Rapid Room‐Temperature Gelation of Crude Oils by a Wetted Powder Gelator

Phase‐selective organogelators (PSOGs) not only exhibit ability to phase‐selectively congeal oil from oily water but also allow easy separation of gelled oil from the body of water. However, all hitherto reported PSOGs either necessitate carrier solvents for their dissolution or suffer from an extremely slow action in gelling oil in the powder form. A previously unexplored generally applicable wetting strategy is now described to dramatically enhance, by up to two orders of magnitude, gelling speed of the resultant wet but non‐sticky gelator in the powder form in crude oils of widely ranging viscosities. Such unprecedented rapid gelling speeds enable rapid gelation of six types of (un)weathered crude oils within minutes at room temperature, making PSOGs one step closer to their eventual practical uses as one of important oil spill control technologies.     

Automated On-Line GPC-GC-FPD Involving Co-Solvent Trapping and the On-Column Interface for the Determination of Organophosphorus Pesticides in Olive Oils

The robustness of an automated on-line GPC-GC-FPD method for the determination of Organophosphorus (OP) Pesticides in olive oil has been significantly improved, now allowing a routine operation. The original GPC-GC transfer technique employed a loop type interface with an early vapor exit and co-solvent trapping. Shooting, caused by boiling delay and malfunctioning of the solvent vapor exit during the transfer of the 3 mL solvent fraction to the retention gap, resulted in insufficient focusing of the OP-pesticides. In this interfacing concept, the GPC fraction is introduced directly into the carrier gas stream during a certain time interval using the Dualchrom pressure- and flow regulation, resulting in a very stable transfer. The interface now basically corresponds to an on-column interface with flow regulation. Via a Pyrex glass door behind the GC-oven door it can be seen that the liquid flow is broken up into alternating gas-liquid segments by the carrier gas flow during transfer. This avoids shooting in the retention gap and broadens the temperature range for successful transfer. By using a smaller sized GPC column the solvent fraction transferred was reduced to 1.3 mL. Methyl acetate/cyclopentane and the co-solvent n-nonane were selected for their lower boiling points. The modified method is very robust and has been applied to the analysis of 28 different OP-pesticides in olive oil with an overall detection limit of 0.002 mg/kg. Routinely 24 h of unattended operation is possible with a cycle time of 75 min.     

谷氨酸在Span80-AOT-APS体系中的迁移行为

报道了谷氨酸在乳状液膜体系中的迁移行为,采用失水山梨醇单油酸酯(span80)-乙基己基琥珀酸酯磺酸钠(AOT)为表面活性剂,对氨基苯磺酸(APS)为载体,煤油为膜溶剂,氯化钾为内相试剂.讨论了制乳时间和乳液与外相混合时间、表面活性剂和流动载体浓度、内相试剂浓度、水乳比和油内比对分离效果的影响.确定了最佳分离条件为制乳...     

The effect of component partitioning on potassium picrate transport across multicomponent supported liquid membranes

Supported liquid membrane experiments were performed with systematically varied liquid membrane compositions including dicyclohexyl-18-crown-6 ether as the carrier and various ratios of methylene chloride and a 35 carbon aliphatic oil. The partitioning of the crown ether species toward the membrane phase increased markedly with methylene chloride addition to the aliphatic oil. p]The unanticipated unsteady state transport of potassium picrate across the liquidfilled microporous membranes resulted from evaporation of methylene chloride from the aqueous reservoirs and subsequent depletion from the membrane phase. The depletion of methylene chloride from the liquid membrane caused progressively reduced partitioning of the carrier and carrier complexes to the membrane relative to the contiguous aqueous phases. The reduction in carrier concentration in the membrane phase resulted in progressively decreased concentration gradients of the carrier complex. The rate of potassium picrate transport decreased during the course of the experiments even though the upstream potassium concentration was insignificantly decreased and the downstream concentration of potassium picrate remained small compared with the upstream concentration. p]These experimental results focus attention upon the important practical problem of non-infinite partitioning of carrier and key solvent components between the membrane phase and the contiguous aqueous phases. Subtle changes in the carrier distribution coefficient markedly compromise process efficacy since the volume ratio of the aqueous and membrane phases is enormous.     

Loop-type interface for concurrent solvent evaporation in coupled HPLC-GC. Analysis of raspberry ketone in a raspberry sauce as an example

Presently, two coupling techniques are used for directly introducing HPLC fractions into capillary GC: The retention gap technique (involving negligible or partially concurrent solvent evaporation) and fully concurrent solvent evaporation. While the former involves use of a conventional on-column injector, it is now proposed that concurrent solvent evaporation technique be carried out using a switching valve with a built-in sample loop. The technique is based on the concept that the carrier gas pushes the HPLC eluent into the GC capillary against its own vapor pressure, generated by a column temperature slightly exceeding the solvent boiling point at the carrier gas inlet pressure. Further improvement of the technique is achieved by flow regulation of the carrier gas (accelerated solvent evaporation) and backflushing of the sample valve (improved solvent peak shape). Concurrent solvent evaporation using the loop-type interface is easy to handle, allows transfer of very large volumes of HPLC eluent (exceeding 1 ml), and renders solvent evaporation very efficient, allowing discharge of the vapors of 1 ml of solvent through the column within 5–10 min.     

Determination of water in organic solvents by flow-injection analysis with Karl Fischer reagent and a biamperometric detection system

A flow-injection system with a biamperometric flow-through detector provided with two platinum plate electrodes was tested for the determination of water with a two-component pyridine-free Karl Fischer reagent. The response was shown to be linear in the concentration range 0.03-0.11% water in methanol, ethanol or 2-propanol, with methanol as the carrier solvent. The maximum sampling frequency was about 150 samples per hr. It appeared to be possible to introduce a membrane separation step, thus allowing for the determination of water in fouled process streams. To avoid direct contact between the Karl Fischer solution and the pumping tubes, and thus extend the lifetime of the tubes, an indirect delivery system, based on replacement of the solution by pumped silicone oil, was also applied.     

流动载体对以二-(2-乙基己基)磺化琥珀酸钠为表面活性剂的W/O型微乳状液迁移痕量铜(Ⅱ)的影响

研究了一些流动载体对以二－（２－乙基己基）磺化琥珀酸钠（ＡＯＴ）为表面活性剂、正庚 烷为油性溶剂的Ｗ／Ｏ型微乳状液在迁移痕量金属离子Ｃｕ２＋的影响。实验结果表明，１－（２－吡 啶偶氮）－２萘酚（ＰＡＮ）能大大促进 Ｃｕ２＋的迁移，使其迁移率从 ７０％上升到 １００％。用高盐度 溶液对微乳进行破乳，得到 Ｃｕ２＋的富集倍数为 ６，回收率约为 １００％。     

镍在乳状液膜体系中的迁移行为

研究了镍在乳状液膜分离体系中的迁移行为。在此分离体系中,以煤油作为膜溶剂,span80为表面活性剂,磷酸三丁酯(TBP)为载体。详细讨论了制乳时间和混合时间、span80和TBP浓度、乳水比和油内比、内相NH。和外相HCl的浓度对镍迁移率的影响,确立了最佳分离条件。     

柴油溶剂中脂肪酶催化高酸值废油脂酯化制备生物柴油

采用0＃柴油作为反应溶剂,利用固定化脂肪酶催化高酸值废油脂与甲醇酯化反应制备生物柴油。来源于Candida antarctica的固定化脂肪酶Novozym435在0＃柴油溶剂中具有极高的催化活性。以酸价高达157×10-3的废油脂为原料,废油脂质量比10%的Novozym435,甲醇与废油脂初始摩尔比2∶1,0＃柴油与废油脂质量比5∶1,摇床摇速170r/min,50℃下反应2h甲酯化率可达95.10%。0＃柴油作为反应溶剂有效地溶解了高酸值废油脂和甲醇,降低了反应体系的黏度和消除了甲醇对Novozym435的负面影响,提高了Novozym435的稳定性。同时,0＃柴油溶剂对未脱胶废油脂中残留的对脂肪酶有害的磷脂等胶类物质具有一定的稀释作用。该工艺省却了溶剂蒸馏的繁琐工序,直接得到脂肪酸甲酯和石化柴油的混合燃料。     

铜在乳状液膜体系中的迁移行为

近年来膜分离技术在环境治理方面得到广泛应用。本文研究了铜在span80-TBP（磷酸三丁酯）-煤油-NH3液膜分离体系中的迁移行为。用TBP作为载体,在溶液中迁移时,在外相与膜相界面上形成中性络合物后穿过膜相,在膜相与内相界面上络合物再与NH3反应,生成铜氨络离子,释放出来的TBP又返回膜相。     

The solvent extraction is a potential choice to recover asphalt from unconventional oil ores

The abundant unconventional oil ores (about 70% of total world oil) are playing an increasingly important role in global energy supply. To obtain asphalt in unconventional oil ores, different methods, including hot water-based extraction, pyrolysis and solvent extraction, were used to recover asphalt from oil ores (i.e., Canadian, Indonesian, and Iranian oil ores). It is found that asphalt recovery obtained by solvent extraction is the highest. Multi-staged single solvent extraction was used to recover asphalt from oil ores (i.e., toluene, tetrahydrofuran: THF, xylene, petroleum: PE, ethanol), resulting in a cumulative asphalt recovery over 98% at ambient conditions by using toluene. Take Iranian oil ores with the highest oil content (83.79 wt%) as an example, great asphalt recovery was obtained by using multi-staged composite solvents extraction (i.e., toluene@xylene, toluene@THF, toluene@PE, toluene@ethanol). It is also found that introduction of toluene in the composite solvents can significantly increase the ability of single solvent’s (xylene, THF, PE and ethanol) asphalt recovery. After solvent extraction, the solvent recovery was more than 95%. This finds suggest that solvent extraction method would be potential choice to recover asphalt from unconventional oil ores, and it possesses great prospect of industrial application in the future.     

Non-polar Solvent Microwave-Assisted Extraction of Volatile Constituents from Dried Zingiber Officinale Rosc.

A new method, non-polar solvent microwave-assisted extraction （NPSMAE）, was applied to the extraction of essential oil from Zingiber officinale Rosc. in closed-vessel system. By adding microwave absorption mediumcarbonyl iron powders （CIP） into extraction system, the essential oil was extracted by the non-polar solvent （ether） which can be heated by CIP. The constituents of essential oil obtained by NPSMAE were comparable with those obtained by hydrodistillation （HD） by GC-MS analysis, which indicates that NPSMAE is a feasible way to extract essential oil from dried plant materials. The NPSMAE took much less extraction time （5 min） than HD （180 min）, and its extraction efficiency was much higher than that of conventional polar solvent microwave-assisted extraction （PSMAE） and mixed solvent microwave-assisted extraction （MSMAE）. It can be a good alternative for the extraction of volatile constituents from dried plant samples.     

乳状液膜法分离水中镉

本文报道了用乳状液膜法分离镉的研究。在此分离体系中,以煤油作为膜溶剂,span80为表面活性剂,磷酸三丁酯(TBP)为载体,液体石蜡为膜增强剂。详细讨论了制乳时间、混合时间、搅拌速度,span80、TBP以及液体石蜡的浓度,乳水比和油内比,内相氨水和外相HCl溶液的浓度对分离的影响,确立了最佳分离条件。     

Oil core-polymer shell microcapsules prepared by internal phase separation from emulsion droplets. I. Characterization and release rates for microcapsules with polystyrene shells

Microcapsules with an oil core surrounded by a polymeric shell have been prepared by the controlled phase separation of polymer dissolved within the oil droplets of an oil-in-water emulsion. The dispersed oil phase consists of the shell polymer (polystyrene), a good solvent for the polymer (dichloromethane), and a poor solvent for the polymer (typically hexadecane). Removal of the good solvent results in phase separation of the polymer within the oil droplets. If the three interfacial tensions between the core oil, the shell-forming polymer, and the continuous phase are of the required relative magnitudes, a polymer shell forms surrounding the poor solvent. A UV-responsive organic molecule was added to the oil phase, prior to emulsification, to investigate the release of a model active ingredient from the microcapsules. This molecule should be soluble in the organic core but also have some water solubility to provide a driving force for release into the continuous aqueous phase. As the release rate of the active ingredient is a function of the thickness of the polymeric shell, for controlled release applications, it is necessary to control this parameter. For the preparative method described here, the thickness of the shell formed is directly related to the mass of polymer dissolved in the oil phase. The rate of volatile solvent removal influences the porosity of the polymer shell. Rapid evaporation leads to cracks in the shell and a relatively fast release rate of the active ingredient. If a more gentle evaporation method is employed, the porosity of the polymer shell is decreased, resulting in a reduction in release rate. Cross-linking the polymer shell after capsule formation was also found to decrease both the release rate and the yield of the active ingredient. The nature of the oil core also affected the release yield.     

废轮胎热解油品的组成与硫含量研究

本文就废轮胎热解是油品组成进行了分析,结果表明,载气种类对油品的组成及硫含量影响较大,在Ｎ２条件下,油品中含有较多的轻质油品,轻质油中中富含高附加值的化学品萜二烯。Ｈ２及Ｈ２Ｏ气氛下的油品中轻质油品含量远低Ｎ２气氛以质油品含量。载气流速对油品的组成影响不大。硫含量分析表明,在Ｎ２条件下各油品的硫含量均高于Ｈ２及Ｈ２Ｏ气氛下的硫含量;各油品中轻质油品硫含量最低,在Ｈ２及Ｈ２Ｏ气氛可下可小于１００ｐｐｍ,中质油品硫含量次之,重质油硫含量最高。     

Ultrasonic nebulization extraction coupled with headspace single-drop microextraction of volatile and semivolatile compounds from the seed of Cuminum cyminum L

Ultrasonic nebulization extraction (UNE) coupled with headspace single-drop microextraction (HS-SDME) was developed. In the UNE process, the analytes were transferred from the aqueous phase to the gas phase. Then the analytes were transferred from the gas phase to the solvent phase by the carrier gas and extracted and enriched with suspended microdrop solvent. Finally, the microdrop solvent injected into GC-MS system. The parameters affecting extraction performance, such as type of suspended solvent, microdrop volume, flow rate of carrier gas, temperature of extraction vessel and extraction time were investigated and optimized. The proposed method can be applied for the extraction and enrichment of the volatile and semivolatile compounds simultaneously. The extraction efficiency of the proposed method was compared with that of ultrasonic extraction (UE) and UE-HS-SDME. Compared with UE-HS-SDME, the contents of constituents in the extract obtained by the proposed method were closer to those obtained by hydrodistillation (HD), which is a standard extraction method.     

Distribution behavior of astatine: Solvent extraction and back extraction

The distribution behavior of astatine was studied at tracer concentrations and over a wide range of carrier iodide concentration in both solvent extraction and back extraction processes. Astatine compounds were extracted instantly into the organic solvent, CS₂ from the carrier free and carrier iodide containing solutions. Back extraction of astatine with various NaOH solutions followed by solvent extraction caused the hydrolysis of astatine. The distribution behavior of astatine was explained by the extraction reaction schemes.     

Dynamic headspace analyses of residual volatiles in pharmaceuticals

Pharmaceutical preparations may be assayed for volatile organic compounds by purging them with a stream of inert carrier gas and collecting the organics onto a suitable sorbent material, from which they may be backflushed to a gas chromatograph. Compared to solvent extraction, the process offers advantages of increased sensitivity, ease of automation, and elimination of the solvent peak. Examples are given of three major sources of volatiles in pharmaceuticals, with the development of a method for quantitating the volatiles using an internal standard.     

改进的微波辅助无溶剂法提取薄荷和陈皮中的挥发油组分

An improved solvent free microwave extraction, in which a kind of microwave absorption medium （carbonyl iron powder） was used, was applied to the extraction of essential oil from dried menthol mint and orange peel without addition of any solvent and pretreatment. It took much less time of extraction （30 min） than microwave-assisted hydrodistillation （90 min） and conventional hydrodistillation （180 min）. The kinds of chemical compositions in essential oil extracted by different methods were almost the same and such improved solvent free microwave extraction can be a feasible way in extraction of essential oil from dried plant materials.     

Finite concentration inverse gas chromatography: Diffusion and partition measurements

Inverse gas chromatography (IGC) is a very fast, accurate, and reliable technique to measure diffusion coefficients. This technique however, has been limited to measurements in the infinite dilution region, i.e., in the region of negligible amount of solvent in the polymer. We have extended the scope of inverse gas chromatography to measure diffusion coefficients at finite concentrations of the solvent. This involves doping the carrier gas with a solvent of interest to achieve finite concentrations of solvent in the carrier gas and hence in the polymer. The carrier gas is passed through a saturator maintained at constant temperature to achieve this purpose. Diffusion coefficients for polyvinyl acetate–toluene, and polystyrene–toluene systems were determined at finite concentrations. The results were compared with the traditional gravimetric sorption and piezoelectric sorption measurements reported in the literature. The data are in excellent agreement with the values reported, correlate well with the Vrentas–Duda free volume theory, and can also be predicted from infinitely dilute data using the free volume theory. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35 : 1279–1290, 1997