Research on Preparation of Perfusion Explosive Using Foamed SF‐3 Double‐Base Propellant

Perfusion explosives were prepared using foamed SF‐3 propellants, which were synthesized by a two‐stage batch foaming process with different saturation time in supercritical fluid CO₂ as a foaming agent. The foamed SF‐3 propellants were characterized by scanning electron microscopy (SEM). Underwater detonation tests and test‐board detonation tests were carried out to investigate detonation performance of the prepared perfusion explosives. Results showed that more saturation time during the foaming process leads to more pores and cracks. Perfusion explosives prepared using foamed SF‐3 propellants exhibited much higher shock wave energy and stronger damage effectiveness than those using unfoamed SF‐3 propellants. Perfusion explosives prepared using foamed SF‐3 propellants with a saturation time of 2 h exhibited the highest shock wave energy and damage effectiveness, which decreased as the saturation time increased.     

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.     

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 %.     

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.     

Supercritical CO2 Extraction Optimization of Onion Oil Using Response Surface Methodology

Response surface methodology was employed to optimize the conditions of supercritical CO₂ extraction of the oil from freeze‐dried onion powder. The effects of pressure, temperature and extraction time on the yield of oil were investigated. The maximum extraction yield of 4.69 ± 0.04 g/kg dry basis was achieved at a pressure of 20.6 MPa, a temperature of 40.6 °C, a time of 260 min, a CO₂ flow rate of 22 L h^–1, and an entrainer ratio of 0.1 mL absolute ethanol per gram dry basis. The chemical composition of the oil was analyzed by gas chromatography‐mass spectrometry. The most representative compounds of the essential oil were organosulfur‐containing compounds and, among these, the main constituents were methyl 5‐methylfuryl sulfide (18.30 %), methyl 3,4‐dimethyl‐2‐thienyl disulfide (11.75 %) and 1‐propenyl propyl disulfide (9.72 %).     

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.     

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 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 %.     

CO2 Adsorption Kinetics of K2CO3/Activated Carbon for Low‐Concentration CO2 Removal from Confined Spaces

K₂CO₃ supported on activated carbon (K₂CO₃/AC) is a promising means to remove low‐concentration CO₂ from confined spaces. In this removal process, physical adsorption plays an important role but it is difficult to quantify the amount of CO₂ adsorbed when both H₂O and CO₂ are present. The linear driving force mass transfer model is adopted to study the CO₂ adsorption kinetic characteristics of K₂CO₃/AC by analyzing the experimental data. The effect of K₂CO₃ and H₂O on the adsorption of CO₂ in K₂CO₃/AC was also evaluated. K₂CO₃ loaded on the support is found to increase the mass transfer resistance but decrease the activation energy required for the physical adsorption process. The presence of water vapor is disadvantageous to achieve high physical adsorption capacity since it enhances the chemical sorption in the competitive dynamic sorption process.     

固体碱K2CO3/Al2O3催化酯交换法合成乙二醇甲醚乙酸酯

以固体碱K2CO3/Al2O3为催化剂,催化乙酸乙酯和乙二醇甲醚酯交换合成了乙二醇甲醚乙酸酯。考察了反应物摩尔比,催化剂用量,反应时间,催化剂重复使用等因素对反应的影响,结果表明:当n(乙酸乙酯)∶n(乙二醇甲醚)=4∶1,K2CO3/Al2O3用量为总反应物质量的1.0%,反应4.5h时,乙二醇甲醚的转化率为98.8%,选择性为100%;催化剂重复使用5次后,乙二醇甲醚的转化率仅下降3.7%。     

发泡工艺对超临界CO2／PP微孔发泡泡孔形态的影响

研究了超临界CO2／PP微孔发泡过程中发泡温度和饱和压力对结晶性聚合物PP泡孔形态的影响。结果表明，温度对泡孔形态影响很大，温度升高，熔体黏度和表面张力降低，泡孔变大，泡孔密度减小。与发泡温度相比，CO2饱和压力对泡孔结构的影响较小。压力太低，CO2的溶解度小，泡孔壁太厚，泡孔分布不均匀。随着压力升高，CO2的溶解度增加，熔体黏度减小，所以泡孔直径和泡孔密度都增加，泡孔壁变薄。     

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.     

Sc-CO2辅助聚合物挤出中螺杆结构对熔体压力的影响

采用Polyflow软件对双螺杆挤出机内不同螺杆元件所形成流道中的熔体流动进行了模拟,分析了不同螺杆元件的建压能力。结合超临界二氧化碳(Sc-CO2)辅助挤出的螺杆组合原则,对不同螺杆元件组合的螺杆结构进行了挤出实验;并通过对熔体压力的模拟值与实际测量值的比较,分析了不同螺杆结构对熔体压力的影响;另外还针对不同材料的挤出加工确定了相应的螺杆结构。     

超临界CO_2中合成的聚丙烯腈的相对分子质量及其分布研究

用凝胶渗透色谱法测试了超临界CO_2下合成的聚丙烯腈的相对分子质量及其分布,并详细研究了各种反应条件如:单体浓度、引发剂浓度、时间及CO_2压力对聚丙烯腈的相对分子质量、相对分子质量分布及转化率的影响。     

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.     

Extrusion Foaming of Poly(styrene‐co‐acrylonitrile)/Clay Nanocomposites Using Supercritical CO2

Supercritical CO₂ has been used as a blowing agent to foam poly(styrene‐co‐acrylonitrile)‐based materials in a single screw extruder specially adapted to allow fluid injection. The cellular morphology depends on foaming temperature, more regular cells being obtained with decreasing extrusion temperature. In a second step, a natural and an organomodified nanoclay have been added for the purpose of imparting some flame resistance to the foamed material. The filler efficiency in reducing sample combustion rate appeared to be dependent on its delamination level inside the matrix and better results were obtained when the organomodified clay was first delaminated in the polymer in an efficient twin screw extruder using water assistance, prior to foaming in the single screw extruder.

     

SO42−/ZrO2 supported on γ‐Al2O3 as a catalyst for CO2 desorption from CO2‐loaded monoethanolamine solutions

In this work, the composite catalysts, SO₄²/ZrO₂/γ‐Al₂O₃ (SZA), with different ZrO₂ and γ‐Al₂O₃ mass ratios were prepared and used for the first time for the carbon dioxide (CO₂)‐loaded monoethanolamine (MEA) solvent regeneration process to reduce the heat duty. The regeneration characteristics with five catalysts (three SZA catalysts and two parent catalysts) of a 5 M MEA solution with an initial CO₂ loading of 0.5 mol CO₂/mol amine at 98°C were investigated in terms of CO₂ desorption performance and compared with those of a blank test. All the catalysts were characterized using X‐ray diffraction, Fourier transform infrared spectroscopy, N₂ adsorption–desorption experiment, ammonia temperature programmed desorption, and pyridine‐adsorption infrared spectroscopy. The results indicate that the SZA catalysts exhibited superior catalytic activity to the parent catalysts. A possible catalytic mechanism for the CO₂ desorption process over SZA catalyst was proposed. The results reveal that SZA1/1, which possesses the highest joint value of Brφnsted acid sites (BASs) and mesopore surface area (MSA), presented the highest catalytic performance, decreasing the heat duty by 36.9% as compared to the catalyst‐free run. The SZA1/1 catalyst shows the best catalytic performance as compared with the reported catalyst for this purpose. Moreover, the SZA catalyst has advantages of low cost, good cyclic stability, easy regeneration and has no effect on the CO₂ absorption performance of MEA. © 2018 American Institute of Chemical Engineers AIChE J, 64: 3988–4001, 2018     

Simultaneous Adsorption of SO2, NO,and CO2 by K2CO3‐Modified γ‐Alumina

The simultaneous adsorption of SO₂, NO, and CO₂ on K₂CO₃‐modified γ‐alumina under different operating conditions was studied in a fixed‐bed reactor. The experimental results showed that the influence of a temperature increase on the simultaneous adsorption of the three gases was complex and different from the effects seen when both chemical adsorption and competitive adsorption existed. An increase in O₂ concentration and small amounts of water could enhance the adsorption of SO₂ and NO while the adsorption of CO₂ was not influenced. The breakthrough curves of the simultaneous adsorption experiments suggested that the investigated adsorbent may be a good candidate for the simultaneous adsorption of SO₂, NO, and part of the CO₂ while the adsorption capacity for CO₂ still needs to be enhanced.     

超临界CO2对改善聚丙烯固相接枝过程的作用及影响因素研究进展

介绍了超临界CO2对聚丙烯固相接枝改性的协助作用,系统讨论了超临界CO2协助技术的优点、协助作用和渗透机理、溶胀过程中各因素对接枝反应的影响以及引发剂和单体的选择.超临界CO2协助固相接枝技术,后处理简单,PP降解程度轻,能够改善接枝过程的不均匀性,是很有发展前景的PP功能化改性方法.     

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).