Supercritical CO2 extraction of Helichrysum italicum: Influence of CO2 density and moisture content of plant material

Kinetics and selectivity of supercritical carbon dioxide (SC CO₂) extraction of Helichrysum italicum flowers were analyzed at pressures in the range of 10-20 MPa and temperatures of 40 °C and 60 °C (density of SC CO₂ from 290 to 841 kg/m³) and also at 10 MPa and 40 °C using flowers with different moisture contents (10.5% and 28.4%). Increased moisture content of H. italicum flowers resulted in enchased solubility of solute enabling decrease of SC CO₂ consumption necessary for achieving desired extraction yield. The most abundant compounds in the supercritical extracts are sesquiterpenes and waxes while monoterpenes and sesquiterpenes are the main constituents of essential oil obtained by hydrodistillation. The optimal set of working parameters with respect to extraction yield, SC CO₂ consumption and chemical composition of extract were defined related to moisture content of raw material and SC CO₂ density.     

Supercritical CO2 extraction of lipids and astaxanthin from Brazilian redspotted shrimp waste (Farfantepenaeus paulensis)

Brazilian redspotted shrimp (Farfantepenaeus paulensis) waste is an important source of carotenoids such as astaxanthin and lipids with a high ω−3 fatty acids content, mainly docosahexaenoic acid (DHA) and eicosapentaenoic acid (EPA). In order to establish an efficient and environmental friendly recovery process, the lipids and astaxanthin were extracted from the freeze-dried redspotted shrimp waste (including head, tail and shell) using supercritical carbon dioxide. The effects of the extraction conditions of pressure (200-400 bar) and temperature (40-60 °C) on the global yield (X₀), astaxanthin extraction yield and astaxanthin concentration in the extract were evaluated. It was found that the pressure and temperature showed a very low significant effect on the lipid extraction yield using supercritical CO₂. In comparison with lipid extraction by solvents, maximum efficiency of supercritical fluid extraction achieved 64% of hexane extraction yield. On the other hand, temperature and pressure had significant effects on astaxanthin extraction yield. Thegreatest amount of extract was obtained at 43 °C and 370 bar, with 39% of recovery.     

Extraction of phenolic compounds from pitanga (Eugenia uniflora L.) leaves by sequential extraction in fixed bed extractor using supercritical CO2, ethanol and water as solvents

With the goal of maximizing the extraction yield of phenolic compounds from pitanga leaves (Eugenia uniflora L.), a sequential extraction in fixed bed was carried out in three steps at 60 °C and 400 bar, using supercritical CO₂ (non-polar) as solvent in a first step, followed by ethanol (polarity: 5.2) and water (polarity: 9.0) in a second and third steps, respectively. All extracts were evaluated for global extraction yield, concentration and yield of both polyphenols and total flavonoids and antioxidant activity by DPPH method (in terms of EC₅₀). The nature of the solvent significantly influenced the process, since the extraction yield increased with solvent polarity. The aqueous extracts presented higher global extraction yield (22%), followed by ethanolic (16%) and supercritical extracts (5%). The study pointed out that the sequential extraction process is the most effective in terms of global extraction yield and yield of polyphenols and total flavonoids, because it produced the more concentrated extracts on phenolic compounds, since the supercritical ethanolic extract presented the highest phenolics content (240.5 mg GAE/g extract) and antioxidant capacity (EC₅₀ = 9.15 μg/mL). The most volatile fraction from the supercritical extract, which is similar to the essential oils obtained by steam distillation or hydrodistillation, presented as major compounds the germacrenos D and B + bicyclogermacrene (40.75%), selina-1,3,7(11)-trien-8-one + selina-1,3,7(11)-trien-8-one epoxide (27.7%) and trans-caryophyllene (14.18%).     

Propolis extracts obtained by low pressure methods and supercritical fluid extraction

Propolis is a natural product used for centuries by human kind, due to several evidenced biological activities: antioxidant, antimicrobial, anti-inflammatory, antitumor and anti-HIV. Extracts from propolis, used in food, pharmaceutical and cosmetic industries, present quality and composition related to the extraction method applied. Natural compounds with biological activity can be obtained by conventional techniques, such as Soxhlet and Maceration, or by alternative methods such as supercritical fluid extraction (SFE). Thus, the aim of this work was to compare propolis extraction yields obtained by different procedures, for instance, SFE in one stage, with CO₂ and CO₂ plus co-solvent, and SFE in two stages, as well as Soxhlet and Maceration as low pressure extraction methods using ethanol, ethyl acetate, chloroform, n-hexane, water and mixtures of water/ethanol. The operational conditions for SFE in one stage with pure CO₂ were: 30, 40 and 50 °C and from 100 to 250 bar. The SFE with co-solvent was performed at 150 bar and 40 °C and ethanol concentrations of 2, 5 and 7% (w/w). The highest yield was obtained by chloroform Soxhlet extraction (73 ± 2%, w/w) whereas for SFE the maximum yield was 24.8 ± 0.9%, using 5% ethanol as co-solvent. For SFE in two stages, 100 and 150 bar were used in the first stage while 250 and 300 bar were applied in the second stage, at 40 °C. The yields were 8.4 ± 0.7 (150 bar) and 5.1 ± 0.7 (250 bar), for stages 1 and 2, respectively. The chemical composition of the propolis material was determined by HPLC analysis. The experimental data were correlated using four models based on differential mass balance equations: (1) the Sovová’s model; (2) the logistic model (3) the diffusion model and (4) the simple single plate model (SSP). The logistic model provided the best adjustment for propolis SFE curves.     

The enantioselective hydrolysis of racemic naproxen methyl ester in supercritical CO2 using Candida rugosa lipase

The enantioselective hydrolysis of racemic naproxen methyl ester by Candida rugosa lipase (CRL) was studied in aqueous buffer solution/isooctane reaction system in the presence of supercritical CO₂. The effects pressure (75–160 bar), temperature (32–42 °C) and reaction time (0.5–12 h) on the enantiomeric excesses of the product (ee_p) and the substrate (ee_s), enantiomeric ratio (E), conversion (x) and enzyme activity were investigated in a batch reactor system. The highest enantiomeric ratio achieved at 120 bar of pressure, 37 °C of temperature and 2 h of reaction time was E = 193 with x = 41.3%, ee_p = 97.9% and ee_s = 68.8%. CRL remained active at least for 12 h at 37 °C and 120 bar in supercritical CO₂ medium. Furthermore, enantiomeric ratio increased with increasing reaction time and reached the value of E = 236 with ee_p = 98.2%, ee_s = 70.0% and x = 41.6% after 12 h of hydrolysis.     

Liquid CO2 extraction of flowers and fractionation of floral concrete of Michelia champaca Linn

Extraction of the fresh flowers of Michelia champaca L. with liquid CO₂ provided a floral extract in 1.0 ± 0.04 wt% yields. The extract so obtained contains far less waxes and is organoleptically very superior. Similarly extraction with pentane gave the so-called ‘Concrete’ in 1.58 ± 0.06 wt%. While the concrete contains co-extracted floral waxes that make it unsuitable for blending with other perfumes, direct extraction with CO₂ is an expensive process mainly due to low bulk density of flowers and their availability during short flowering season. On the other hand, fractionation of the concrete with liquid CO₂ to separate the waxy components has provided solvent and almost wax free fractions. The duration of extractive fractionation has been optimized for selective extraction with liquid CO₂ at 62 bar. These liquid CO₂ fractions of concrete and liquid CO₂ extract of flowers were analyzed by GC and GC/MS and their composition compared with that of concrete and partially de-waxed absolute obtained in the conventional way. The major fragrance compounds enriched in the direct liquid CO₂ extract were methyl benzoate (11.5 ± 0.8%), phenyl ethyl alcohol (5.0 ± 0.6%), phenyl acetonitrile (10.4 ± 1.1%), indole (1.2 ± 0.3%), methyl anthranilate (1.3 ± 0.5%), E-β-ionone (1.5 ± 0.4%), and Z-methyl jasmonoate (1.0 ± 0.3%). The liquid CO₂ fractionation of concrete is a practical process and the first fraction is comparable with direct liquid CO₂ flower extract in terms of composition of the major compounds.     

Antiradical Efficiency of Essential Oils from Plant Seeds Obtained by Supercritical CO2, Soxhlet Extraction,and Hydrodistillation

The effect of supercritical CO₂ (SCCO₂) extraction conditions (pressure and temperature) on the system performance as well as the antiradical efficiencies of the essential oils from Japanese pepper (Xanthoxylum piperitum DC.), cardamom (Elettaria cardamomum Maton), and fennel (Foeniculum vulgare) seeds were investigated. A control study with the conventional Soxhlet extraction and hydrodistillation was also conducted to compare the performance of those processes. Antiradical efficiencies were investigated by utilizing 1,1-diphenyl-2-picrylhydrazyl (DPPH) assay with a UV-vis spectrophotometer. Higher pressure and temperature had positive effects on the supercritical process performance due to higher CO₂ density and substrate solubility in SCCO₂. Antiradical efficiencies of cardamom and pepper were almost the same, being significantly higher than that of fennel seeds. However, this effect decreased dramatically for all the spices when the extraction method was changed to Soxhlet extraction and hydrodistillation. SCCO₂ extraction was found to yield more quality and effective essential oils than Soxhlet extraction and hydrodistillation.     

Simultaneous desorption–crystallization of CO2–CaCO3 in multi-stage flash (MSF) distillers

In this work, the desorption–crystallization of CO₂–CaCO₃ in MSF distillers was simulated by coupling mass transfer with chemical reaction and correlating the CaCO₃ crystallization rates to the CO₂ release rates. The model was applied to two 20-stage reference MSF once-through and recycles distillers. The CO₂ release rates decreased exponentially from the first stage to the last stage. The CO₂ release rates increased with increasing top brine temperature (TBT) and so CaCO₃ deposition rates did. The CaCO₃ deposition rates increased by 76.9, 102.5 and 123.0 g per ton distillate at 90, 100 and 110 °C, respectively. This corresponded to fouling resistance of 0.64, 0.83 and 1.00 m²K/kW, respectively. The results were fully discussed and interpreted.     

Technical optimization of the extraction of andrographolide by supercritical CO2

An experimental design has been built in order to study the influence of different parameters on the crystallization ratio and purity of andrographolide extraction using supercritical CO₂: pressure (8–24 MPa), temperature (40–70 °C) and extraction duration (45–105 min). Crystallization ratios are between 14.32 and 72.29 wt%, and purities are between 43.11 and 79.78 wt%, indicating that the experimental design covers a large range of results. The results indicate that pressure and extraction duration are the most influencing parameters.     

Supercritical carbon dioxide extraction of sesquiterpenes from valerian root

Supercritical carbon dioxide extraction of sesquiterpenes from valerian root was investigated. Extractions from cultivar Arterner züctung and two wild grown valerian subspecies were performed. The influence of extraction conditions on extraction yield and chemical composition of obtained extracts was investigated at temperatures from 40 °C to 50 °C and pressures from 10 MPa to 20 MPa. Chemical composition of obtained extracts was analyzed by GC/FID and GC/MS methods. The influence of particle size on extraction process was investigated at 40 °C and 10 MPa. The major constituents of supercritical extracts were valerianol, valerenal, bornyl acetate and kessanyl acetate. Optimal extraction conditions for the cyclopentanoid sesquiterepenes isolation, referred to the content of cyclopentanoid sesquiterpenes in extract, were found to be 50 °C and 15 MPa. Extract obtained from the cultivar was characterized by the higher content of cyclopentanoid sesquiterpenes, as well as valerenal comparing to extracts from wild grown species. At 40 °C and 20 MPa 19.6% of cyclopentanoid sequiterpenes isolated with methanol can be extracted. At 40 °C and 10 MPa, 17.4% of cyclopentanoid sequiterpenes isolated with methanol can be extracted. However, the extract obtained with methanol was characterized by the high content (42.51%) of unwanted isovaleric as well as by the lower content of cyclopentanoid sequiterpenes than the extracts obtained with supercritical carbon dioxide. The process of supercritical extraction was influenced by particle size. In order to simulate the process, mathematical model on the secretory structure scale was derived. Results of the model showed good agreement with the experimental data.     

Supercritical CO2 extraction of glycosides from Stevia rebaudiana leaves: Identification and optimization

The aim of this work was to optimize the glycoside composition of Stevia rebaudiana leaves using supercritical fluid extraction (SFE). A Box-Behnken statistical design was used to evaluate the effect of various values of pressure (150–350 bar), temperature (40–80 °C) and concentration of ethanol-water mixture (70:30) as co-solvent (0–20%) by CO₂ flow rate of 15 g min⁻¹ for 60 min. The most effective variables were co-solvent concentration (P < 0.005) and temperature (P ≤ 0.005). Evaluative criteria for both dependent variables (stevioside and rebaudioside A yields) in the model was assigned maximum. Optimum extraction conditions were elicited as 211 bar, 80 °C and 17.4% which yielded 36.66 mg/g stevioside and 17.79 mg/g rebaudioside A. Total glycosides composition were close to those obtained using conventional water extraction (64.49 mg/g) and a little higher than ethanol extraction (48.60 mg/g) demonstrating challenges for industrial scale application of SFE.     

Extraction of sage (Salvia officinalis L.) by supercritical CO2: Kinetic data, chemical composition and selectivity of diterpenes

The supercritical carbon dioxide (SFE) extraction of Dalmatian sage (Salvia officinalis L.) was investigated and compared to extraction performed by Soxhlet ethanol-water (70:30) mixture extraction (SE) and hydrodistillation (HD). The supercritical extraction allowed isolation of wide spectrum of phytochemicals, while other applied methods were limited to either volatiles (HD) or high molecular compounds isolation (SE). The kinetics of the supercritical extraction and fractionation within the pressure range of 10-30 MPa at 50 °C were also analyzed as well as the chemical compositions of total extract and partial or differential fractions isolated at different CO₂ consumption. Volatile fraction could be isolated at low pressure and low CO₂ consumption, whereby the pressures between 10 and 15 MPa followed by increased CO₂ consumption were favourable for obtaining desired selectivity of diterpenes which contain compounds with expressed antioxidative characteristics.     

超临界萃取技术结合超声强化技术提取鹿茸中性激素和IGF-1

Supercritical CO2 (SC-CO2) extraction technology and ultrasonic technology were used to extract two active sex hormones, estradiol and progesterone, and insulin-like growth factor-1 (IGF-1) from antler velvet. The effects of SC-CO2 extraction condition on the extraction yield and content of sex hormones, the ultrasonic extraction condition on the content of IGF-1 and the SC-CO2 extraction condition on the activity remaining of IGF-1 were studied. The optimal conditions were obtained. The experimental results showed that, in presence of 75% ethanol as the co-solvent, the mean yield and content of estradiol and progesterone were 87.67 pg&#8226;g－1 and 1224.10 pg&#8226;g－1, 12.38 ng&#8226;g－1 and 354.06 ng&#8226;g－1, respectively, with extraction pressure of 30 MPa, temperature of 35°C, extraction time of 30 min and CO2 consumption of 15 L&#8226;g－1 at the flow rate of 2.0 L&#8226;min－1. The highest content of IGF-1 was 7425.75 ng&#8226;g－1 antler velvet residue, when the pH10 ammonia-ammonium chloride buffer solution was used as the solvent, the ratio of solvent to sample was 20/1 (volume/mass), the extraction temperature was 0-35°C, and the ex-traction time was 4×15 min. Under these conditions, 93.68% activity remaining of IGF-1 in the residue was ob-tained, while little IGF-1 activity exists in traditional residue. The experimental results indicate that the technology of SC-CO2 with co-solvent is of advantage for getting high content sexual hormones and keeping high activity of IGF-1 in the residue, which can not be achieved by traditional extraction methods.     

Guava (Psidium guajava L.) seed oil obtained with a homemade supercritical fluid extraction system using supercritical CO2 and co-solvent

In this work we designed and built a homemade supercritical fluid extraction (HM-SFE) system, in which pure CO₂ and CO₂ with co-solvents were used. The HM-SFE was made by means of thermal dilatation-contraction (TDC). This HM-SFE system was used for obtaining guava (Psidium guajava L.) seed oil, using supercritical CO₂ adding ethanol as co-solvent (CO₂ SC/EtOH), extractions were performed at 313 K and different pressures (10, 20 and 30 MPa), each one in four stages of 30 min, the extract with higher yield was subjected to transesterification and high-resolution gas chromatography (HRGC) analysis. The highest extraction yield was obtained at 30 MPa (17.30% w/w), this yield was higher than one observed in a previous work using SC-CO₂, and near to the one obtained by Soxhlet extraction (20.2% w/w). HRGC enabled the identification of components of the derivatized extract as methyl esters of palmitic, oleic, linoleic, and stearic fatty acids. The results obtained with HM-SFE system was compared with a commercial SFE system, obtained very similar results. In this work was possible to construct a low cost and simple manner HM-SFE system which was employed for obtaining guava seed oil, using CO₂ SC/EtOH.     

Feasibility of Na-based thermochemical cycles for the capture of CO2 from air—Thermodynamic and thermogravimetric analyses

Three Na-based thermochemical cycles for capturing CO₂ from air are considered: (1) a NaOH/NaHCO₃/Na₂CO₃/Na₂O cycle with 4 reaction steps, (2) a NaOH/NaHCO₃/Na₂CO₃ cycle with 3 reactions steps, and (3) a Na₂CO₃/NaHCO₃ cycle with 2 reaction steps. Depending on the choice of CO₂ sorbent – NaOH or Na₂CO₃ – the cycles are closed by either NaHCO₃ or Na₂CO₃ decomposition, followed by hydrolysis of Na₂CO₃ or Na₂O, respectively. The temperature requirements, energy inputs, and expected products of the reaction steps were determined by thermodynamic equilibrium and energy balance computations. The total thermal energy requirement for Cycles 1, 2, and 3 are 481, 213, and 390 kJ/mol of CO₂ captured, respectively, when heat exchangers are employed to recover the sensible heat of hot streams. Isothermal and dynamic thermogravimetric runs were carried out on the pertinent carbonation, decomposition, and hydrolysis reactions. The extent of the NaOH carbonation with 500 ppm CO₂ in air at 25 °C – applied in Cycles 1 and 2 – reached 9% after 4 h, while that for the Na₂CO₃ carbonation with water-saturated air – applied in Cycle 3 – was 3.5% after 2 h. Thermal decomposition of NaHCO₃ – applied in all three cycles – reached completion after 3 min in the 90–200 °C range, while that of Na₂CO₃ – applied in Cycle 1 – reached completion after 15 min in the 1000–1400 °C range. The significantly slow reaction rates for the carbonation steps and, consequently, the relatively large mass flow rates required, introduce process complications in the scale-up of the reactor technology and impede the application of Na-based sorbents for capturing CO₂ from air.     

Gasification of charcoal using supercritical CO2 at high pressures

A novel one-shell high temperature and high pressure semi-continuous reactor has been developed for the study of the Boudouard reaction at temperatures up to 820 °C and pressures up to 32.5 MPa. Semicontinuous gasification of charcoal using supercritical CO₂ has been achieved at conversions up to 90.8% (w/w) at LSHV between 20 and 30 h⁻¹ after 5–9 h. A gasification model is proposed and validated. Effective rates of gasification (1.32 ± 0.12) × 10⁻⁶ to (6.10 ± 2.03) × 10⁻⁵ s⁻¹ were obtained. The results indicated that this method is technically feasible for the on-line production of high pressures streams of CO/CO₂ in the lab for carrying out further chemistries, avoiding the use of CO high pressure bottles.     

Bioactive extracts of orange (Citrus sinensis L. Osbeck) pomace obtained by SFE and low pressure techniques: Mathematical modeling and extract composition

The objective of this study was to obtain orange (Citrus sinensis L. Osbeck) pomace extract using supercritical fluid extraction (SFE) with CO₂ and with CO₂ and co-solvent. In order to evaluate the high pressure method in terms of process yield, extract composition and biological activity, low pressure methods were also applied to obtain orange extracts, such as ultrasound (UE) and soxhlet (SOX), with different organic solvents, and hydrodistillation (HD). The SFE conditions were temperatures of 313.15 K and 323.15 K and pressures from 100 to 300 bar. The SFE kinetics and mathematical modeling of the overall extraction curves (OEC) were also investigated. The antioxidant potential of the extracts was evaluated by the DPPH method, by the Folin-Ciocalteau method and by the β-carotene/linoleic acid bleaching method. The antimicrobial activity of the extracts was also studied. The main compounds identified were l-limonene, palmitic and oleic acids, n-butyl benzenesulfonamide and β-sitosterol.     

Synthesis of yttrium aluminum garnet (YAG) powder by homogeneous precipitation combined with supercritical carbon dioxide or ethanol fluid drying

YAG precursors were synthesized by the urea method in aqueous solution using supercritical carbon dioxide and ethanol fluid drying technique, respectively. The composition of the precursors, the phase formation process and the properties of the calcined powders were investigated by means of XRD, IR, TG/DSC, BET, TEM and SEM. Compared with the classically prepared powders at room temperature in air, the amorphous precursor dried by supercritical CO₂ fluid was loosely agglomerated and directly converted to pure YAG at about 900 °C. The resultant YAG powders showed good dispersity with an average crystallite size about 20 nm and specific surface area of 52 m² g⁻¹. However, the precursor dried by supercritical ethanol fluid was crystalline. Extensive phase segregation occurred during the drying process and resulted in the formation of separate phases such as monoclinic Y(OH)₃ and pseudoboehmite. YAM and YAP phases appeared in the calcination process and phase pure were not detected until 1200 °C.     

Study on supercritical extraction of lipids and enrichment of DHA from oil-rich microalgae

The present study aims to isolate the lipids from microalgae by supercritical CO₂ (SC-CO₂) extraction followed by a further enrichment of crude lipids to produce high-purity docosahexenoic acid (DHA) by an urea complexation method. Our systematic approach indicates the optimum conditions of supercritical CO₂ extraction were obtained as follows: 35 MPa, 40 °C, ethanol (95%, v/v) as the co-solvent, and the mass ratio of material to co-solvent 1:1. Under these conditions, 33.9% of lipid yield and 27.5% of DHA content were achieved. Despite the relatively low lipid yield, supercritical CO₂ extraction has exhibited many advantages over the Soxhlet extraction for the DHA enrichment such as high DHA purity and superb product quality. Furthermore, urea complexation method on DHA enrichment considerably increased the DHA purity from 29.7% to 60.4% with an enrichment ratio of 60.6%, under the optimum complexation conditions of urea/fatty acid 2:1, complexation time 8 h, and the complexation temperature of −10 °C.     

气溶胶溶剂萃取技术制备β-谷甾醇亚微粒

The submicroparticles of β-sitosterol were produced by using an aerosol solvent extraction system (ASES) and characterized by scanning electronic microscope (SEM), X-ray diffraction (XRD), and Fourier transform infrared (FT-IR) analysis. The effects of operational parameters including pressure, temperature, solution concentration, and ratio of flow rate (CO2/solution, r) on particle size (PS), yield, and morphology were investigated. The results showed that microparticles of β-sitosterol (less than 1000 nm size and larger than 70% yield) could be obtained at 10-15 MPa, 35-50°C, 15 mg&#8226;ml－1, 10/1(r); β-sitosterol particles were found to occur as three mophologies: flakes, rods, and spheres by varying ratio of flow rate or solution concentration. In contrast, the crystallinity of β-sitosterol decreased, whereas its molecular structure remained almost unchanged after being ASES-treated. Therefore, ASES was an effective method to produce submicroparticles of β-sitosterol.