COSMO-RS modeling on the extraction of stimulant drugs from urine sample by the double actions of supercritical carbon dioxide and ionic liquid

This work presents the first research linking chemical engineering and sport science as far as we know. The COSMO-RS (conductor-like screening model for real solvents) model was used to make a priori prediction for the extraction of stimulants from aqueous solution by the double action of supercritical carbon dioxide (SC CO₂) and ionic liquid. It was found that the suitable ionic liquids should have small molecular volume, unbranched group and no sterical shielding effect around anion charge center, and thus [C₂MIM]⁺[OAc]^- is the best among all the ionic liquids investigated. The calculated results from the COSMO-RS model were qualitatively consistent with those from experiments. On this basis, partition coefficients of amphetamine (C9N) and nikethamide (C10N) between aqueous phase and supercritical fluid (or MTBE) phase at different temperatures were calculated. It was shown that the separation efficiency of supercritical extraction with ionic liquid is generally higher than that of traditional liquid-liquid extraction. The modeling present can also be extended to the separation of trace amount of organic substances from aqueous solutions for other purposes.     

超临界CO_2萃取苕叶细辛挥发油

采用正交实验法对超临界CO2萃取苕叶细辛挥发油的条件进行了研究。考察了萃取温度、压力、CO2流量等因素在不同水平下对苕叶细辛挥发油提取率的影响。得到了超临界CO2萃取苕叶细辛挥发油的最佳实验条件:萃取压力20MPa,温度40℃,CO2流量35kg/h和萃取时间80min,得率为1 72%。水蒸气蒸馏提取得率为0 24%。超临界CO2萃取的收率高,萃取时间短。     

Reactive extraction of succinic acid using supercritical carbon dioxide

Reactive extraction using supercritical carbon dioxide (scCO₂) and tri-n-octylamine (TOA) was evaluated as a separation method of succinic acid from an aqueous solution. The reactive extraction of succinic acid was performed at varying initial acid concentrations in aqueous solution (0.07–0.45 mol?dm^?3), temperature (35–65°C) and pressure (8–16 MPa). The succinic acid separation was conducted in both batch mode and semi-continuous mode. The highest reactive extraction efficiency of approx. 62% was obtained for the process conducted in semi-continuous mode at 35°C and 16 MPa for the initial acid concentrations in aqueous phase of 0.39 mol?dm^?3.     

Separation of ethylene oxide from its aqueous solution by supercritical fluid extraction

The nature of an inert additive (n-pentane) that is expediently used at the step of distillation separation of a diluted ethylene oxide solution in supercritical carbon dioxide is determined. An experimental study is performed to find the characteristics of the extraction step of separation of ethylene oxide from its aqueous solution using supercritical carbon dioxide in the presence of n-pentane.     

Supercritical CO2-assisted preparation of a PMMA composite membrane for bisphenol A recognition in aqueous environment

This work reports a novel strategy to prepare affinity composite membranes using supercritical fluid technology. By blending molecularly imprinted polymeric particles with PMMA, a porous hybrid structure with affinity to the template molecule, bisphenol A, was prepared using a supercritical carbon dioxide (scCO₂)-assisted method. Membranes were characterized in terms of morphology, mechanical performance and transport properties. The ability of the polymers and hybrid membranes to adsorb bisphenol A was tested in aqueous solutions and fitted to a linearized Langmuir equation, showing that adsorption takes place at homogeneous affinity binding sites within the imprinted surface. Filtration experiments showed that the imprinted hybrid membrane was able to adsorb higher amounts of template even in non-equilibrium dynamic binding conditions. The hybridization of the PMMA membrane herein reported conveys two important improvements over neat PMMA membrane: it introduced molecular affinity towards the template molecule and significantly increased the permeability of the porous structures, which are key parameters in processes that involve membranes. This technique could expand the applications of polymeric beads powders and enhance the efficiency of the membrane's transport properties. Our work presents a new method to confer affinity to a porous structure by immobilization of imprinted polymers, combining polymer synthesis and membrane formation using supercritical fluid technology.     

The Possibility of Reprocessing of Spent Nuclear Fuel Using Supercritical Fluids

For the first time, the possibility of dissolution of spent nuclear fuel from a nuclear power plant in liquid and supercritical carbon dioxide was demonstrated. As shown by the example of spent nuclear fuel, the dissolution and the extraction of actinides and fission products by solutions of tributyl phosphate and nitric acid adducts TBP(HNO₃)_1.8 in carbon dioxide can be used as one of the stages of spent nuclear fuel reprocessing.     

A STUDY ON SUPERCRITICAL FLUID EXTRACTION OF L-PROLINE

The extraction of L-proline from the fermentation broth filtrate with the supercritical fluid was studied. It has been proved that L-proline and most amino acids are hardly dissolved in the pure supercritical carbon dioxide fluid. When the methyl alcohol was added as an entrainer in L-proline solution or carbon dioxide fluid, the solubility of L-proline in the supercritical fluid would be greatly increased, but ethyl alcohol was unsatisfactory as an entrainer.The influences of extraction pressure, temperature, time, flow rate of fluid, concentrations of L-proline and entrainer on the yield of L-proline have been investigated for searching the optimal extraction conditions.     

Effect of different PVDF and additives on the properties of hollow fiber membranes contactors for CO2 separation

In the present work, different poly(vinil fluoride) (PVDF) were selected for preparing membranes, based on the fact that they are able to form polymer solutions with different viscosities. This characteristic can affect spinning, as well as, mass transfer between the polymer solution and precipitation bath; therefore, each PVDF solution can differently affect membrane formation. The effect of different additives in the polymer solutions was also investigated. Flat sheet and hollow fiber membranes were characterized by Scanning Electron Microscopy analysis, contact angle, gas permeation, porosity, and membrane gas–liquid contactor tests, aiming carbon dioxide removal. The hollow fibers prepared by the polymer which formed a less viscous solution (named PVDF-I) had a faster light transmittance decay, which started around 150 s before the more viscous solution (PVDF-II). Hollow fibers obtained using PVDF-I and propionic acid, in the polymer solution, presented the best gas–liquid contactor performance. CO₂ removal increased from 21 to 35.1%, for PVDF-II and PVDF-I, respectively, using aqueous diethanolamine solution, as absorbent liquid. In conclusion, even though PVDF-I and PVDF-II membranes were obtained by using the same spinning conditions and experimental methodology, the difference between the polymers properties certainly affected the final membrane morphology and transport properties.     

超临界二氧化碳萃取在石油工业中的应用探究

随着化工工程的发展,超临界技术得以发展并被广泛的应用到了各个领域之中,尤其是石油化工行业。二氧化碳、乙醇、丙烯等气体都可作为流体萃取的溶剂,而在石油工业中,二氧化碳萃取具有独特的优势。对以二氧化碳为溶剂的超临界流体萃取技术在石油工业中的应用情况进行分析与探究。     

缔合模型用于超临界萃取溶解度计算

基于在超临界萃取过程中,同时存在超临界流体相－固相相平衡和超临界相缔合反应平衡的假设,提出一一个用于超临界萃取溶解度计算的缔合模型。该模型式用于２７个固体溶质和５个液体溶质在超临界溶剂中溶解度的计算,其平均相对偏差绝大多数体系均小于１０％。     

Crystallization of sulfamethizole using the supercritical and liquid antisolvent processes

Sulfamethizole was crystallized using both the supercritical and liquid antisolvent processes. Acetone and N,N-dimethyl formamide (DMF) were selected as solvents for the pharmaceutical compound, and carbon dioxide and distilled water were used as antisolvents. In the supercritical antisolvent process, the effects of experimental conditions such as carbon dioxide injection rate, type of solvent, and temperature were investigated. In the liquid antisolvent process, the effect of ultrasound on the properties of crystal was examined. The various crystal habits such as tabular, platy, acicular, and prismatic were observed depending on the process and experimental conditions. Differential scanning calorimetry (DSC) measurement revealed that the carbon dioxide injection rate affected the crystallinity of sulfamethizole particles. Larger crystals were obtained at higher temperatures in the two antisolvent processes. The particle size distribution was mostly affected by the antisolvent injection rate and the application of ultrasound.     

Separation of Phenantrene from Anthracene Oil using Supercritical Carbon Dioxide

Supercritical fluid extraction (SFE) is a relatively new separation technique that has received much attention in recent years. This process is an alternative to distillation or liquid extraction. Its main advantage over the conventional ones is that the dissolved extract may be completely separated from the supercritical fluid simply by decreasing the pressure. In recent years considerable effort has been devoted to the measurement of equilibrium solubility data for solids in supercritical fluids. A coal tar distillate, anthracene oil, which contains 34.46 mass‐% phenanthrene, 33.8 mass‐% anthracene, 13.89 mass‐% carbazole and other impurities, was used as the model mixture. In this study, an experimental flow‐type apparatus has been designed to determine solubility data for the main components of anthracene oil (phenanthrene, anthracene, and carbazole) as a binary, quaternary, and multi component mixture in supercritical carbon dioxide. The equilibrium solubilities were measured at 45 °C isotherm, over a pressure range of 98–200 bar. The separation of phenanthrene from anthracene oil has been also studied by supercritical carbon dioxide at different temperatures and pressure in an extracting vessel containing 27 sieve trays.     

Extraction of Furfural with Carbon Dioxide

Abstract

A new approach to separate furfural from aqueous waste has been investigated. Recovery of furfural and acetic acid from aqueous effluents of a paper mill has successfully been applied on an industrial scale since 1981.

The process is based on the extraction of furfural and acetic acid by the solvent trooctylphosphineoxide (TOPO). Common extraction of both substances may cause the formation of resin residues. Improvement was expected by selective extraction of furfural with chlorinated hydrocarbons, but ecological reasons stopped further development of this project.

The current investigation is centered in the evaluation of extraction of furfural by supercritical carbon dioxide. The influence of temperature and pressure on the extraction properties has been worked out. The investigation has considered the multi-component system furfural-acetic acid-water-carbon dioxide. Solubility of furfural in liquid and supercritical carbon dioxide has been measured, and equilibrium data for the ternary system furfural-water-CO₂ as well as for the quaternary system furfuralacetic acid-water-CO₂ have been determined. A high-pressure extraction column has been used for evaluation of mass transfer rates.     

CLATHRATE HYDRATE FORMATION ENHANCES NEAR-CRITICAL AND SUPERCRITICAL SOLVENT EXTRACTION EQUILIBRIA

Pre-concentration of dilute aqueous solutions by hydrate formation can improve the effective distribution coefficient and selectivity of solvent extraction. Many solvents can serve simultaneously to promote solution concentration by hydrate formation and also to extract non-polar solutes from the resulting concentrated solution. This concept is illustrated for systems with supercritical ethylene and with near-critical liquid carbon dioxide, and its application to conventional solvents is discussed.     

EVALUATION OF PACKED COLUMNS IN SUPERCRITICAL EXTRACTION PROCESSES

The purpose of the present work is to add to the base of knowledge in the use of packed columns when used in supercritical extraction service. Experimental studies were performed on a 2·54 cm diameter supercritical fluid extraction column operated in both spray and packed column arrangements. The packing used was 6· mm Raschig rings with a surface area of 722 m²/m³. The supercritical systems studied were carbon dioxide/ethanol/water and carbon dioxide/isopropanol/water at 102 atmospheres and 35^°C and 102 atmospheres and 40^°C, respectively. In order to compare supercritical with conventional extraction, similar data were obtained in the same column with the toluene/acetone/water system at one atmosphere and 24^°C.     

Supercritical fluid extraction of α- and β-acids from hops compared to cyclically pressurized solid–liquid extraction

In this paper, two solid–liquid extraction techniques, supercritical fluid extraction (SFE) with and without modifiers and cyclically pressurized solid–liquid extraction with a Naviglio Extractor, were compared on the basis of extraction of acidic compounds contained in hops flowers. The hops extracts were analyzed by electro-kinetic capillary chromatography (MECK). The results showed that the technique using supercritical carbon dioxide was more effective for the isolation of β acids; the use of ethanol as a co-solvent, as reported in the literature, produced a heterogeneous extract, while cyclically pressurized solid–liquid extraction showed a greater extraction capacity for α acids. Consequently, both techniques are valid for the extraction of α and β acids from hops. By suitably varying the parameters of the two extractive procedures, it will be possible to obtain extracts for use in the production of beer and dietary supplements and drugs. Furthermore, based on the SFE CO₂ extraction process, a mathematical model was applied to the examined process, and a numerical simulation was performed, leading to a model that provides direction for the optimization of further experiments.     

Untersuchung des dynamischen Prozessverhaltens bei Betriebsstörungen im Bereich der chemischen Absorption

The knowledge of the dynamic chemical absorption process behavior is essential for the prevention of emergency situations. For this reason, a rate-based model for dynamic simulations was developed and validated. As an example, the reactive absorption of carbon dioxide by aqueous monoethanolamine solution was modeled. Subsequently, this model was used to simulate step responses caused by changes in individual entry parameters in an industrial-scale absorption column. With the aid of these step responses, fast simplified models can be developed that can be used for prevention of incidents in real time.     

Recovery of grape seed oil by liquid and supercritical carbon dioxide extraction: a comparison with conventional solvent extraction

In this work the extraction of grape seed oil by means of liquid and supercritical carbon dioxide as solvent is described. The operating conditions to determine the maximum extraction yield were studied. The efficiency of supercritical fluid extraction (SFE) was similar to that obtained by conventional liquid extraction, but the quality of the supercritically extracted oil was higher, equivalent to a degummed, liquid- extracted oil. It is considered that SFE is competitive with conventional liquid extraction, because the solvent distillation and oil refining stages can be omitted.     

超临二氧化碳萃取分离异丙醇-水的相平衡研究

用静态法测定了高压下CO_2-i-C_3H_7OH二元系和CO_2-i-C_3H_7OH-H_2O三元系的相平衡数据.实验证明超临CO_2能从水溶液中萃取分离异丙醇,并打破了常压下异丙醇-水的恒沸组成.用SRK方程和Huran-Vidal混合规则,建立了CO_2-i-C_3H_7OH-H_2O三元系的热力学模型.此模型只用二元作用系数,能成功地预测三元气液平衡和平衡系线随温度压力剧烈变化的行为.最后,通过实验数据分析和模型预测,探讨了影响超临CO_2从水溶液中萃取分离异丙醇的各种条件.     

超临界流体技术及其在生物工程中的应用

介绍了在生物工程有着广泛的应用前景的多种超临界流体技术，包括提取生物活性物质的超临界流体萃取，超临界条件二氧化碳中制备手性药物制备和淀粉水解制取葡萄糖的非水酶催化反应，超临界水条件下纤维素水解制备葡萄糖，超临界流体中的细胞破碎，制备缓释药物和色说载体的超临界流体溶液快速膨胀和气体抗溶剂结晶和沉淀技术。