properties. A longer ultrasonic processing time caused less un-emulsified diesel fuel, smaller sizes and a more even distribution of dispersed-phase droplets in the outer oil phase and larger emulsion viscosity. However, a longer ultrasonic processing time also produced a larger temperature rise in the emulsion, leading to the deterioration of the emulsion stability. The O/W emulsion was found to have the lowest percentage of separation and thus the highest emulsion stability among the O/W/O, O/W and W/O emulsions. In addition, in comparison with the W/O emulsion, the O/W emulsion was shown to have a smaller size and a more even distribution of the dispersed-phase droplets. It also had a lesser rise in emulsion temperature when the ultrasonic processing time increased. The control of the ultrasonic processing time is important to successfully prepare the three-phase O/W/O emulsion. Too long a vibration time at the second-stage of emulsification is shown to cause the dispersed-phase pellets to contract and congregate with the inner-phase droplets. The three-phase emulsion structure then finally disappears and transforms into a two-phase emulsion. The addition of 2% by volume of the emulsifier mixture of Span80 and Tween80 with a HLB = 8, as suggested by this study for the preparation of stable two- and three-phase emulsions, were observed to have the lowest percentage of separation of the W/O and O/W/O emulsions. For preparing a stable O/W emulsion, the proportion of the emulsifier could be as low as 1.5% by volume. The percentage of separation of the O/W/O emulsion was lower and less influenced by the change in emulsion temperature than was the W/O emulsion with the same water content. However, the O/W/O emulsion was found to have a larger viscosity and a more significant variation of its viscosity, depending on the ultrasonic processing time, than the W/O emulsion.     

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.