Characterization and supercritical carbon dioxide extraction of walnut oil

Walnut (Juglans regia L.) oil was extracted with compressed carbon dioxide (CO₂) in the temperature range of 308 to 321 K and in the pressure range of 18 to 23.4 MPa. The influence of particle size was also studied at a superficial velocity of 0.068 cm/s, within a tubular extractor of 0.2 L capacity (cross-sectional area of 16.4 cm²). FFA, sterol, TAG, and tocopherol compositions were not different from those of oil obtained with n-hexane. The main FA was linoleic acid (56.5%), followed by oleic acid (21.2%) and linolenic acid (13.2%). The main TAG was LLL (linoleic, linoleic, linoleic) (24.4%), followed by OLL (oleic, linoleic, linoleic) (19.6%) and LLLn (linoleic, linoleic, linolenic) (18.4%). The main component of sterols was β-sitosterol (85.16%), followed by campesterol (5.06%). The amount of cholesterol was low (0.31 and 0.16% for oils extracted by n-hexane and supercritical fluid extraction, respectively. The CO₂-extracted oil presented a larger amount of tocopherols (405.7 μg/g oil) when compared with 303.2 μg/g oil obtained with n-hexane. Oxidative stability determined by PV and the Rancimat method revealed that walnut oil was readily oxidized. Oil extracted by supercritical CO₂ was clearer than that extracted by n-hexane, showing some refining. A central composite, nonfactorial design was used to optimize the extraction conditions using the software Statistica, Version 5. The best results were found at 22 MPa, 308 K, and particle diameter (Dp) −0.1 mm.     

Effects of supercritical CO2 extraction parameters on soybean oil yield

A series of operational parameters of supercritical fluid extraction of soybean oil (pressure: 300–500 bar, temperature: 40–60 °C, CO₂ mass flow rate: 0.194–0.436 kg/h and characteristic particle size: 0.238–1.059 mm) were investigated in a laboratory scale apparatus. The results show that the extraction yields were significantly affected by applied operational extraction parameters. The increase in pressure, temperature and solvent flow rate improved the extraction yield. The extraction yield increased as the particle size decreased depending on decreasing intra-particle diffusion resistance. To describe the extraction process Sovova's model was used and very good agreement with the experimental results was obtained. Based on the experimental data the internal and external mass transfer coefficients were estimated. To explore the influence of the extractor size on this process, soybean samples were extracted using different extraction basket volumes (0.2 L and 5 L) and related model parameters were examined. The mass transfer coefficient in the fluid phase increased with the increase in extractor size, while the mass transfer coefficient in the solid phase was independent of the extractor size.     

Response Surface Analysis and Modeling of Flaxseed Oil Yield in Supercritical Carbon Dioxide

Supercritical fluid extraction of flaxseed oil with carbon dioxide was performed. Effects of particle size, pressure, temperature and the flow rate of supercritical carbon dioxide (SC-CO₂) were investigated. Response surface methodology was used to determine the effects of pressure (30–50 MPa), temperature (50–70 °C) and SC-CO₂ flow rate (2–4 g/min) on flaxseed oil yield in SC-CO₂. The oil yield was represented by a second order response surface equation (R ² = 0.993) using the Box-Behnken design of experiments. The oil yield increased significantly with increasing pressure (p < 0.01), temperature (p < 0.05) and SC-CO₂ flow rate (p < 0.01). The maximum oil yield from the response surface equation was predicted as 0.267 g/g flaxseed for 15 min extraction of 5 g flaxseed particles (particle diameter <0.850 mm) at 50 MPa pressure and 70 °C temperature, with 4 g/min solvent flow rate. Total extraction time at these conditions was predicted as 22 min.     

Extraction of sunflower oil with supercritical CO2: Experiments and modeling

Extraction of sunflower oil from sunflower seeds (Heliantus annuus L.) using supercritical CO₂ was studied. The shrinking core model was applied to the modeling of the packed-bed extraction process. The experimental data were obtained for extraction conducted at the pressures of 20, 30, 40, 50 and 60 MPa; the temperatures of 313, 333 and 353 K, the CO₂ flow rates of 1–4, and 6 cm³ CO₂ min⁻¹; the mean particle diameters of 0.23, 0.55, 1.09, 2.18 mm. The supercritical CO₂ extraction process was modeled by a quasi steady state model as a function of extraction time, pressure, temperature, CO₂ flow rate, and particle diameter. The supercritical CO₂ extraction process. The intraparticle diffusion coefficient (effective diffusivity) D_e was used as adjustable parameter. The model using the best fit of D_e was correlated the data satisfactorily.     

Supercritical fluid extraction of daphne (Laurus nobilis L.) seed oil

Laurus nobilis L., commonly known as daphne tree, is an evergreen that belongs to the Lauraceae family. Daphne trees produce grape-sized shiny purplish berries having three parts: flesh, skin, and an inner kernel (single seed). This study examines supercritical CO₂ (SC-CO₂) extraction of oil from daphne seeds. The oil yield of ground seeds varied from 14 to 28% depending on the method and particle size used for oil recovery. Yields were similar for both petroleum ether and SC-CO₂ extraction. The extraction yield decreased significantly with increasing particle size. The amount of extract collected increased exponentially with increasing SC-CO₂ pressure. The highest extraction yield was obtained at the highest temperature studied, 75°C. More than 45% of the oil was lauric acid. SC-CO₂ is a viable technique to obtain high-purity L. nobilis L. seed oil, which is a potential ingredient for the cosmetic industry.     

Synthesis and characterization of functional gradient copolymers of glycidyl methacrylate and butyl acrylate

Epoxy-functional spontaneous gradient copolymers of glycidyl methacrylate (G) and n-butyl acrylate (B) were synthesized via atom transfer radical polymerization (ATRP). The copolymerization reactions were carried out in toluene solution at 70 °C, using methyl 2-bromopropionate (MBrP) as initiator and copper chloride with N,N,N′,N′′,N′′-pentamethyldiethylenetriamine (PMDETA) as the catalyst system. The kinetic behaviour of the statistical copolymerizations was studied in a wide composition interval with molar fractions of G ranging from 0.10 to 0.75. The synthesized copolymers were characterized by size exclusion chromatography (SEC) and nuclear magnetic resonance (NMR) spectroscopy. ¹H NMR was employed to determine the copolymer composition, demonstrating the gradient character of the copolymers along the main chain in the whole monomer conversion interval. Apart from this, the sequence distribution and stereoregularity were analyzed. These microstructural experimental data agreed well with those calculated from Mayo-Lewis terminal model (MLTM) and a Bernoullian statistic with an isotacticity parameter of σ_G = 0.28 and a coisotacticity parameter of σ = 0.30.     

Optimization of Supercritical Carbon Dioxide Extraction of Gardenia Fruit Oil and the Analysis of Functional Components

Supercritical carbon dioxide (SC-CO₂) extraction of whole fruit oil from Gardenia jasminoides Ellis was performed. The effect of extraction pressure, temperature and CO₂ flow rate on the oil yield was investigated by response surface methodology (RSM). The results showed that experimental data had a good fit to the proposed model (R ² = 0.938). Extraction pressure, CO₂ flow rate, the quadratics of pressure, and the interaction between pressure and flow rate showed significant effects on the oil yield (p < 0.05). The optimum parameters that maximized the yield of gardenia fruit oil (GFO) were: extraction pressure of 36.8 MPa, temperature of 65 °C, and CO₂ flow rate of 15 kg/h. The main fatty acid of GFO was linoleic acid (about 44%), followed by palmitic acid (about 26.4%) and oleic acid (about 24.6%). α-Tocopherol was dominant in the total tocopherols of GFO, and showed the main antioxidant activity. The fatty acid composition and tocopherols content of GFO were not remarkably affected by the extraction by SC-CO₂ and n-hexane.     

Direct preparation of battery-grade lithium carbonate via a nucleation–crystallization isolating process intensified by a micro-liquid film reactor

With the lithium-ion battery industry booming, the demand for battery-grade lithium carbonate is sharply increasing. However, it is difficult to simultaneously meet the requirements for the particle size and the purity of battery-grade lithium carbonate. Herein, the nucleation–crystallization isolating process (NCIP) is applied to prepare battery-grade lithium carbonate without any post-treatment procedure. The nucleation process is intensified by a micro-liquid film reactor (MLFR), where the feedstock solution is subject to intensive shear force and centrifugal force. The feedstock solutions are mixed rapidly and a large number of nuclei form instantly in the MLFR. After nucleation, the crystallization process is achieved in another reactor. A few new nuclei form in the crystallization process. The nucleation intensification in the MLFR is verified by computational fluid dynamics (CFD) simulations and experimental results. The particle size distribution is narrower and the impurity residue in the products is far lower than that prepared by a traditional precipitation method. The effects of nucleation and crystallization on the particle size distribution and purity were investigated. In the optimized operation parameters, the particle size distribution of the Li₂CO₃ product is D₁₀ = 2.856 μm, D₅₀ = 5.976 μm, and D₉₀ = 11.197 μm, and the purity is 99.73%, both of which meet the requirements of battery-grade Li₂CO₃. Moreover, the lithium recovery rate is increased to 88.21% compared to that prepared by a traditional precipitation method (79.0%). This work provides an alternative way for the preparation of high-purity chemicals by process intensification.     

Supercritical fluid extraction of oil from millet bran

Proso millet bran [Panicum miliaceum (L.)], variety Dakota White, was extracted with supercritical carbon dioxide (SC-CO₂) to yield crude oil. The effects of operating parameters (pressure, temperature, and specific solvent flow) and of features of the raw material (moisture content and particle size) on oil extraction were investigated. Complete de-oiling of ground millet bran pellets was achieved under 300 bar at 40°C with a specific solvent flow of 2–10 h⁻¹ within 200 to 500 min. Solvent requirements were 20–30 kg CO₂/kg raw material. Composition of crude SC-CO₂ oil extracted under optimal conditions, i.e., fatty acid profile, amount of unsaponifiables, tocopherols, free fatty acids, sterols, sterol esters, waxes, hydrocarbons, and phospholipids, was compared to that of crude oil obtained by petroleum ether extraction. These two oils were similar in terms of fatty acid profile and amount of free fatty acids, unsaponifiables, peroxides, and tocopherols. They differed in respect to phospholipids (present in petroleum etherextracted oil and absent in SC-CO₂ extracted oil), metals, and waxes (lower levels in SC-CO₂ extracted oil). The effects of extraction procedures on oxidative stability of crude SC-CO₂ oil were studied. Ensuring that all pieces of the extractor in contact with the oil were in stainless steel; cleaning the separator, i.e., washing with KOH, rinsing, purging with N₂ and CO₂, and heating; performing a couple of extractions before the main extraction; and achieving the extraction without interruption all positively influenced the oxidative stability of the oil. Conversely, increasing CO₂ purity above 99.5% had no effect. Oxidative stability of the SC-CO₂ oil extracted under these conditions was only slightly lower than that of the oil extracted with petroleum ether.     

Supercritical CO2 extraction of essential oil from yarrow

Essential oil was extracted from yarrow flowers (Achillea millefolium) with supercritical CO₂ at pressure of 10 MPa and temperatures of 40–60 °C, and its composition and yield were compared with those of hydrodistillate. The yield of total extract, measured in dependence on extraction time, was affected by extraction temperature but not by particle size of ground flowers. CO₂-extraction of cuticular waxes was lowest at 60 °C. Major essential oil components were camphor (26.4% in extract, 38.4% in distillate), 1,8-cineole (9.6% in extract, 16.2% in distillate), bornyl acetate (16.7% in extract, 4.3% in distillate), γ-terpinene (9.0% in extract, 9.4% in distillate), and terpinolene (7.6% in extract, 3.9% in distillate). Compared to hydrodistillation, the yield of monoterpenes was lower due to their incomplete separation from gaseous CO₂ in trap but the yield of less volatile components like monoterpene acetates and sesquiterpenes was higher. Hydrolysis of γ-terpinene and terpinolene, occuring in hydrodistillation, was suppressed in supercritical extraction, particularly at extraction temperature of 40 °C.     

Optimisation of SFE method on-line coupled to FT-IR spectroscopy for the real-time monitoring of the extraction of tagitinin C in T. diversifolia

The monitoring in real time of dynamic extractions of tagitinin C from Tithonia diversifolia leaves was carried out with a home made high-pressure fiber optic cell which coupled a supercritical fluid extractor with carbon dioxide as the extraction medium and a FT-IR spectrometer equipped with a mercury cadmium telluride detector (MCT). The shape of extraction curves obtained during the monitoring was used to decide when to stop the supercritical fluid extraction (SFE).No significant density dependence of the molar absorption coefficient or wavenumber of the CO stretching vibration (ν_CO) of tagitinin C at 1668 cm⁻¹ was noticed.The physical characteristics of SCCO₂ governing the extraction yield of the active component from leaves were optimized by means of a central composite design (CCD). The studied variables were temperature (40, 60 and 80 °C) and pressure (8.0, 14.0 and 20.0 MPa) of the supercritical fluid.The composition profile of T. diversifolia extracts obtained by SFE was investigated in the range from 3400 to 2600 cm⁻¹ according to the pressure and temperature conditions of SCCO₂. The qualitative approach of the extracts composition was accomplished through the CH stretching vibrations (ν_CH) of components.     

Microencapsulation of a Low-trans Fat in Trehalose as Affected by Emulsifier Type

A low-trans fat blend formulated with high linoleic sunflower seed oil (SFO) and a high melting fraction (HMF) of milk fat was encapsulated by freeze-drying emulsions. The selected emulsifiers were a mixed of the palmitic sucrose esters (SE) P-170 and P-1670, sodium caseinate (NaCas) or a blend of SE and NaCas. The ability to retain the core material with time was studied by storing the powders at different water activities (a _w). Efficiency of encapsulation was strongly dependent on emulsifier type. NaCas formulation was more efficient retaining core material during storage. The formulation with a protein and a small surfactant had the lowest performance. The stabilizer also influenced droplet size distribution and matrix crystallinity. For NaCas-stabilized powder volume weighted mean diameter (D _4,3) remained small for up to 2 months of storage (0.56 ± 0.5 μm) and then grew notably in agreement with matrix collapse. There were no significant differences in D _4,3 with water content. For NaCas/SE-stabilized powder, however, D _4,3 was high at the beginning (100 ± 0.5 μm) and then decreased most likely due to particle break-up. Although particle size distribution showed the same behavior for all a _w, retention was strongly dependent on water content. Retention with time was determined by the counteracting effects of these factors.     

Synthesis of a biocompatible polymer using siloxane-based surfactants in supercritical carbon dioxide

Poly(N-vinyl-2-pyrrolidone) (PVP) particles were prepared by dispersion polymerization in the presence of 2,2′-azobisisobutyronitrile as the initiator and siloxane-based surfactant in supercritical carbon dioxide (scCO₂). The dispersants used in this study were non-ionic, non-reactive and commercially produced siloxane-based surfactants (Monasil PCA and KF-6017). We investigated the effect of kinds and concentrations of the surfactants, in addition to the reaction temperature and the concentration of the monomer on the particle size and morphology. PVP microspheres were prepared in 0.23–0.74 μm size range with Monasil PCA and 0.71–1.98 μm size range with KF-6017, respectively. The resulting polymer particle of >90% yield was obtained. Particle size slightly increased with the amount of monomer in polymerization with Monasil PCA. In the case of KF-6017 as the surfactant, there was not an obvious variation in particle size with increasing monomer. Particle size of PVP decreased as surfactant concentration increased from 5.0 to 15.0 wt.% basis on concentration of monomer. The narrow particle size distribution (D_n = 0.23 μm and PSD = 1.06) was presented at the high concentration of Monasil PCA (15 wt.% on monomer concentration). As indicated by the reaction temperature and the addition of organic solvent, which affected solubility of monomer, polymer and surfactant in scCO₂, particle size and particle size distribution of PVP varied. PVP particles with Monasil PCA strongly aggregated at 75 °C in contrast to KF-6017 which showed discrete particles at 65 and 70 °C, but particle size distribution was broad. Particle size was slightly reduced with a little amount of hexane, with an inverse relationship of adding hexane reduced the particle size. The amount of the relative residual surfactants on surface of the polymer after extracting with supercritical fluid process (SFE) was measured by using SEM/EDS and EPMA analysis to map out the distribution of silicon element qualitatively. The original polymer particle before the extraction using CO₂ had the high level of silicon element, but the average level of silicon element became low after CO₂ extraction.     

Modeling solvent extraction of vegetable oil in a packed bed

A one-dimensional model was developed for solvent extraction of oil from a packed bed of oil-bearing vegetable materials. The equilibrium relationship between the residual oil content of marc and oil concentration of stagnant miscella in pores of the bed material was generated through experiments with rice bran and hexane. The nondimensional parameters recognized from the model describing extraction were initial Reynolds number (Re_i), initial Schmidt number (Sc_i), bed void fraction (ε_b), particle porosity (ε_p), ratio of bed diameter to particle diameter (D_t/d_p), ratio of bed depth to bed diameter (L/D_t), ratio of particle surface area to bed cross-section (a_pAL/A=a_pL), and recycle of solvent and equilibrium distribution coefficient (EDC). For reducing the time required to extract to the same residual oil content of marc, higher values of Re_i, ε_b, and a_pL were beneficial, whereas higher values of Sc_i, ε_p, D_t/d_p, L/D_t, and EDC were detrimental.     

Supercritical fluid extraction of peach (Prunus persica) almond oil: Kinetics, mathematical modeling and scale-up

Peach almonds contain oil with important therapeutic and nutritional properties due to the presence of unsaturated fatty acids, high content of oleic acid and other substances. In this study, peach almond oil was obtained by means of supercritical fluid extraction (SFE), with yield up to 24% w/w. The objective of this work was to evaluate the effect of the operation variables in the process kinetics in order to define scale-up parameters, like extractor volume and solvent flow rate. In spite of the importance for industrial application, the definition of a scale-up methodology is difficult. Therefore, the main goal of this work was to study the kinetic aspects of the SFE by modeling the extraction curves and, with these results, suggests a scale-up methodology. The parameters evaluated were extraction pressure, CO₂ flow rate and particle size. The mass transfer models used to describe the extraction curves were logistic model, diffusion model and Sovová model. Four scale-up methodologies, based on mass transfer mechanisms, were applied. The results indicate the best curve fitting by means of Sovová’s model, while the best scale-up criterion was maintaining the ratio Q_CO2/M (solvent flow rate/raw material mass) constant. This study also indicated the convection as the dominant mass transfer mechanism, while the diffusion was the limiting factor. Moreover, the SFE of peach almond oil could be predicted by the scale-up method used.     

Optimization of the Extraction of <Emphasis Type="Italic">Alpinia oxyphylla</Emphasis> Essence Oil in Supercritical Carbon Dioxide

The essence oil of the Alpinia oxyphylla seed has been used as a vasodilatatory and analgesic agent in pharmacology. The extraction of the essence oil in supercritical carbon dioxide (SC-CO₂) from Alpinia oxyphylla seeds was investigated. Small particles were obtained after breaking open, sieving, and drying from the Alpinia oxyphylla seeds. The small particles were placed in a 5-L extraction tank in a temperature-controlled system. The CO₂ flow rate of the system was set at 1 L/min in this study. Response surface methodology with a three-factor and three-level Box-Behnken experimental design was used to evaluate the effects of the reaction parameters such as extraction time (1, 2, 3 h), temperature (45, 55, 65 °C), and pressure (20, 30, 40 MPa), on the extraction yield of the essence oil from Alpinia oxyphylla seeds. The results indicate that the extraction pressure was the most important parameter affecting the yield of the essence oil. A model for the estimation of the yield was developed. Based on the analysis of ridge max, the optimal extraction conditions were established as an extraction time of 2.8 h, a temperature of 67.5 °C, and a pressure of 28.5 MPa, with an expected yield of 2.78%. Extraction of Alpinia oxyphylla essence oil in SC-CO₂ under these optimal conditions was conducted, and a yield of 2.77 ± 0.19% was obtained.     

Supercritical Carbon Dioxide Extraction of <Emphasis Type="Italic">Microula sikkimensis</Emphasis> Seed Oil

The seed oil of Microula sikkimensis had been intensively studied due to its pharmacological actions. In the present study, seed oil of Microula sikkimensis was extracted using supercritical fluid extraction (SFE). Determinations of the extracts composition were performed by gas chromatography (GC). An orthogonal array design (OAD), OA₉ (3⁴), was employed for optimization of the supercritical fluid extraction of the compound with regard to the various parameters. Four factors, namely pressure (21.0–27.0 MPa), the dynamic extraction time, temperature, and CO₂ flow rate of the supercritical fluid, were studied and optimized by a three-level OAD. The effects of the parameters on the yield of seed oil were studied using analysis of variance (ANOVA). The results revealed that the pressure had a significant effect on the yield of seed oil (p < 0.05), while the other three factors, i.e., CO₂ flow rate, dynamic extraction time and temperature, were not identified as significant factors under the selected conditions based on ANOVA. The results show that the best values for the extraction condition of seed oil was pressure 24.0 MPa, extraction time 3 h, temperature 45 °C and a CO₂ flow rate 20 L/h in the 20-L vessel.     

A ferromagnetic linear trinuclear Ni(II)-Schiff base complex supported by phenoxo and cinnamato bridges

A new linear trinuclear nickel(II) complex, [Ni₃(salme)₂(OCn)₄] (Hsalme = 2-[(3-methylamino-propylimino)-methyl]-phenol, OCn = cinnamate), showing weak ferromagnetic coupling (J = 1.8(1) cm⁻¹) through phenoxo and a novel tridentate bridging mode (1κ²OO′:2κO′) of the cinnamate ligand has been synthesized and structurally characterized by X-ray crystallography.     

Preparation of ferric oxide powders by ultrasonic-assisted impinging stream reaction

In this paper, Fe₃O₄ powder was prepared by the chemical precipitation method using impinging stream technology. The influences of feed flow rate, L/D, reactant concentration, ratio of iron ion concentration, reaction temperature, and impact time on the size and distribution of particles were investigated by the orthogonal experiment method. The microstructure and morphology of Fe₃O₄ powders were characterized by scanning electron microscopy, X-ray diffractometer, and granulometer. The results showed that when ratio of iron ion concentration c(Fe²⁺):c(Fe³⁺) = 0.75, reactant concentration c(Fe³⁺) = 0.4 mol · L⁻¹, feed flow rate Q = 800 L · h⁻¹, L/D = 3, reaction temperature T = 20°C, impact time t = 50 min, the prepared Fe₃O₄ had an average particle size of 1.815 μm and the most uniform distribution. The influence of ultrasonic enhancement on the mixing process and powder preparation in an impinging stream reactor was investigated. The size and distribution of the powders were significantly affected by ultrasonic enhancement. With the increase in ultrasonic power, the particle size of the powders decreased and the distribution became narrower. The particle size was reduced by 68.78%, and the particle distribution range was narrowed by 84.34% under ultrasound enhancement. This study promised the effective utilization of ultrasonic cavitation in the optimization of experimental equipment and the preparation of ultrafine powder, which provides a basis for process optimization of powder preparation.     

超临界CO2萃取丁香油的数值模拟

为了预测超临界CO₂萃取挥发油动态过程,根据挥发油在超临界CO₂与物料之间的质量传递平衡,采用集总参数法建立超临界CO₂萃取丁香油过程的数学模型。结合不同温度、压力、粒径和CO₂流速条件下的实验结果,对方程进行了合理的简化,并利用实验数据拟合出模型中CO₂密度、粒径和流速的系数。验证结果表明模型的计算值和实验值的平均相对误差在6. 88%～57. 78%之间,建立的数值模型能较好地描述实际的超临界CO₂萃取丁香油行为。