超声强化超临界流体萃取技术及其最新进展

文章较系统地介绍了超声强化超临界CO2萃取装置的设计,讨论了超声强化超临界CO2萃取技术的应用、萃取模型及其超声强化机理。超声强化与其他强化方法相比较,具有无污染、强化效率高等优点,超声波加入不仅降低了萃取系统的压力、萃取温度以及夹带剂用量和萃取时间,而且提高了萃取率,同时萃取对象的结构并没有发生变化。文章还提出了以后研究的重点。     

Preparation of budesonide-poly (ethylene oxide) solid dispersions using supercritical fluid technology

The purpose of this study was to investigate the possibility of preparing solid dispersions of the poorly soluble budesonide by supercritical fluid (SCF) technique, using poly (ethylene oxide) (PEO) as a hydrophilic carrier. The budesonide-PEO solid dispersions were prepared, using supercritical carbon dioxide (SC CO₂) as the processing medium, and characterized by scanning electron microscopy (SEM), powder X-ray diffraction (PXRD), differential scanning calorimetry (DSC), solubility test and dissolution test in order to understand the influence of the SCF process on the physical status of the drug. The endothermic peak of budesonide in the SCF-treated mixtures was significantly reduced, indicating that budesonide was in amorphous form inside the carrier system. This was further confirmed by SEM and PXRD studies. The enhanced dissolution rates of budesonide were observed from SCF-treated budesonide-PEO mixtures. The amorphous characteristic of the budesonide, the better mixing of drug and PEO powders in the presence of SC CO₂, together with the improved wettability of the drug in PEO, produced a remarkable enhancement of the in vitro drug dissolution rate. Thus, budesonide-PEO solid dispersions with enhanced dissolution rate can be prepared using organic solvent-free SCF process.     

Quantitative analysis of cosmetics waxes by using supercritical fluid extraction (SFE)/supercritical fluid chromatography (SFC) and multivariate data analysis

Waxes play an indispensable role in the formulation of modern cosmetics. Quantitative measurement of the level of different waxes in cosmetics is essential to the understanding of the performance characteristics of the cosmetics. Conventionally, waxes in cosmetics are extracted by Soxhlet extraction using an organic solvent. This extraction is not quantitative. By using SFE, quantitative extraction of the waxes was easily obtained. Due to the complexity of the natural waxes and the coexistence of several types of waxes in a cosmetics product, the level of different waxes in a mixture is best determined by using SFC and multivariate data analysis. Application of this approach in analysis of waxes in mascaras is reported.     

Statistical mechanical description of supercritical fluid extraction and retrograde condensation

The phenomena of supercritical fluid extraction (SFE) and its reverse effect, which is known as retrograde condensation (RC), have found new and important applications in industrial separation of chemical compounds and recovery and processing of natural products and fossil fuels. Full-scale industrial utilization of SFE/RC processes requires knowledge about thermodynamic and transport characteristics of the asymmetric mixtures involved and the development of predictive modeling and correlation techniques for performance of the SFE/RC system under consideration. In this report, through the application of statistical mechanical techniques, the reasons for the lack of accuracy of existing predictive approaches are described and they are improved. It is demonstrated that these techniques also allow us to study the effect of mixed supercritical solvents on the solubility of heavy solutes (solids) at different compositions of the solvents, pressures, and temperatures. Fluid phase equilibrium algorithms based on the conformal solution van der Waals mixing rules and different equations of state are presented for the prediction of solubilities of heavy liquid in supercritical gases. It is shown that the Peng-Robinson equation of state based on conformal solution theory can predict solubilites of heavy liquid in supercritical gases more accurately than the van der Waals and Redlich-Kwong equations of state.     

Automatic on-line coupling of supercritical fluid extraction and capillary electrophoresis

An interface for the automatic coupling of a supercritical fluid extractor (SFE) with capillary electrophoretic (CE) equipment, both commercially available, was developed with a view to improving sample treatment, which is a crucial step in capillary electrophoresis. Extracted analytes were collected in a trap following depressurization in the SFE and were transferred to the CE equipment across the interface. The key elements of the experimental assembly are a laboratory-made programmable arm and the autosampler of the CE equipment, both of which are controlled by a built-in microprocessor using an appropriate electronic interface and customized software. This combined system was successfully used to determine cresols and chlorophenols in liquid samples (river water and human urine) with increased precision, throughput, and automatability. The proposed arrangement opens up interesting prospects for the direct determination of analyte traces in solid samples without human intervention.     

Decontamination of hazardous substances from solid matrices and liquids using supercritical fluids extraction: a review

Supercritical fluid has been adopted as an extraction media to remove various kinds of substances from distinct types of solid matrices since three decades ago. Compared to conventional extraction mode, supercritical fluid extraction technology is preferred because of the flexibility in adjusting its dissolving power and inherent elimination of organic solvent which means reducing time and money needed for subsequent purification. Utilization of this method as an environmental remedial technology, however, has become a trend only after its accomplishment in analytical chemistry was acknowledged. This review tries to summarize in a comprehensive manner the multitude aspects involved in hazardous compounds removal from miscellaneous class of environmental matrices. The industrial adsorbent regeneration using supercritical fluid technology is also discussed. Although, this technology has been successfully realized for environmental remediation in laboratory and on pilot-plant scale, its commercialization attempts still lack significant technology improvement in order to reach the economic feasibility.     

On-line nonmetal detection for argon supercritical fluid extraction using inductively coupled plasma optical emission spectroscopy

This paper describes the development of a solventless instrumental method for determining organic contaminants in soil by coupling argon supercritical fluid extraction (SFE) to inductively coupled plasma atomic emission spectroscopy (ICP-AES). In this method, organic compounds are first extracted by Ar SFE, transferred to the ICP directly in the supercritical (SC) argon, fragmented in the plasma, and then determined via their nonmetal atomic emissions. Supercritical Ar is superior to SC CO(2) for use in ICP-AES because it overcomes the disadvantages of plasma blowout, noisy baselines, and CO(2) interference in the determination of carbon. All instruments employed were commercially available, and the interface between the SFE and the torch of the ICP consisted of a simple glass capillary tube. Four nonmetals, C, S, P, and Si, were selected for this preliminary study. The selectivities obtained for these nonmetals, referenced to carbon, were found to be 345, 38?000, and 1400 for sulfur, phosphorus, and silicon, respectively. With the exception of carbon, the mass detection limits are in the range of 0.06-1.8 μg. For this work, the mass detection limit of carbon is 66 μg and is limited by the smallest aliquot of material that can be injected by syringe. Finally, total petroleum hydrocarbons (TPHs) were determined in two "real world" contaminated soil samples via the carbon emission at 247.9 nm. Dodecane was used as the standard reference compound because its response was found to be similar to other petroleum hydrocarbons (e.g., kerosene, gasoline, no. 1 fuel oil, and no. 2 fuel oil). Additionally, it was found necessary to add a small amount (i.e., 250 mg) of drying agent to the SFE vessel in order to prevent the plasma from extinguishing from the extracted water. The results of the on-line Ar SFE/ICP-AES determinations of TPH in the two samples agreed well with those obtained from conventional off-line CO(2) SFE and off-line Ar SFE.     

固相萃取-高效液相色谱法测定水中邻苯二甲酸酯类的方法研究

建立了固相萃取-高效液相色谱法测定水中5种邻苯二甲酸酯类的方法。通过正交实验确定了固相萃取的最优化条件：洗脱剂组成（乙醚：甲醇）19：1,洗脱速率1．0mL／min,洗脱体积9mL,清洗剂组成（甲醇：水）1：19。液相色谱的最佳条件：检测波长224nm,流速1．0mL／min,采用梯度洗脱,开始时甲醇-水（75：26,V／V）,保持6min,第7min甲醇比例上升到100％。结果,5种物质峰面积对浓度进行线性回归的相关系数均大于0．9992,该方法的最低检出限在（0．01～0．07）pg／L之间,加标回收率82．1％～97．4％,相对标准偏差（RSD）1．1％～2．4％。     

Direct on-line continuous supercritical fluid extraction and HPLC of aqueous pyrethrins solutions

A new method, employing supercritical fluid extraction (SFE) connected on-line with high-performance liquid chromatography, was developed for the determination of pyrethrins and piperonyl butoxide in aqueous solutions. The principle of the laboratory-made device for SFE is based on the low mutual solubility of water and supercritical (liquid) CO2. This device works in continuous mode that offers extraction of unlimited sample volumes. Different extraction temperatures and pressures were tested to find optimum extraction conditions. The addition of organic modifier and inorganic salt to the water sample to increase extraction recovery was investigated. The method was evaluated, and it was applied for the extraction of aqueous samples spiked with commercial insecticides. The working concentration range of the method was from the limit of quantification (0.1 microg L(-1)) to the solubility of the analytes in water.     

In-line catalytic purification of carbon dioxide used in analytical-scale supercritical fluid extraction

Supercritical fluid extraction analyses are often compromised by trace impurities present in the solvent carbon dioxide. These impurities, commonly used as lubricants in the specialty gas industry, can produce significant background levels, increasing limits of detection and quantification. This problem is especially severe when electron capture detection (ECD) is used for trace concentrations of analytes (e.g., polychlorinated biphenyls and chlorinated pesticides). In this study, an in-line catalyst-based purification system was successfully employed to remove ECD-responsive contaminants from CO2. Low-purity (98%) "Bone Dry" CO2 was purified to levels cleaner than a very-high-purity grade of CO2 specified at less than 10 ppt ECD-responsive contaminants. Purification was successfully applied to extremely sensitive on-column experiments as well as higher flow rate off-line experiments. In addition to lowering limits of detection and quantification, significant cost savings can be realized by purifying inexpensive, low-purity CO2 instead of relying on much more expensive, prepurified CO2.     

Accelerated solvent extraction (ASE) of environmental organic compounds in soils using a modified supercritical fluid extractor

Accelerated solvent extraction (ASE) has been applied to the quantitative extraction of a selected list of semi-volatiles, which include polycyclic aromatic hydrocarbons (PAHs), phenols, polychlorinated biphenyls (PCBs) and total petroleum hydrocarbons. Two conventional supercritical fluid extraction (SFE) systems, the Suprex Prep Master and SFE/50 systems have been modified to function as ASE systems. Using solvent instead of supercritical fluid, extraction in an enclosed system proceeded under high pressure and temperature. Parameters such as extraction temperature and effect of modifiers were investigated. Although limited by a 150 degrees C maximum oven temperature, effective extraction could be carried out in less than 25 min for all the compounds studied. The technique was applied to a variety of real matrices contaminated with hydrocarbons, PAHs and phenols. Validations of the technique were performed using standard reference materials. Recoveries for these matrices were good (>75%) and precision (R.S.D.) was generally less than 10%. Primarily a rapid field extraction technique, comparison with other rapid extraction such as sonication and microwave assisted extraction (MAP) were made. Recoveries were found to be comparable to MAP and superior to sonication. On the present ASE system, only sequential extraction can be carried out but given the rapid nature of the process, about 15 samples can be carried out in a working day.     

Design for on-line coupling of supercritical fluid extraction with liquid chromatography: quantitative analysis of polynuclear aromatic hydrocarbons in a solid matrix

Supercritical fluid extraction (SFE) was directly coupled with high-performance liquid chromatography (LC) via the simplest interface--only one six-port injection valve. By using water to eliminate decompressed CO2 gas in the solid-phase octadecylsilica trap, high extraction recovery (> or = 95%) of polynuclear aromatic hydrocarbons (PAHs) from a sand matrix was achieved under optimized conditions. The volume of rinse water had little influence on the recovery, due to the very low solubility of PAHs in water and the sorption properties of the C-18 trap. Different amounts of sand matrix with a fixed mass of analytes have also been tested. No decrease in recovery was found when the matrix (sand) increased from 1 to 10 g. Methanol and acetone were used as a CO2 modifier to enhance the extraction efficiency. Finally, PAHs in naturally contaminated soil were successfully extracted and quantitatively determined by this hyphenated system. Compared to the EPA method (Soxhlet extraction following by GC/MS), on-line SFE-LC gave precise results in a much shorter time.     

Collection efficiency of various solid-phase traps for off-line supercritical fluid extraction.

Solid-phase extraction tubes were evaluated as traps for off-line supercritical fluid extraction. Normal- and reversed-phase traps were studied with hydrocarbons, phenols, and a "test mixture" in order to determine the trapping efficiency. These traps were then used for the extraction of PCBs from river sediment. Polyethylene frits were also investigated for their use as solid-phase traps in SFE.     

Improved solvent trapping of volatiles in supercritical fluid extraction by pressurizing the collection vial

The high flow rates that result after decompression make the trapping of analytes one of the more difficult aspects of a supercritical extraction. By elevation of the pressure on the collection vial, the flow may be reduced and trapping efficiency improved, considerably. The effects of different collection vial pressures were evaluated. The best results were obtained at 25 atm. With the collection vial at 25 atm, the trapping efficiencies of different solvents were then investigated. Also considered were the effects of solvent volume, extraction flow rate, collection solvent geometry, and restrictor temperature. For a 30 min extraction--with the restrictor line at 200 degrees C--quantitative recoveries were obtained with analytes as volatile as chlorobenzene (approximately 90%) in 1 mL of solvent. Mild precooling of the collection vessel allowed quantitative recoveries to be obtained down to benzene (94.2%).     

In-membrane preconcentration/membrane inlet mass spectrometry of volatile and semivolatile organic compounds

The on-line determination of volatile and semivolatile organic compounds (SVOCs) is reported using membrane inlet mass spectrometry with in-membrane preconcentration (IMP-MIMS). Semivolatile organic compounds in aqueous samples are preconcentrated in a flow-through silicone hollow-fiber membrane inlet held in a GC oven. The sample stream is replaced with air, and the SVOCs are thermally desorbed into the mass spectrometer by rapid heating of the membrane. The method is evaluated for the on-line determination of 4-fluorobenzoic acid, 3,5-difluorobenzoic acid, 2-chlorophenol, p-tert-butylphenol, and dimethyl sulfoxide (DMSO) in water. The selectivity of the IMP-MIMS technique for SVOCs in the presence of VOCs is demonstrated. Cryotrapping and a rapid gas chromatographic separation step were added between the membrane and the mass spectrometer ion source for the determination of SVOCs in complex mixtures. The procedure is demonstrated for the determination of dimethyl sulfoxide (DMSO) in equine urine, using internal standardization with DMSO-d6. Full-scan electron ionization (EI) mass spectrometric detection showed good linearity (R = 0.998) and RSDs, relative to the internal standard, of 2.2% for desorption only and 4.6% for desorption and cryotrapping.     

Decontamination of uranium-contaminated waste oil using supercritical fluid and nitric acid

The waste oil used in nuclear fuel processing is contaminated with uranium because of its contact with materials or environments containing uranium. Under current law, waste oil that has been contaminated with uranium is very difficult to dispose of at a radioactive waste disposal site. To dispose of the uranium-contaminated waste oil, the uranium was separated from the contaminated waste oil. Supercritical R-22 is an excellent solvent for extracting clean oil from uranium-contaminated waste oil. The critical temperature of R-22 is 96.15 °C and the critical pressure is 49.9 bar. In this study, a process to remove uranium from the uranium-contaminated waste oil using supercritical R-22 was developed. The waste oil has a small amount of additives containing N, S or P, such as amines, dithiocarbamates and dialkyldithiophosphates. It seems that these organic additives form uranium-combined compounds. For this reason, dissolution of uranium from the uranium-combined compounds using nitric acid was needed. The efficiency of the removal of uranium from the uranium-contaminated waste oil using supercritical R-22 extraction and nitric acid treatment was determined.     

Influence of water on the supercritical fluid extraction of naphthalene from soil.

Supercritical fluid extraction (SFE) is an innovative soil remediation technology. To aid system evaluation and design, thermodynamic and kinetic parameters have been measured using a naphthalene contaminated, loamy sand at various water contents. The experimental results show that supercritical carbon dioxide can easily extract naphthalene from soil when the water content is below 10%. At low water contents, mass transfer is rapid and the equilibrium partition coefficient is independent of the soil's water content. However, the overall mass transfer coefficient, (kova), decreases by at least a factor of 200 as the water content increases from 10 to 20%.     

Determination of the quaternary ammonium surfactant ditallowdimethylammonium in digested sludges and marine sediments by supercritical fluid extraction and liquid chromatography with postcolumn ion-pair formation

To study the phasing-out of the quaternary ammonium surfactant ditallowdimethylammonium cation (DTDMAC), concentrations of the cation in anaerobically stabilized sewage sludges were determined before and after its replacement by better degradable compounds. DTDMAC was quantitatively extracted from digested sludges using 380 atm of supercritical CO(2) modified with 30% methanol at 100 °C. Determination of DTDMAC was performed by normal-phase HPLC with postcolumn ion-pair formation and extraction with no sample cleanup. Mean concentrations of DTDMAC in sludges from five different municipal sewage treatment plants in Switzerland decreased from 3.67 g/kg (in 1991) to 0.96, 0.47, and 0.21 g/kg of dry sludge in 1992, 1993, and 1994, respectively. The precision of the method in digested sludge for 0.1-6.0 g/kg of dry matter, as indicated by the relative standard deviation, was typically 7%. The influence of the sample matrix was studied by performing supercritical fluid extraction (SFE) in coastal marine sediments. While SFE and a conventional liquid extraction method gave equal DTDMAC concentrations in sludges, the extraction of marine sediment samples yielded 30-40% higher DTDMAC values for SFE compared to those obtained by liquid extraction. The 94% drop in DTDMAC concentrations in digested sludges is due to the replacement of this substance and is a clear result of the producers' voluntary ban on its use in Europe.