Supercritical carbon dioxide extraction and characterization of Laurus nobilis essential oil

Supercritical carbon dioxide extraction allowed essential oil of Laurus nobilis to be obtained. Extraction conditions were as follows: pressure, 90 bar; temperature, 50 degrees C; and carbon dioxide flow, Phi = 1.0 kg/h. Waxes were entrapped in the first separator set at 90 bar and -10 degrees C. The oil was recovered in the second separator working at 15 bar and 10 degrees C. The main components were 1,8-cineole (22.8%), linalool (12.5%), alpha-terpinyl acetate (11.4%), and methyleugenol (8.1%). Comparison with the hydrodistilled oil did not reveal any significant difference. Collection of samples at different extraction times during supercritical extraction allowed the change of the oil composition to be monitored. Lighter compounds such as hydrocarbon and oxygenated monoterpenes were extracted in shorter times than the heavier hydrocarbon and oxygenated sesquiterpenes.     

Supercritical carbon dioxide processing of pyrethrum oleoresin and pale

Possible refining of crude hexane extract (CHE) from pyrethrum flowers and further refining of Pyrethrum Board of Kenya (PBK) pale product is investigated with both liquid and supercritical carbon dioxide. The experiments were carried out in a small pilot plant with a 200 mL extractor and three cyclonic separators in series. To understand the dynamics of pyrethrin extraction, CHE was extracted in a single step; pyrethrin concentration was found to be improved from 0.16 to 0.50 g/g. The effects of temperature and pressure on the quality of the extract were studied at 29 degrees C and 80 bar and at 40 degrees C and 100 bar. Liquid CO(2) processing (29 degrees C, 80 bar) yielded slightly better product quality. A comparison study of CHE and PBK pale processing with supercritical CO(2) (40 degrees C, 100 bar) showed that the final products were similar in terms of pyrethrin content. Extraction of both PBK pale and CHE in two steps with different operating conditions improved their purity.     

Supercritical extraction of essential oil from aniseed (Pimpinella anisum L) using CO2: solubility,kinetics, and composition data

Supercritical fluid extraction (SFE) from aniseed using carbon dioxide was performed at 30 degrees C and pressures of 80-180 bar. The chemical composition of the SFE extract was determined by GC-MS; the quantitative analysis was done by GC-FID and TLC. The total amount of extractable substances or global yield (mass of extract/mass of feed) for the SFE process varied from 3.13 to 10.67% (mass). The solubilities of the anise essential oil in CO(2) were 0.0110, 0.0277, 0.0143, and 0.0182 kg of solute/kg of CO(2) at 80, 100, 140, and 180 bar, respectively. The major compounds identified and quantified in the extracts were anethole ( approximately 90%), gamma-himachalene (2-4%), p-anisaldehyde (<1%), methylchavicol (0.9-1.5%), cis-pseudoisoeugenyl 2-methylbutyrate ( approximately 3%), and trans-pseudoisoeugenyl 2-methylbutyrate ( approximately 1.3%). The Sovová model described quite well the experimental overall extraction curves.     

Comparison of eucalyptus camaldulensis Dehn. oils from Mozambique as obtained by hydrodistillation and supercritical carbon dioxide extraction

Leaf oils of E. camaldulensis Dehn. from Mozambique obtained by hydrodistillation and by supercritical carbon dioxide extraction under different conditions were compared with regard to their major components. The oil obtained by hydrodistillation showed high concentrations of 1,8-cineole (43%), alpha-pinene (5.5%), beta-pinene (3.4%), p-cymene (5.2%), terpinen-4-ol (3.1%), and globulol (4.1%). The extracts obtained by supercritical carbon dioxide extraction have lower amounts of 1,8-cineole, alpha-pinene, beta-pinene, and terpinen-4-ol, but have higher amounts of allo-aromadendrene and globulol. At the same time, distilled oil of E. radiata was extracted from an inert matrix (Celite) and the extract showed a higher content of 1,8-cineole at 80 bar and 60 degrees C than the feed, suggesting that a multiple-stage supercritical carbon dioxide extraction of the E. camaldulensis studied can produce an oil close to the market requirements set by the European pharmacopoeias.     

Supercritical CO(2) extraction of beta-carotene and lycopene from tomato paste waste

Lycopene and beta-carotene were extracted from tomato paste waste using supercritical carbon dioxide (SC-CO(2)). To optimize supercritical fluid extraction (SFE) results for the isolation of lycopene and beta-carotene, a factorial designed experiment was conducted. The factors assessed were the temperature of the extractor (35, 45, 55, and 65 degrees C), the pressure of the extraction fluid (200, 250, and 300 bar), addition of cosolvent (5, 10, and 15% ethanol), extraction time (1, 2, and 3 h), and CO(2) flow rate (2, 4, and 8 kg/h). The total amounts of lycopene and beta-carotene in the tomato paste waste, extracts, and residues were determined by HPLC. A maximum of 53.93% of lycopene was extracted by SC-CO(2) in 2 h (CO(2) flow rate = 4 kg/h) at 55 degrees C and 300 bar, with the addition of 5% ethanol as a cosolvent. Half of the initially present beta-carotene was extracted in 2 h (flow rate = 4 kg/h), at 65 degrees C and 300 bar, also with the addition of 5% ethanol.     

Essential oils from plants and in vitro shoots of Hypericum androsaemum L

The essential oil yields obtained by hydrodistillation of the aerial parts of Hypericum androsaemum cultivated plants varied from 0.94 to 4.09 mg/g of biomass dry weight, depending of the harvest time. The respective analyses performed by gas chromatography and gas chromatography-mass spectrometry revealed more than 80 compounds, 72 of which were identified. Most of the compounds were sesquiterpene hydrocarbons, which, depending of the harvest time, corresponded to 43-78% of the total essential oil. The other compounds were distributed as monoterpene hydrocarbons, oxygen-containing sesquiterpenes, n-alkanes, 1-alkenes, and oxygen-containing monoterpenes, these being a minor group. In H. androsaemum in vitro shoots, sesquiterpene hydrocarbons represented >80% of the respective essential oil. Differences in the essential oil composition were found depending on the harvest time and origin, in vivo versus in vitro, of the plant material. The essential oil sampled in November was characterized by the highest levels of sesquiterpene hydrocarbons and a high number of n-alkanes and 1-alkenes, from C(18) to C(28), whereas that sampled in June of the following year showed the highest levels of n-nonane and 1-octene as well as monoterpene hydrocarbons, the second most representative group.     

Selective recovery of tagatose from mixtures with galactose by direct extraction with supercritical CO2 and different cosolvents

A selective fractionation method of carbohydrate mixtures of galactose/tagatose, using supercritical CO(2) and isopropanol as cosolvent, has been evaluated. Optimization was carried out using a central composite face design and considering as factors the extraction pressure (from 100 to 300 bar), the extraction temperature (from 60 to 100 degrees C), and the modifier flow rate (from 0.2 to 0.4 mL/min, which corresponded to a total cosolvent percentage ranging from 4 to 18% vol). The responses evaluated were the amount (milligrams) of tagatose and galactose extracted and their recoveries (percent). The statistical analysis of the results provided mathematical models for each response variable. The corresponding parameters were estimated by multiple linear regression, and high determination coefficients (>0.96) were obtained. The optimum conditions of the extraction process to get the maximum recovery of tagatose (37%) were 300 bar, 60 degrees C, and 0.4 mL/min of cosolvent. The predicted value was 24.37 mg of tagatose, whereas the experimental value was 26.34 mg, which is a 7% error from the predicted value. Cosolvent polarity effects on tagatose extraction from mixtures of galactose/tagatose were also studied using different alcohols and their mixtures with water. Although a remarkable increase of the amount of total carbohydrate extracted with polarity was found, selective extraction of tagatose decreased with increase of polarity of assayed cosolvents. To improve the recovery of extracted tagatose, additional experiments outside the experimental domain were carried out (300 bar, 80 degrees C, and 0.6 mL/min of isopropanol); recoveries >75% of tagatose with purity >90% were obtained.     

Designed polar cosolvent-modified supercritical CO2 removing caffeine from and retaining catechins in green tea powder using response surface methodology

This study examines cosolvent-modified supercritical carbon dioxide (SC-CO2) to remove caffeine from and to retain catechins in green tea powder. The response surface method was adopted to determine the optimal operation conditions in terms of the extraction efficiencies and concentration factors of caffeine and catechins during the extractions. When SC-CO2 was used at 333 K and 300 bar, 91.5% of the caffeine was removed and 80.8% of catechins were retained in the tea: 3600 g of carbon dioxide was used in the extraction of 4 g of tea soaked with 1 g of water. Under the same extraction conditions, 10 g of water was added to <800 g of carbon dioxide in an extraction that completely removed caffeine (that is, the caffeine extraction efficiency was 100%). The optimal result as predicted by three-factor response surface methodology and supported by experimental data was that in 1.5 h of extraction, 640 g of carbon dioxide at 323 K and 275 bar with the addition of 6 g of water extracted 71.9% of the caffeine while leaving 67.8% of the catechins in 8 g of tea. Experimental data indicated that supercritical carbon dioxide decaffeination increased the concentrations of caffeine in the SC-CO2 extracts at 353 K.     

Volatile chemicals identified in extracts from leaves of Japanese mugwort (Artemisia princeps pamp.)

Extracts from leaves of Japanese mugwort (Artemisia princeps Pamp.) were obtained using two methods: steam distillation under reduced pressure followed by dichloromethane extraction (DRP) and simultaneous purging and extraction (SPSE). A total of 192 volatile chemicals were identified in the extracts obtained by both methods using gas chromatography (GC) and gas chromatography-mass spectrometry (GC-MS). They included 47 monoterpenoids (oxygenated monoterpenes), 26 aromatic compounds, 19 aliphatic esters, 18 aliphatic alcohols, 17 monoterpenes (hydrocarbon monoterpenes), 17 sesquiterpenes (hydrocarbon sesquiterpenes), 13 sesquiterpenoids (oxygenated sesquiterpenes), 12 aliphatic aldehydes, 8 aliphatic hydrocarbons, 7 aliphatic ketones, and 9 miscellaneous compounds. The major volatile constituents of the extract by DRP were borneol (10.27 ppm), alpha-thujone (3.49 ppm), artemisia alcohol (2.17 ppm), verbenone (1.85 ppm), yomogi alcohol (1.50 ppm), and germacren-4-ol (1.43 ppm). The major volatile constituents of the extract by SPSE were 1,8-cineole (8.12 ppm), artemisia acetate (4.22 ppm), alpha-thujone (3.20 ppm), beta-caryophyllene (2.39 ppm), bornyl acetate (2.05 ppm), borneol (1.80 ppm), and trans-beta-farnesene (1. 78 ppm).     

Supercritical CO(2) and subcritical propane extraction of pungent paprika and quantification of carotenoids, tocopherols, and capsaicinoids.

Ground paprika (Capsicum annuum L.) was extracted with supercritical carbon dioxide (SC-CO(2)) and subcritical propane at different conditions of pressure and temperature to estimate the yield and variation in carotenoid, tocopherol, and capsaicinoid contents and composition. The yield of paprika extract was found to be affected by the extraction conditions with SC-CO(2) but fairly constant at different conditions with subcritical propane. The maximum yields of oleoresin were 7.9 and 8.1% of ground paprika by SC-CO(2) and subcritical propane, respectively. The quantitative distribution of carotenoids, tocopherols, and capsaicinoids between paprika extract and powder was influenced by extraction conditions. SC-CO(2) was inefficient in the extraction of diesters of xanthophylls even at 400 bar and 55 degrees C, whereas tocopherols and capsaicinoids were easy to extract at these conditions. Under mild conditions subcritical propane was superior to SC-CO(2) in the extraction of carotenoids and tocopherols but less efficient in the extraction of capsaicinoids.     

Volatiles obtained from whole and ground grain samples by supercritical carbon dioxide and direct helium purge methods: observations on 2,3-butanediols and halogenated anisoles.

Volatile compounds were obtained from whole and ground grain samples by two methods. In the supercritical fluid extraction (SFE) method, volatiles were extracted from the grain with supercritical carbon dioxide, trapped at -78 degrees C, and then transferred via a purge-and-trap instrument to a gas chromatograph with mass and infrared detectors (GC-MS/IR) for separation and identification. In the direct-helium-purge method (DHP), volatiles were purged directly from the grain into the purge-and-trap instrument for subsequent transfer to the GC-MS/IR system. With SFE, extraction of volatiles was favored by ground grain, low pressures (相似文献   

Use of adsorbent and supercritical carbon dioxide to concentrate flavor compounds from orange oil.

Orange oil is composed largely of terpene hydrocarbons but is a source of flavor and fragrance compounds (oxygenated) that are present in low concentrations. To increase the ratio of oxygenated compounds to terpene hydrocarbons, orange oil was partially fractionated by adsorption of the oxygenated compounds onto porous silica gel, with full utilization of its adsorbent capacity, and then further purified by desorption into supercritical carbon dioxide. The desorption of 24 compounds was monitored by GC and GC-MS. Adsorption alone removed three-fourths of the terpene hydrocarbons, and fractional extraction by supercritical carbon dioxide (SC-CO(2)) improved the separation further. Response surface methodology was used in the experimental design, and regression analysis was used to determine the effects of process variables. Extraction at low temperatures and flow rates improved separation by SC-CO(2). Decanal was concentrated to 20 times that of the feed oil by using SC-CO(2) at 13.1 MPa, 35 degrees C, and 2 kg/h. The systems were operating at close to equilibrium conditions because of the fine dispersal of the oils and the excellent mass transfer properties of supercritical carbon dioxide.     

Extraction of azadirachtin A from neem seed kernels by supercritical fluid and its evaluation by HPLC and LC/MS

A new supercritical extraction methodology was applied to extract azadirachtin A (AZA-A) from neem seed kernels. Supercritical and liquid carbon dioxide (CO(2)) were used as extractive agents in a three-separation-stage supercritical pilot plant. Subcritical conditions were tested too. Comparisons were carried out by calculating the efficiency of the pilot plant with respect to the milligrams per kilogram of seeds (ms/mo) of AZA-A extracted. The most convenient extraction was gained using an ms/mo ratio of 119 rather than 64. For supercritical extraction, a separation of cuticular waxes from oil was set up in the pilot plant. HPLC and electrospray mass spectroscopy were used to monitor the yield of AZA-A extraction.     

Supercritical carbon dioxide extraction of oil and squalene from amaranthus grain

Supercritical carbon dioxide (SC CO(2)) was used for the extraction of oil and squalene from Amaranthus grain. Very small amounts of oil could be extracted by SC CO(2) from undisrupted grains, although SC CO(2) possesses higher diffusivity. Grinding increased the extraction rate and oil yield, and smaller particle size gave higher extraction rate. The oil yield and initial extraction rate increased linearly with the increasing SC CO(2) flow rate from 1 to 2 L/min. Increasing the flow rate of SC CO(2) above 2 L/min resulted in only a slight increase of oil yield and extraction rate. In the pressure range of 150-250 bar, extraction decreased with increasing temperature at a constant pressure, whereas at a pressure of 300 bar, the extraction yield increased with increasing temperature. Possible reasons for this are discussed. Effects of temperature and pressure on squalene yield were different from those on oil yield. A good oil yield (4.77 g of oil/100 g of grain) was obtained at 40 degrees C and 250 bar. The highest squalene yield (0.31 g of squalene/100 g of grain) and concentration (15.3% in extract) were obtained at 50 degrees C and 200 bar, although the oil yield under this condition was low (2.07 g of oil/100 g of grain). The moisture content within 0-10% had little influence on yields of oil and squalene at 40 degrees C and 250 bar. Finally, the oil yield and the squalene concentration in the extracts by SC CO(2) were compared to those by solvent extraction.     

Effect of variety and maturation of cheese on supercritical fluid extraction efficiency

Supercritical fluid extraction (SFE) has been utilized by the food industry in many applications to extract, fractionate, and recover compounds from various food matrices. However, little research has been conducted using SFE as an alternative process for producing reduced-fat cheese. Lipids in cheeses may be selectively extracted due to the nonpolar properties of supercritical carbon dioxide (SC-CO2), without leaving residual chemicals as is the case in solvent extraction. The objective of this study was to evaluate the influence on the extraction process due to cheese variety and protein breakdown by age. A Latin square design was utilized to test the extractability of lipids from Parmesan and Cheddar cheeses, aged young (9-10 months) or old (24 months). Extraction took place in a 500 mL SFE vessel using 100 g of grated cheese samples. The SFE parameters of the extraction were 350 bar, 35 degrees C, and supercritical carbon dioxide at a flow rate of 20 g/min for 55 min. Compositional analysis measured all treated samples and controls of total lipids, lipid profiling, total protein, protein/peptide analysis, moisture, ash, and pH. Cheese type was a major variable in fat extraction. The extraction in Cheddar showed an average fat reduction of 53.56% for young cheese, whereas that in old Cheddar was 47.90%. However, young Parmesan was reduced an average of 55.07%, but old Parmesan was reduced at 68.11%, measured on a dry basis. SFE extracted triglycerides and cholesterol, but did not remove phospholipids. This investigation introduces the observations of the effect of Cheddar and Parmesan varieties on SFE, offering data on the important parameters to consider in the design of SFE processes to reduce fat in cheese.     

Supercritical fluid extraction of the pesticides carbosulfan and imidacloprid from process dust waste

Large amounts of contaminated process dust remain from the procedure of pesticide treatments applied to seed pellets. A pilot study in analytical-scale supercritical fluid extraction (SFE) was performed to determine the possibility of using supercritical carbon dioxide for the extraction of the nonpolar insecticide carbosulfan and the more polar insecticide imidacloprid present in contaminated dust waste, at concentrations of up to 20% (w/w). The effects of various experimental conditions, such as temperature, flow rate, and addition of modifier, on the recovery of the analytes were evaluated by extracting the pesticides both from spiked support material and from real dust samples. It was found that carbosulfan could easily be extracted from the dust waste within 30 min at 138 bar and 40 degrees C with a recovery of 98.9% (RSD = 2.3%, n = 10), compared to values obtained with a validated liquid extraction method. A sufficient removal of the more polar substance imidacloprid required the addition of a modifier, and the results showed a strong dependence of the extraction efficiency on the choice of modifier. Extractions at 276 bar and 80 degrees C with a solvent consisting of supercritical carbon dioxide modified with methanol (5%) gave a recovery of 97.0% (RSD = 3.6%, n = 10) using a 40 min extraction time. The results indicate that it seems to be possible to use process-scale SFE for the decontamination of pesticides from dust waste. The conditions outlined also permit analytical determinations of the two insecticides based on a combination of SFE and liquid chromatography.     

Isolation of tetra-acyl sucrose esters from turkish tobacco using supercritical fluid CO2 and comparison with conventional solvent extraction

Pure supercritical CO2 at various pressures and temperatures was used to effect the fractionation of tetra-acyl sucrose esters (SE) from dried, ground Turkish tobacco without any further pretreatment of the matrix. It was determined that SE cannot be extracted using low density CO2 (150 atm, 60 degrees C, and 0.62 gm/mL or 200 atm, 100 degrees C, and 0.49 gm/mL), whereas other analytes, which strongly interfere with the conventional solvent extraction of SE, can be easily removed under the same conditions. At the higher temperature (100 degrees C), these same analytes that interfere with the conventional solvent extraction of SE are even more readily removed, while the very poor extractability of SE is not affected. It was demonstrated, however, that SE can be removed from the pre-extracted tobacco with supercritical CO2 if the density is greater than (or equal to) 0.73 gm/mL. The supercritical fluid extraction method has been compared with other previous extraction methods that employ conventional solvents. This study provides one of the clearest examples of how the variable density property of a supercritical fluid can be utilized to effect the fractionation of a complex mixture.     

Countercurrent supercritical fluid extraction and fractionation of high-added-value compounds from a hexane extract of olive leaves

Countercurrent supercritical fluid extraction (CC-SFE) at a pilot scale plant was used for fractionation of high-added-value products from a raw extract of olive leaves in hexane. Compounds found in the raw extract were waxes, hydrocarbons, squalene, beta-carotene, triglycerides, alpha-tocopherol, beta-sitosterol, and alcohols. The CC-SFE extraction process was investigated according to a 2(3) full factorial experimental design using the following variables and ranges: extraction pressure, 75-200 bar; extraction temperature, 35-50 degrees C; and ethanol as modifier, 0-10%. Data were analyzed in terms of extraction yield, enrichment, recovery, and selectivity. Higher extraction yields were attained at 200 bar. For most of the compounds analyzed enrichment was attained at the same conditions, that is, 75 bar, 35 degrees C, and 10% ethanol. Hydrocarbons were usually recovered in the separators, whereas waxes and alpha-tocopherol remain in the raffinate. Selectivity data reveal that alpha-tocopherol is the most easily separable compound. The influence of the experimental factors on the recovery of all the compounds was studied by means of regression models. The best fitted model was attained for beta-sitosterol, with R2 = 99.25%.     

Organ- and season-dependent variation in the essential oil composition of Salvia officinalis L. cultivated at two different sites.

More than 50 compounds were identified in essential oils from stems and leaves of Salvia officinalis L. plants harvested in July, in Arouca, in northern Portugal. About 40 of those compounds were also present in flower essential oils, collected from the same plants. alpha-Thujone was the major compound, representing about 55, 30, and 18% of the essential oils from stems, leaves, and flowers, respectively. Significant percentage variations in the main compound classes of the essential oils from shoots sampled over the year were recorded at two different sites in northern Portugal. From December to April, oxygenated monoterpenes (MO) decreased from approximately 67-72% to values of 42-43% of the essential oils. During the same time interval, the percentage of monoterpene hydrocarbons (MH) rose from 8-11% to 17-22%. At both sites, sesquiterpene hydrocarbons (SH) rose from approximately 7% in February to 19-22% in April, decreasing thereafter to approximately 9% in July. Oxygenated sesquiterpenes (SO) increased from a minimum of approximately 5% in July to a maximum of 8-11% in February, decreasing thereafter. The compounds that mostly accounted for the essential oil composition variation were alpha-pinene, beta-pinene, and camphene, as MH; alpha-thujone and camphor, as MO; alpha-humulene and beta-caryophyllene, as SH; and viridiflorol, as SO.     

Supercritical carbon dioxide extraction of essential oils from Perovskia atriplicifolia Benth

The supercritical fluid extraction (SFE) of the aerial parts of Perovskia atriplicifolia Benth. was studied. The effect of different parameters such as pressure, temperature, modifier identity, and modifier volume on the SFE of the plant was investigated. The extracts were analyzed by GC and GC-MS and compared with the essential oil obtained from P. atriplicifolia Benth by steam distillation. The supercritical extracts and the steam-distilled products had very different compositions. The main constituents of the oil obtained by steam distillation were 1,8-cineole, limonene, camphor, beta-caryophyllene, alpha-pinene, camphene, and alpha-humulene. On the other hand, the major components of SFE extracts were 1,8-cineole, limonene, camphor, beta-caryophyllene, gamma-cadinene, alpha-pinene, and alpha-terpinyl acetate. The results showed that increasing the temperature from 35 to 65 degrees C (at a constant pressure of 100 atm) drastically reduced the number of extracted components. Also, the number of extracted constituents and the percent of main analytes increased when lower pressures were used. Using different modifiers (e.g., methanol, ethanol, dichloromethane, and hexane) for the extraction of the plant at low pressure (100 atm) and temperature (35 degrees C) showed that hexane was more selective than the other modifiers.