超临界甲醇中前驱物对制备超细镍粉体的影响

本文以不同的镍基前驱物（氧化镍、乙酸镍、硝酸镍）在超临界甲醇条件下制备超细镍粉体,考察了体系温度、压力、反应时间以及前驱物种类对制备超细镍粉体的影响。通过SEM和XRD对制备产物的形貌和物相进行表征分析。结果表明,超临界甲醇的还原性随着温度和压力的升高而显著增强,在反应体系中,甲醇既起到溶剂作用又起到还原剂的作用。此外,通过考察前驱物种类对制备过程的影响可知,前驱物的种类对制备超细镍有显著的影响,乙酸镍在超临界甲醇250 ℃,9 MPa条件下即能够得到纯的超细镍,硝酸镍则需要更高的温度和压力（280 ℃,14.0 MPa）,而以氧化镍为前驱物时即使在300 ℃,20 MPa的条件下也只得到镍和氧化镍的混合物。     

Transpiring wall reactor in supercritical water oxidation

Reactor corrosion and plugging problems have hindered the commercialization of supercritical water oxidation (SCWO) for wastewater purification. The use of transpiring wall reactor (TWR) is an effective means to overcome the above two problems by forming a protective water film on the internal surface of the reactor to aviod contacting corrosive species and precipitated organic salts. This work mainly aims to objectively review experimental investigations and numerical simulation results concerning TWR. Subsequent investigations for parameters optimizations of TWR are also proposed in order to ultimately build effective regulation methods of obtaining excellent water film properties. All this information is very important in guiding the structure design and operation parameters optimization of TWR.     

Flow separation from a spherical particle in supercritical water

Flow separation from a spherical particle in supercritical water (SCW) is the basic flow structure in supercritical water fluidized bed (SCWFB). In order to study flow separation from a spherical particle in SCW in detail, a numerical model fully accounting for variations in thermo-physical properties has been developed in the pseudo-critical zone. Flow separation parameters (separation angle, length of wake vortex, width of wake vortex, and drag coefficient) for forced convection, assisting convection, and opposing convection have been obtained at intermediate Reynolds numbers. Results show that variable viscosity has a remarkable effect on flow separation, and the decreasing viscosity results in higher velocity gradient around the sphere particle surface and a larger wake vortex on the rear particle surface. A simple expression of Cd/Cdc=(μw/μf)^0.15$\text{Cd}/{\text{Cd}}_{\text{c}}={({\mu }_{\text{w}}/{\mu }_{\text{f}})}^{0.15}$ is achieved to predicate the drag coefficient of the SCW flow with μw/μf${\mu }_{\text{w}}/{\mu }_{\text{f}}$ between 0.7 and 1.0. Free convection inhibits the flow separation of the assisting convection, but enhances the flow separation of the opposing convection. Three flow separation zones (the rear-end separation zone, the transition zone, and the reversed flow zone) are observed for the opposing convection.     

Modified supercritical CO2 extraction of amine template from hexagonal mesoporous silica (HMS) materials: Effects of template identity and matrix Al/Si molar ratio

In this work, the primary amine template has been extracted from freshly synthesized hexagonal mesoporous silica (HMS) materials by means of modified supercritical carbon dioxide at 60–85 °C under 10.0–20.0 MPa. The influences of amine identity and matrix Al/Si ratio on the extraction efficiencies and structural properties of HMS thus obtained are investigated in detail. The results show that the extraction efficiency is strongly dependent on the pore size of the HMS materials produced by five different templates. For aluminium-incorporated samples, the extraction efficiency is observed to decrease with the Al/Si molar ratio since as the Al/Si molar ratio increases, more amine will get protonated and the matrix/template interactions become stronger, subsequently rendering the extraction more difficult and the efficiency decrease. The formic acid modifier has resulted in better extraction performance than methanol, yielding higher extraction efficiencies. The SFE-treated materials exhibit better structural properties like higher pore volume and specific surface area as compared to those prepared by conventional calcinations. Besides, results of pyridine adsorption and conversion of 2-propanol to propylene suggest that the SFE-treated HMS materials may have higher acidity than the directly calcined samples.     

Numerical simulation of particle formation in the rapid expansion of supercritical solution process

In this paper, we numerically study particle formation in the rapid expansion of supercritical solution (RESS) process in a two dimensional, axisymmetric geometry, for a benzoic acid + CO₂ system. The fluid is described by the classical Navier–Stokes equation, with the thermodynamic pressure being replaced by a generalized pressure tensor. Homogenous particle nucleation, transport, condensation and coagulation are described by a general dynamic equation, which is solved using the method of moments. The results show that the maximal nucleation rate and number density occurs near the nozzle exit, and particle precipitation inside the nozzle might not be ignored. Particles grow mainly across the shocks. Fluid in the shear layer of the jet shows a relatively low temperature, high nucleation rate, and carries particles with small sizes. On the plate, particles within the jet have smaller average size and higher geometric mean, while particles outside the jet shows a larger average size and a lower geometric mean. Increasing the preexpansion temperature will increase both the average particle size and standard deviation. The preexpansion pressure does not show a monotonic dependency with the average particle size. Increasing the distance between the plate and the nozzle exit might decrease the particle size. For all the cases in this paper, the average particle size on the plate is on the order of tens of nanometers.     

Surface hierarchical porosity in poly (ɛ-caprolactone) membranes with potential applications in tissue engineering prepared by foaming in supercritical carbon dioxide

This article describes the preparation of porous poly (ɛ-caprolactone), PCL, membranes by supercritical CO₂ (SCCO₂) foaming, displaying surface hierarchical macroporosity which could be tailored by careful control of the pressure, in the range of 150–250 bar, and depressurization processes in several steps, showing also pore interconnectivity between both membrane faces. The membranes exhibited two distinct types of surface macroporosity, the larger with diameter sizes of 300–500 μm were surrounded by and also composed of smaller pores of 15–50 μm (same size as inner pores). Membranes were prepared by solvent casting and submitted to different SCCO₂ foaming. Parameters such as membrane thickness, CO₂ flow, foaming time, pressure, temperature and the depressurization processes (rate and profiles), were varied to determine their influence on final porosity and to decipher which parameters were the most critical ones in terms of surface hierarchical pore organization. No remarkable changes in PCL crystallinity were found when membranes were processed under SCCO₂. Finally, biological evaluation of the porous membranes was achieved by seeding human skin fibroblasts on the prepared membranes. The results, in terms of cell adhesion, spreading, proliferation and metabolic activity indicate that these membranes could hold promise for the fabrication of meshes with controlled porosity for tissue engineering applications.     

Environmentally benign supercritical CO2 extraction of galanthamine from floricultural crop waste of Narcissus pseudonarcissus

The influence of diverse factors on the supercritical fluid extraction (SFE) with supercritical CO₂ (scCO₂) of galanthamine from bulbs of Narcissus pseudonarcissus cv. Carlton was investigated. The parameters that were studied were CO₂ density (temperature and pressure), flow rate and plant material particle size and pre-treatment. The highest yield (303 μg/g) was achieved by extracting 53–1000 μm particle-size powdered dried bulb material moistened with NH₄OH (25%, v/v) at 70 °C, 220 bar (690 kg/m³) for 3 h. Other N. pseudonarcissus alkaloids such as O-methyllycorenine and haemanthamine were also obtained. N. pseudonarcissus alkaloids as free bases are highly soluble in CO₂ at a high pH as opposed to the slightly soluble salt form in which they are generally found in plants. Therefore, plant material pre-treatment with a base is an essential step for galanthamine extraction. Scanning electron microscope (SEM) results also revealed that the desorption of N. pseudonarcissus alkaloids from the plant material rather than the solubility of the alkaloids in the scCO₂ plays a major role in this scCO₂ extraction. This extraction method has a good potential for industrial application.     

Extraction of oil and β-sitosterol from peach (Prunus persica) seeds using supercritical carbon dioxide

Oil was extracted from the peach (Prunus persica) seeds by supercritical carbon dioxide. Principal phytosterols (stigmasterol, campesterol and β-sitosterol) that have been known to have cholesterol lowering properties were investigated in the extracted oil. Based on gas chromatography–mass spectrometry (GC–MS) analysis, β-sitosterol was identified in the peach seed oil. The effects of temperature, pressure, flow rate of supercritical CO₂, mean particle size of the seeds and extraction time on the amounts of extracted oil and β-sitosterol were investigated. Supercritical fluid extractions were performed in a range of 35–55 °C, 160–240 bar, 4–8 ml CO₂/min, 0.3–1.7 mm and 1–4 h for mentioned parameters. The results indicated that the amounts of oil and β-sitosterol extracted from the peach seeds were optimal with values of 35.3 g/100 g seed and 1220 mg/kg seed respectively at 40 °C, 200 bar, 7 ml/min, 0.3 mm and 3 h.     

Removal of contaminants from polluted drilling mud using supercritical carbon dioxide extraction

Liquid drilling fluid is often called drilling mud is heavy, viscous fluid mixtures use to carry rock cuttings to the surface and lubricate and cool the drill bit. During carrying cuttings they contaminated which not only reduce their functionality but also make them a hazardous and dangerous wastes which cannot be discharged anywhere without treatment. Due to this fact, in the present study, supercritical extraction process was used to remove contaminants from the drilling mud. Regarding this, effect of different parameters including extraction temperature (313–338 K) and pressure (100–200 bar), flow rate of CO₂ (0.05–0.36 cm³/s) and static time (20–130 min) on the removal of contaminations from drilling mud was examined using the design of experiment of changing one factor at a time. The obtained results revealed that the optimum operational conditions that lead to the highest removal degree of contaminations are temperature and pressure of 333 K and 180 bar, respectively, flow rate of lower than 0.1 cm³/s and the static time of 110 min. In addition, to examine the effect of the supercritical extraction on the crystalline structure modification and removal contaminations X-ray diffraction (XRD) and scanning electron microscopy (SEM) analyses were performed which confirmed the successful removal of contaminations from the drilling mud without significant crystalline modification.     

Response surface optimization of Smyrnium cordifolium Boiss (SCB) oil extraction via supercritical carbon dioxide

In this study, the essential oil of aerial parts of a species of a plant called Smyrnium cordifolium Boiss (SCB) was extracted by supercritical CO₂. The essence was analyzed by the method of GC/MS. Design of experiments was carried out with response surface methodology by Minitab 16 software to optimize four operating variables of supercritical carbon dioxide (SC-CO₂) extraction (pressure, temperature, CO₂ flow rate and extraction dynamic time). This is the first report announcing optimization of the operation of supercritical extraction of SCB in laboratorial conditions. Optimizing process was done to achieve maximum yield extraction. Independent variables were dynamic time (t_d), pressure (P), temperature (T) and flow rate of SC-CO₂ (Q) in the range of 30–150 min, 10–30 MPa, 40–60 °C and 0.5–1.7 ml/min, respectively. The experimental optimal recovery of essential oil (0.8431, w/w%) was obtained at 13.43 MPa, 40 °C, 150 min (dynamic) and 1.7 ml/min (CO₂ flow rate).