Remediation of diesel oil contaminated sand by micro-emulsion

Micro-emulsion has unique advantages in repairing diesel oil contaminated sand due to its low interfacial tension and strong solubility. By Winsor phase diagram, it was found that with the increase of salinity, the phase of microemulsion transformed from Winsor Ⅰ to Winsor Ⅲ to Winsor Ⅱ. Under cryogenic electron microscope, it was observed that Winsor Ⅰ was O/W type, Winsor Ⅱ was W/O type, and Winsor Ⅲ type was bi-continuous type. The effect of inorganic salts, alcohol and temperature on the oil removal rate of diesel oil contaminated sand was investigated by static recovery of micro-emulsion precursor. The results showed that for the anionic microemulsion system, with the increase of salinity and alcohols, the oil yield of the upper phase increased first and then decreased, and the two components had a certain compensation effect. For non-ionic micro-emulsion system, with the increase of temperature, the oil yield in the upper phase rose first and then decreased. At the same time, the influence of leaching conditions on oil removal rate was investigated by one-dimensional sand column leaching experiment. It was found that for diesel oil contaminated sand with 15% oil content, when the formulation was 2.00 wt% SDBS, 4.05 wt% n-butanol and 0.40 wt% sodium chloride, the optimum leaching conditions were leaching rate of 4 ml·min~(-1) and leaching amount of 400 ml. Under such conditions, the oil removal rate was up to 82.84%, that is, the oil content of the sand was reduced to 2.57%. Moreover, the micro-emulsion has good cyclicity, and it can still achieve high oil yield after six cycles.     

Phase Behavior of Sodium Dodecyl Sulfate-n-Butanol-Kerosene-Water Microemulsion System

Experiments were carried out to investigate the influences of cation from electrolytes and acidity/alkalinity on the phase behavior of sodium dodecyl sulfate-n-butanol-organics-water （with electrolytes） microemulsion sys-tem. The organics used is commercial kerosene. The volume ratio of water to organics is 1︰1. The results show that the type and valence of electrolyte cations are important factors influencing the microemulsion behavior. Biva-lent Ca2＋is more effective than monovalent K＋and Na＋for the formation of Winsor type III and II microemulsion. For electrolytes with the same monovalent cation Na＋, i.e. NaCl and Na2CO3, anions in the electrolyte have some effect. Bivalent anion 23CO - leads to a lower activity of cation Na＋than monovalent anion Cl-. NaOH （or KOH） behaves similar with NaCl （or KCl）. When HCl is used as electrolyte, its acidity plays an important role. Phase in-version of microemulsion from type III （or II） to type I is observed through precipitation of Ca2＋using Na2CO3, neutralization of HCl by NaOH, and addition of water to the system, which releases the oil from the microemulsion.     

Double emulsions of water-in-oil-in-water stabilized by α-form fat microcrystals. Part 1: Selection of emulsifiers and fat microcrystalline particles

Double emulsions are commonly stabilized by monomeric and/or polymeric emulsifiers. Pickering stabilization by solid particles such as colloidal microcrystalline cellulose has been mentioned only once as a possible technique to stabilize the external interface of the water-in-oil-in-water emulsion. No further work was carried out exploring this option. The present study shows that solid microcrystalline fat particles of α-form are capable of adsorbing at the water-oil interface and, together with other hydrophobic emulsifiers, can stabilize water-in-oil (W/O) emulsions. The crystals must be submicron in size in order to effectively adsorb and arrange at the interface. Large crystals do not fit and were found to flocculate as free crystals in the continuous oil phase. The α-form crystals can be obtained by flash-cooling saturated triglycerides in vegetable oils in the presence of emulsifiers, such as polyglycerol polyricinoleate (PGPR), that stabilize the dispersion and serve as α-tending crystal structure modifiers. It was assumed that PGPR also serves as a cross-linker or bridge between the crystalline fat particles and the water, and facilitates the anchoring of the fat particles in the oil phase in one direction while dangling itself in the water phase. The double emulsion droplets prepared with these W/O emulsions are relatively large in size (6–18 μm), but stable to coalescence. The marker (NaCl) does not seem to release with time, suggesting that the fat particles form microcapsules on the water interface, totally sealing the water from releasing its addenda. The systems seem to have a significant potential for food emulsions.     

Kinetics of lipase catalyzedenantioselective esterification of racemic ibuprofen in isooctane

The kinetics of Candida rugosa lipase catalyzed esteritlcation of racemic ibuprofen with n-butanol in isooctane was studied. The kinetic study was carried out with the addition of 0.1% and 2% (by volume) of water for enzyme activation respectively when celite was added into isooctane for enzyme dispersion. The specific initial rate for S-ibuprofen can be fitted with the Ping Pong Bi Bi mechanism with dead-end competitive inhibition by the alcohol. The time courses of the enantioselective esteriflcation of the two ibuprofen enantiomers with different initial substrate concentrations and water contents were simulated with a model in which both effects of enzyme inactivation by long term reaction and reversed hydrolytic reaction under high water content were taken into consideration.     

表面活性剂对HCl-FeCl3溶液中锌精矿在浆萃取浸出率的影响

The effects of surfactant on the solvent extraction in leaching sphalerite were investigated. It is found that sodium dodecyl sulfonate is the effective surfactant in improving the zinc recovery from sphalerite in the aqueous FeCl3-HCl-tetrachloroethylene system. Through the measurements of surface tension and viscosity of the sphalerite slurry modified with different surfactants, it is concluded that sodium dodecyl sulfonate in the concentration range of 0.05 to 0.2g L-1 can improve the viscosity of sphalerite slurry in the water, decrease the surface tension of leaching solution, prevent the aggregation of ore particles, and give very high zinc extraction .     

微滤膜聚并破乳的机理研究

A study on the membrane coalescence demulsification was carried out with four working systems of water/n-butyl alcohol, water/n-octanol, water/30% TBP(in kerosene) and water/kerosene. The membranes made of polytetrafluoroethylene (PTFE) with 1.0μm pore size were used. The results indicated that the excellent demulsification efficiency for emulsions with various oil contents was obtained. A conductivity probe was used to study the demulsification mechanism. An electrode probe was designed and used to determine the oil content near the membrane surface. The obtained data showed that the oil content in the permeated stream was much higher than that in the feed emulsion. A physical mechanism to explain the membrane demulsification was put forward.     

微量酸催化麻疯树籽油制备生物柴油(英文)

Biodiesel produced from crude Jatropha curcas L.oil with trace sulfuric acid catalyst(0.02%-0.08% oil) was investigated at 135-184 ℃.Both esterification and transesterification can be well carried out simultane-ously.Factors affecting the process were investigated,which included the reaction temperature,reaction time,the molar ratio of alcohol to oil,catalyst amount,water content,free fatty acid(FFA) and fatty acid methyl ester(FAME) content.Under the conditions at 165 ℃,0.06%(by mass) H2SO4 of the oil mass,1.6 MPa and 20:1 methanol/oil ratio,the yield of glycerol reached 84.8% in 2 hours.FFA and FAME showed positive effect on the transesterification in certain extent.The water mass content below 1.0% did not show a noticeable effect on trans-esterification.Reaction kinetics in the range of 155 ℃ to 175 ℃ was also measured.     

采用增大凝结液滴方法的锥芯超音速旋流分离装置性能研究

To improve the separation performance of a supersonic gas separation device for the treatment of gas mixture with a single heavy component, a novel structure with shorter settlement distance was constructed and a method of droplet enlargement was applied. A series of experiments were carried out in the improved separation device under various conditions, using air-ethanol vapor as the medium and micro water droplets as nucleation centers. The effects of the inlet pressure, temperature and relative humidity, the swirling intensity, and mass flow rate of water on the separation performance were investigated. The separation was improved by increasing the inlet pressure and relative humidity. With the decrease of swirling intensity and mass flow rate of water, the separation efficiency increased first and then decreased. The inlet temperature had a slight effect on the separation. The results showed that the separation performance was effectively improved using the proposed structure and method, and the best separation in this study was obtained with the ethanol removal rate about 55% and dew point depression 27 K. The addition of water had little pollution to the air-ethanol vapor system since the water carry-over rate was within the range of %-0 in most cases.     

鼓泡塔中低浓度表面活性剂对CO2吸收传质系数的影响（英文）

The effect of different surfactants (n-octyltrimethylammonium bromide (OTABr), sodium dodecyl benzene sulfonate (SDBS) and Tween 80) with different critical micelle concentrations (CMC) on the CO2 absorption into aqueous solutions in a bubble column is analyzed in the present work. The presence of these surfactants in-creased the gas–liquid interfacial area, and decreased the liquid phase mass transfer coefficient, but with signif-icant different extent. The results indicated that the CMC can be a key parameter affecting the mass transfer of CO2 absorption into a dilute aqueous solution of a surfactant. Sardeing's model was used to fit the experimental data successfully by re-correlating the parameters.     

Highly efficient[C8mim][Cl] ionic liquid accompanied with magnetite nanoparticles and different salts for interfacial tension reduction

The 1-octyl-3-methylimidazolium chloride, [C_8 mim][Cl] ionic liquid(IL) was used as a novel surfactant in n-heptane/water system. The interfacial tensions(IFT) were measured and corresponding variations were investigated. An IFT reduction of 80.8% was appropriate under the IL CMC of about 0.1 mol·L~(-1) and stronger effects were achieved when magnetite nanoparticles and salts were present profoundly under alkaline p Hs.The equilibrium IFT data were accurately simulated with the Frumkin adsorption model. Hereafter, the saturated surface concentration, equilibrium constant and interaction parameter were obtained and their variations were demonstrated. Further, emulsion stability and contact angle of oil/water interface over quartz surface were studied. The oil/water emulsion stability was hardly changed with nanoparticles; however, the stability of oil/water + IL emulsions was significantly improved. It was also revealed that the presence of sodium and calcium chloride electrolytes fortifies the IL impact, whereas sodium sulfate weakens. From dynamic IFT data and fitting with kinetic models, it was found that the IL migration toward interface follows the mixed diffusion–kinetic control model. Consequently, the IL diffusion coefficient and the appropriate activation energy were determined.     

正丁醇对二(2-乙基己基)琥珀酸酯磺酸钠微乳液体系的影响

通过在二(2-乙基己基)琥珀酸酯磺酸钠(AOT)/正庚烷/水的三元体系中加入正丁醇,得到了新的四元体系。绘制了25℃时AOT/正丁醇/正庚烷/水四元体系能够稳定存在的相图,发现在一定R值(水和AOT的摩尔比)条件下该相图出现了分为两个区域的现象。利用电导率数据研究了由W/O型微乳液→双连续微乳液→棒状液晶→层状液晶→双连续微乳液→O/W型微乳液的结构转变。通过稀释法求得AOT/正丁醇/正庚烷/水微乳液体系的结构参数,结果表明:含水量增加,两个区域的自由能-△G0c→i都减小,对微乳液体系的稳定不利;含水量越低,越有利于微乳液的形成和稳定;AOT/正丁醇/正庚烷/水四元体系比以AOT作表面活性剂的三元体系有更大的微乳液区域,是一个适合制备所需功能性纳米粒子的体系。     

Solubilization of lycopene in jojoba oil microemulsion

The unique properties of jojoba oil make it an essential raw material in the manufacture of cosmetics. New, totally dilutable U-type microemulsions of water, jojoba oil, alcohols, and the nonionic surfactant polyoxyethylene-10EO-oleyl alcohol (Brij 96V) have been formulated recently. Here, these microemulsions are shown to be capable of solubilizing lycopene, a nutraceutical insoluble in water and/or oil, much more effectively than the solvent (or a solvent and surfactant blend) can dissolve them. In water-in-oil (W/O) and oil-in-water (O/W) microemulsions with 10 and 90 wt% water, respectively, the normalized maximal solubilization efficiency α is ca. 20-fold larger than its solubility. The solubilization capacity of the system is mainly surfactant-concentration dependent. The lycopene resides at the interfaces of the W/O and O/W microemulsions and engenders significant structural changes in the organization of the microemulsion droplets. In the absence of lycopene, the droplets are spherical; when lycopene is added, compaction of the droplets and formation of threadlike droplets are observed. On further addition of lycopene, the bridging effect wanes and the droplets revert to a spherical shape. The enhanced solubilization demonstrated for lycopene opens up new options for formulators interested in making liquid and transparent products for cosmetic or pharmaceutical uses.     

基于相图法的W/O型微乳液体系稳定性分析

以辛基苯基聚氧乙烯醚(TX-10)、十二烷基磺酸钠(SDS)和十六烷基三甲基溴化铵(CTAB)为表面活性剂,以正戊醇、正己醇和正庚醇为助表面活性剂,以正戊烷为油相,制备了油包水型(W/O)微乳液.用相图法分析了微乳液体系的热力学稳定性,计算了水核半径的大小,并考察了影响微乳液W/O区域范围的各种因素.结果表明:这几种微乳液体系在实验条件下能自发形成:微乳液的水核半径处于纳米量级,可作为制备纳米粒子的超微反应器;以TX-10为表面活性剂时,水核可以包容更多的水分子,微乳液的W/O区域较大;而以CTAB为表面活性剂时,由于其极性头之间的空间和静电排斥作用强,微乳液的W/O区域最小;以硝酸镧溶液作为分散相时,微乳液的W/O区域变化较小;随着温度的升高,微乳液的W/O区域显著减小.     

Effect of Alkyl Sulfate on the Phase Behavior of Microemulsions Stabilized with Monoacylglycerols

In this study the effect of an anionic surfactant (sodium dodecyl sulfate SDS) and oils (hydrocarbons: C12–C16) on the formation and phase behavior of the systems of oil/monoacylglycerols (MAG):SDS/propylene glycol/water has been investigated. The effects of the surfactant mixture on the phase behavior and the concentration of water or oil in the systems were studied at three temperatures (50, 55, 60 °C). Electrical conductivity measurement, FT-IR spectroscopy and differential scanning calorimetry methods were applied to determine the structure and type of the microemulsions formed. The dimension of microemulsion droplets was characterized by dynamic light scattering. It has been stated that the concentration of SDS has a strong influence on the shape and extent of the microemulsion areas. Addition of an ionic surfactant to the mixture with MAG promotes an increase in the area of microemulsion formation in the phase diagrams, and these areas of the isotropic region change with the temperature. It was shown that the presence in the systems of a surfactant more hydrophilic than MAG caused an increase in water content in the microemulsions. It was found that, depending on temperature and concentration of the surfactant mixture, it was possible to obtain a W/O type microemulsion with a dispersed particles size distribution ranging from 20 to 50 nm and containing about 17–38% water in the system. Among different alkanes (from C12 to C16), hexadecane embedded microemulsions showed a maximum water solubilization capacity.     

柴油微乳液拟三元相图的研究

绘制了复合表面活性剂(D0821/Tx-4/AEO-3)/正戊醇/柴油/水体系在不同温度及不同正戊醇质量分数时的一系列拟三元相图。结果表明,正戊醇质量分数及温度对拟三元相图及水最大增溶量有很大影响,醇量太大或太小形成的微乳区面积均较小;温度升高,微乳区面积及水最大增溶量也大大减少;随着正戊醇质量分数的增大,每一个温度下的微乳区及其最大增溶水量都逐渐向AEO-3/正戊醇/油角漂移。     

Triton X-100/正构醇/石油醚/水反相微乳液性质的研究

通过测定微乳液的电导率值,确定配制W/O型Triton X-100/正构醇/石油醚/水微乳液的最大增溶水量;根据微乳液含水量与电导率关系曲线及体系的拟三元相图,讨论了正构醇种类、正构醇含量、乳化剂与油相质量比对W/O型微乳液的结构、电导率、增溶水量的影响。结果表明:乳化剂与油相质量比大于1时,正戊醇、正己醇和正庚醇为助剂配制的Triton X-100/正构醇/石油醚/水体系微乳液有较大的增溶水量,而乳化剂与油相质量比大于1.5时,以正丁醇为助剂配制的Triton X-100/正构醇/石油醚/水体系微乳液才有较大的增溶水量;正构醇的链长及加入量影响微液滴界面膜的强度,从而影响微乳液的增溶水量、电导率及微乳液形成区域的大小;对于Triton X-100/正构醇/石油醚/水体系,正戊醇是形成W/O型微乳液的较好助剂,当正戊醇与Triton X-100的质量比为0.5时,W/O型微乳液的形成区域最大。     

New Interfacial Rheology Characteristics Measured Using a Spinning Drop Rheometer at the Optimum Formulation. Part 2. Surfactant–Oil–Water Systems with a High Volume of Middle-Phase Microemulsion

This article is a continuation of our first study on dilational interfacial rheology properties at optimum formulation for surfactant-oil–water systems at low surfactant concentration just above the cμc. Here, we have investigated a high content of middle-phase microemulsion with an optimum WIII phase behavior for a system containing sodium dodecyl sulfate, n-pentanol, and kerosene. A new oscillating spinning drop interfacial rheometer was used to measure the interfacial properties. The very low dilational elasticity moduli and phase angle found at or near hydrophilic–lipophilic deviation (HLD) = 0 are related to the presence of the bicontinuous phase microemulsion and to the fast surfactant exchanges between the bulk and the interface, regardless of the phases involved in the measurement using the spinning drop apparatus, i.e., the two-phase excess oil and excess water (O-W) or the bicontinuous microemulsion and excess water (M-W). We show that at or near optimum formulation, the interfacial tension and the dilational modulus for the M-W case almost instantly reach equilibrium, because of the high surfactant content in the microemulsion and the fast exchanges between the bulk and the interface. In contrast, when both excess phases (O-W) are measured, the changes in these properties are slower, due to the scarce presence of surfactants in both phases. The possibility of having almost all the surfactants trapped in the middle-phase bicontinuous microemulsion could explain the emulsion instability in all the WIII range. This is behaving as if there were no surfactant available in the oil and water phases to stabilize the oil or water droplets thus formed.     

含亲水性丙烯酸酯单体的微乳液聚合研究

在构建含亲水丙烯酸酯单体微乳液聚合体系的基础上,描绘了微乳液体系的拟三元相图,考察了乳化剂和助乳化剂类型对微乳液相行为的影响,并进行了该体系正相微乳液聚合。结果表明正戊醇、环己醇、乙醇等作为助乳化剂协同阴离子乳化剂十二烷基硫酸钠(SDS)可以形成稳定的单相微乳液,但是这些微乳液体系在聚合过程中很容易生成凝胶;环己烷作为助乳化剂虽然在配制过程中不能形成稳定的透明或半透明体系,但是在反应过程中则比较稳定,能形成半透明状的聚合物微乳液;阴离子乳化剂与其它非离子乳化剂组合以及单独使用非离子乳化剂均难以制备稳定的微乳液。     

Gemini表面活性剂微乳液相行为的影响因素研究

研究了Gemini表面活性剂微乳液的界面相行为,考察了中间联接基团长度、表面活性剂和助表面活性剂的配比、醇链长和烷烃链长对相图的影响。结果表明：短链联接基团较易形成单相微乳液,表面活性剂用量较少且有较高的含水量;随着烷烃链长增加,形成O/W区域所需表面活性剂含量增加,且区域面积在逐渐减小;醇链长改变时,沿着油-（S＋A）轴都能形成W/O型微乳液。