Effect of Stearic Acid as a Co‐solvent on the Solubility Enhancement of Aspirin in Supercritical CO2

The solubility of aspirin in supercritical CO₂ (SC‐CO₂) with stearic acid as a co‐solvent was measured at various pressures and temperatures. The experimental data were obtained by a static method. Stearic acid had a significant effect on the enhancement of solubility, as the aspirin solubility increased by up to 16 times. Further, the effect of stearic acid on the solubility enhancement of aspirin was compared with that of other co‐solvents. Different semi‐empirical models from the literature were applied for correlating the experimental data, proving good agreement with the experimental data. The model of Sung and Shim exhibited the lowest deviation from the obtained data. The results of the solubility test can be employed to produce aspirin‐based pharmaceuticals using supercritical fluid technology (SFT).     

Effect of Solvent on Nanoparticle Production of β‐Carotene by a Supercritical Antisolvent Process

Production of micro‐ to nano‐sized particles of β‐carotene was investigated by means of solution‐enhanced dispersion by supercritical fluids (SEDS). β‐Carotene was dissolved in dichloromethane (DCM), N,N‐dimethylformamide (DMF), n‐hexane, or ethyl acetate, and supercritical CO₂ served as an antisolvent. The effects of the organic solvents, operating pressure, and temperature were examined. The morphologies of the particles produced by the SEDS were observed by field emission‐scanning electron microscopy and particle sizes were determined by image analysis. Irregularly shaped microparticles were produced in the system with DCM and DMF solution. Plate‐like microparticles were generated by using n‐hexane solution and irregular nanoparticles by ethyl acetate solution. The optimum operating conditions were found to be ethyl acetate as solvent in a defined pressure and temperature range.     

In‐line Rheological Behaviors of Gun Propellant Substitute Assisted with Supercritical CO2 in Extrusion Processing

To improve the rheological behaviors of gun propellants, SC‐CO₂ was injected into the gun propellant substitute in extrusion processing. A slit die rheometer was used to investigate the in‐line rheological behaviors of CA solution. A Power model was applied to describe the rheological behaviors of CA/SC‐CO₂ mixtures. The viscosity and pressure of CA solution obviously decrease with the assistance of SC‐CO₂. The viscosity of CA solution reduces by 16.64 % at 55 °C and 10 s⁻¹ with the presence of SC‐CO₂. Increasing the processing temperature makes the viscosity of CA/SC‐CO₂ mixture decrease remarkably, but it weakens the plasticization of SC‐CO₂ to CA. Although the increasing solvent content improves the flow of the CA/SC‐CO₂ mixture, it lowers the strength of CA/SC‐CO₂ mixture, which is not in favor of the quality of product. The investigation of the in‐line rheological behaviors of CA/SC‐CO₂ mixture is fundamental and important for the safe extrusion of gun propellants assisted with SC‐CO₂.     

超临界二氧化碳萃取技术应用状况

介绍了超临界二氧化碳萃取技术的特性、原理,应用情况及国内现状。     

Cost‐effective Synthesis of α‐LiAlO2 Powders for Molten Carbonate Fuel Cell Matrices

Lithium aluminate (α‐/β‐LiAlO₂) particles were fabricated using three methods. The first method used organic glycerin and triethylene glycol which functioned as a catalyst for fabrication of α‐LiAlO₂ particles with Al(OH)₃ and LiOH·H₂O as the starting materials. As a result of the heat‐treatment of the starting materials, α‐/β‐LiAlO₂ particles could be obtained. The amount of α‐LiAlO₂ particles in α‐/β‐LiAlO₂ increased slightly as more organics were added. Additionally, when synthesised α‐/β‐LiAlO₂ particles were heat‐treated in a CO₂ gas flow, β‐LiAlO₂ was partially transformed to α‐LiAlO₂. In the second method, molten salts (Li₂/Na₂/K₂CO₃) were used as a catalyst to fabricate α‐LiAlO₂ as a major phase, however, this method requires a washing process which can produce unexpected impurities. In the third method, pure α‐LiAlO₂ was obtained by heat‐treatment of cheap sources such as Li₂CO₃ and Al(OH)₃ at 600–800 °C. The mean particle size (604 nm–11.85 μm) and the specific surface area (3.22–11.4 m² g^–1) of α‐LiAlO₂ were suitable for reinforcing the matrix and tape casting. Lastly, this study examined the effect of CO₂ for the synthesising of α‐LiAlO₂ particles.     

Concentration of Natural Vitamin E Using a Continuous Countercurrent Supercritical CO2 Extraction‐Distillation Dual Column

A continuous countercurrent supercritical CO₂ extraction‐distillation dual‐column process was developed to extract and concentrate natural vitamin E (VE) from soybean oil deodorizer distillate (SODD). The experimental results demonstrated that process parameters such as extraction pressure, temperature, and solvent‐to‐feed ratio significantly impacted on the extraction efficiency of natural VE. A new five‐parameter mass transfer model for the continuous countercurrent supercritical CO₂ extraction‐distillation dual‐column process was presented based on the Penetration and Double‐Film theories. The calculated values of the mathematical model agreed well with the experimental data, with absolute average relative deviation values of less than 25 %.     

Influence of Supercritical CO2 Pretreatment of Corn Stover with Ethanol‐Water as Co‐Solvent on Lignin Degradation

The process of delignification during the pretreatment of corn stover in supercritical CO₂ with ethanol‐water as co‐solvent was investigated. After pretreatment, many lignin droplets were found deposited on the fiber surface which hinder cellulose digestibility. These lignin droplets were removed by ethanol‐water and after washing the optimal glucose yield increased significantly. Lignin degradation reactions competed with condensation reactions during pretreatment. The cleavage of ether bonds and the high solubility of lignin fragments in ethanol‐water co‐solvent were the key factors for lignin removal and degradation behavior during pretreatment.     

Application of Ultrasound‐Assisted Supercritical Extraction to Soil Remediation

The coupling of ultrasound to supercritical extraction with carbon dioxide has been evaluated as a green remediation technique for soils contaminated with pesticides. The study used samples of soil spiked with atrazine, an organophosphate and contaminant of widespread use. The influence of the operating temperature and pressure on the extraction of atrazine was studied. The extraction of atrazine was enhanced with the use of ultrasound relative to the results obtained from conventional supercritical extraction. This study, operated in semi‐continuous mode, demonstrates the possibility of increasing the yield of supercritical extraction by coupling with ultrasound instead of adding co‐solvents, which is a greener alternative for removing contaminants such as pesticides from soil matrices.     

Research on Perfusion Explosives from SF‐3 Double‐Base Propellants Using Supercritical CO2

Perfusion explosives were prepared using porous SF‐3 propellants, which were synthesized by a supercritical fluid foaming process. Scanning electron microscopy (SEM) was used to characterize the porous SF‐3 propellants. Massive holes were generated after the foaming process. The density of perfusion explosives using foamed SF‐3 propellants exceeds 1.3 g cm⁻³, and the detonation velocities exceed 6000 m s⁻¹. Underwater energy tests and high‐speed photography were carried out to investigate the detonation performance of perfusion explosives. The results showed that perfusion explosives using unfoamed SF‐3 propellants could not be detonated. However, perfusion explosives using their foamed analogs could be detonated herein.     

Fabrication of Silicone Rubber Foam with Tailored Porous Structures by Supercritical CO2

In spite of great concern on the wide application of silicone rubber foams, few works have been reported about easy‐operating foaming method. In this study, the effects of silica content and foaming process on the porous structure of high‐temperature‐vulcanized silicon rubber foams are evaluated, which are prepared by supercritical CO₂ at different conditions, with fumed silica used for reinforcement. Silicone rubber foams with cell size in 8–120 μm, cell density in 10⁵–10⁸ cm⁻³, and density between 0.45 and 0.9 g cm⁻³ are prepared under different saturation conditions. The results show that increasing silica content can decrease cell size. It is also found that cell density improves exponentially with increasing saturation pressure and decreasing saturation temperature. Besides, it demands less than 1 h for specimens to reach equilibrium on thickness around 3 mm. All the results indicate that the porous structures of silicone foams can be tailored by foaming process parameters facilely and are predictable with fitted equation.

     

Scheduling Model for a Multi‐Product Batch Plant Using a Pre‐Ordering Approach

A scheduling model for a multi‐product, multistage batch plant with parallel units is presented. The objective is to maximize the weighted completion times of orders in every processing stage while imposing a penalty on the slower orders. The proposed model uses the continuous‐time representation mode and describes the allocations of tasks, units and stages by a set of binary variables. In order to reduce the model size and provide a more effective solution to the model, a pre‐ordering approach that sorts the processing sequence of orders is developed. The pre‐ordering approach identifies the infeasible assignments through which the number of binary variables is significantly reduced. Illustrative examples are provided to show that the size of the proposed model is small, and therefore, needs much less computational effort in comparison with the existing models in the literature.     

The Influence of Supercritical Carbon Dioxide (SC‐CO2) on Electrolytes and Hydrogenation of Soybean Oil

The electrochemical hydrogenation of soybean oil with supercritical carbon dioxide (SC‐CO₂) has been studied to seek ways for substantial reduction of the trans fatty acids (TFA). The solubility of CO₂ in electrolytes and the conductivity of electrolytes were investigated using a self‐made electrochemical hydrogenation reactor. The optimum hydrogenation parameters were assessed. Both the solubility of CO₂ in electrolytes and the conductivity of electrolytes increased with increasing CO₂ pressure. When the pressure reached a critical point of CO₂, the solubility of CO₂ expressed as a mole fraction was 0.42 in cathode electrolyte and 0.1 in anode electrolyte. At 8 MPa, the conductivity of electrolytes was 1.5 times higher than that at 2 MPa. When the pressure was higher than the critical point of CO₂, the solubility of CO₂ in electrolytes and the conductivity of electrolytes reached a stable value. The optimum condition for electrochemical hydrogenation of soybean oil in SC‐CO₂ were reaction pressure (8 MPa), reaction temperature (48 °C), current (125 mA), agitation speed (300 rpm), and reaction time (8 h). Fatty acid profile, iodine value, and TFA content were evaluated at the optimum parameters. This investigation showed that the electrochemical hydrogenation of soybean oil in SC‐CO₂ was improved. The reaction time was shortened by 4 h, and TFA content was reduced by 35.8% compared to traditional hydrogenation process.     

Supercritical CO2 Extraction of Essential Oil from Algerian Rosemary (Rosmarinus officinalis L.)

The present study presents experimental results concerning the supercritical CO₂ extraction of essential oil from Algerian rosemary leaves. The effects of key operating parameters such as pressure, temperature, particle size and CO₂ mass flow rate on the extraction yield were investigated. The obtained yields were in the range of 0.95–3.52 g oil/g dry rosemary, and the best value was observed at a pressure of 22 MPa, a temperature of 40 °C, a flow rate of 7 g/min, and a particle size of 1 mm. The performance of the local rosemary used was assessed by comparison of the obtained yields with values reported in the literature for essential oils derived from different rosemary sources. The GC and the GC‐MS analyses showed that the major compound detected in the essential oil was camphor, at 48.89 wt %.     

超临界二氧化碳萃取大蒜油实验研究

建立了一套超临界流体萃取实验装置,系统研究了超临界二氧化碳萃取大蒜油的实验工艺,考察了萃取压力、萃取温度、流体流量以及原料厚度对大蒜油收率的影响,确定了各因素对萃取率指标影响的主次程度依次为:压力、流体流量、原料厚度、温度;确定了实验范围内的最佳萃取工艺条件为:压力25MPa、温度40℃、CO2流量0.3～0.4m3·h-1、大蒜厚度1～0.5mm。     

Supercritical CO2 Spray Drying of Ethyl Cellulose (EC) for Preparing Microparticles

Even though common spray drying has been widely used for drying food and related products, the effect of drying conditions of supercritical CO₂ spray drying on the particle sizes of dried products has not been well studied. The objective of this study was to study the effect of drying conditions and design parameters on the particle sizes of biomaterials dried with supercritical CO₂ spray drying. The ethyl cellulose (EC) microparticles were prepared with supercritical CO₂ as the dry medium using an experimental spray-drying apparatus. This research studied the influences of spray nozzle diameter, mass ratio of gas to liquid, solution concentration, temperature, and pressure on the physical characteristics of ethyl cellulose microparticles. The results indicated that the average size of the dried particles ranged from 1.07 to 9.84 µm. The spray nozzle with 8-mm diameter produced smaller microparticles with narrower distribution than the 4-mm spray nozzle. The average particle size increased with the increase of the ratio of gas to liquid. Also, the average size and distribution of the microparticles increased with the rise of temperature and solution concentration but decreased with the increase of pressure.     

Supercritical CO2 Extraction of Chlorophyll a from Spirulina platensis with a Static Modifier

Supercritical CO₂ extraction with a static modifier was applied to extract chlorophyll a from Spirulina platensis. The effects of the process were investigated by single‐factor and response surface analysis experiments. The optimal process parameters for supercritical CO₂ extraction were determined to be: ethanol/water as the modifier, 40 vol.‐% water content in the modifier, 21.2 mL modifier volume, 1 h static soaking time, 2 h dynamic extraction time, 48.7 MPa extraction pressure, 326.4 K extraction temperature, and 10 g min^–1 CO₂ flow rate. The optimized chlorophyll a extraction yield was 6.84 mg g^–1. A comparison of the experimental results suggested that the yield of chlorophyll a by supercritical CO₂ extraction with modifier was higher than that obtained by conventional solvent extraction.     

Supercritical carbon dioxide‐assisted loosening preparation of dry leather

The physical modification of the dry leather using supercritical carbon dioxide (SC‐CO₂) was studied in this article. A series of loosening processes of the leather fibers were carried out by changing the experimental conditions such as experimental pressure, experimental temperature, and time. The samples were characterized by scanning electronic microscopy (SEM), Brunauer–Emmett–Teller (BET) and X‐ray diffraction (XRD). SEM images show that samples were loosened by SC‐CO₂ and the leather fibers in micron size arrange more orderly after treatment. The BET surface area of treated samples increase from 1.67 m²/g to 6.33 m²/g with the changing of conditions. The optimal treatment conditions were determined. Moreover, XRD patterns indicate that aggregation structure of collagen fibers in the sample was altered by SC‐CO₂, and it can be found that the loosening of leather mostly happened in amorphous regions of collagen fibers. Besides, the percent breaking elongation of the samples was examined by means of a tensile analyzing test, and it indicates that the elongation at break of all the treated samples in SC‐CO₂ can increase to 128.2% compared with 95.9% of the original ones. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Optimization of Supercritical Extraction of Linalyl Acetate from Lavender via Box‐Behnken Design

Essential oil was extracted from lavender using supercritical carbon dioxide by means of a newly developed periodic static‐dynamic (PSD) procedure and the conventional semicontinuous (SC) technique. Applying GC‐FID analysis in conjunction with Box‐Behnken design, an optimum overall extraction yield (94.4 %) was obtained via PSD in contrast to 90 % for the SC method. The results indicate that supercritical fluid extraction is a viable technique for separation of constituents such as linalyl acetate, linalool, fenchone, and camphor for pharmaceutical and medicinal applications. Furthermore, a substantial reduction of energy consumption and solvent consumption is achieved with the developed PSD process compared to the conventional SC method.     

CO2 Methanation on Nickel Catalysts Supported on Mesoporous High‐Surface‐Area MgSiO3

Nickel catalysts prepared on high‐surface‐area mesoporous MgSiO₃ were synthesized and applied in methanation of CO₂. N₂ adsorption analysis confirmed the presence of the mesoporous structure on the synthesized samples and revealed that the increase in nickel content resulted in a shift of the pore size distributions to smaller pore sizes. Temperature‐programmed reduction analysis illustrated an improvement in reducibility of the catalysts by a higher nickel content. Catalytic results indicated enhanced CO₂ conversion with the increase in nickel percentage up to 15 wt %. The catalysts with higher percentage of nickel provided lower CO₂ conversion and CH₄ selectivity. The %15Ni/MgSiO₃ catalyst exhibited high catalytic stability under optimized conditions.     

Effect of Hydrophobic Plant Extract on the Physicochemical Properties of a Transparent Fabric Softener

This article investigates the effect of hydrophobic supercritical CO₂ raspberry seed extracts on the physicochemical and functional properties of a modern, transparent fabric softener. The addition of a hydrophobic extract to a transparent softener formulation increased the turbidity and dynamic viscosity of the product compared to the reference formulation (with no added extract). In addition, fabric rinsed in a bath containing the transparent fabric softener enriched with the hydrophobic extract was characterized by a higher degree of softness and slightly lower values of fabric rewettability (two parameters determining the usable properties of this type products) in relation to the values determined for a fabric exposed to the rinsing process in an aqueous solution of the transparent fabric softener without added extract. The results obtained in the assessment of physicochemical properties point to the modification of the structure of fabric softener resulting from the growth of surfactant aggregates due to solubilization of the hydrophobic extract. As a consequence, the deposit—an adsorption layer of surfactants (responsible for key characteristics relevant to the performance of this type of products) remaining on the fabric after the rinsing process—is modified.