Supercritical fluid extraction (SFE), which has received much interest in its use and further development for industrial applications, is a method that offers some advantages over conventional methods, especially for the palm oil industry. SC-CO₂ refers to supercritical fluid extraction (SFE) that uses carbon dioxide (CO₂) as a solvent which is a nontoxic, inexpensive, nonflammable, and nonpolluting supercritical fluid solvent for the extraction of natural products. Almost 100% oil can be extracted and it is regarded as safe, with organic solvent-free extracts having superior organoleptic profiles. The palm oil industry is one of the major industries in Malaysia that provides a major contribution to the national income. Malaysia is the second largest palm oil and palm kernel oil producer in the World. This paper reviews advances in applications of supercritical carbon dioxide (SC-CO₂) extraction of oils from natural sources, in particular palm oil, minor constituents in palm oil, producing fractionated, refined, bleached, and deodorized palm oil, palm kernel oil and purified fatty acid fractions commendable for downstream uses as in toiletries and confectionaries.
There has been growing interest among food scientists in producing a toxin-free fat as an end product with varying physical or nutritional properties of interest to the food industry. Oleoresin is a rich source of bioactive compounds which consumers can easily add to a large variety of food. Dabai (Canarium odontophyllum) pulp oleoresin (DPL) was extracted using supercritical carbon dioxide (SC-CO2) extraction, a green extraction technology. This study investigates the quality of SC-CO2 extracted DPL in discovering its potential as a new alternative fat. The extraction experiment was carried out at a pressure of 40 MPa and a temperature of 40 °C. DPL is a saturated fatty acid (SFA)-rich fat due to its high SFA composition (47.72 ± 0.01%). In addition, the low content of peroxide value (PV) (5.60 ± 0.09 mEq/kg) and free fatty acids (FFA) (3.40 ± 0.03%) indicate the quality and stability of DPL for various applications besides food consumption. DPL also has a low slip melting point (SMP) (20.20 ± 0.03 °C), and HPLC-FID revealed that DPL contained 0.13 ± 0.02 mg/100 g of vitamin E (α-tocopherol), indicating its potential application as a solid fat with a bioactive compound. This present work demonstrates the possible prospect of DPL in the formulation of end products for food industries.
In this study, optimization of supercritical reactive extraction directly from Jatropha seeds in a high pressure batch reactor using Response Surface Methodology (RSM) coupled with Central Composite Rotatable Design (CCRD) was performed. Four primary variables (methanol to solid ratio (SSR), reaction temperature, time and CO2 initial pressure) were investigated under the proposed constraints. It was found that all variables had significant effects towards fatty acid methyl esters (FAME) yield. Moreover, three interaction effects between the variables also played a major role in influencing the final FAME yield. Optimum FAME yield at 92.0 wt.% was achieved under the following conditions: 5.9 SSR, 300°C, 12.3 min and 20 bar CO2. Final FAME product was discovered to fulfil existing international standard. Preliminary characterization analysis proved that the solid residue can be burnt as solid fuel in the form of biochar while the liquid product can be separated as specialty chemicals or burned as bio-oil for energy production.
Fish oil was extracted from the viscera of African Catfish using supercritical carbon dioxide (SC-CO(2)). A Central Composite Design of Response Surface methodology (RSM) was employed to optimize the SC-CO(2) extraction parameters. The oil yield (Y) as response variable was executed against the four independent variables, namely pressure, temperature, flow rate and soaking time. The oil yield varied with the linear, quadratic and interaction of pressure, temperature, flow rate and soaking time. Optimum points were observed within the variables of temperature from 35 °C to 80 °C, pressure from 10 MPa to 40 MPa, flow rate from 1 mL/min to 3 mL/min and soaking time from 1 h to 4 h. However, the extraction parameters were found to be optimized at temperature 57.5 °C, pressure 40 MPa, flow rate 2.0 mL/min and soaking time 2.5 h. At this optimized condition, the highest oil yields were found to be 67.0% (g oil/100 g sample on dry basis) in the viscera of catfish which was reasonable to the yields of 78.0% extracted using the Soxhlet method.
Crude palm oil contains 600 to 1000 ppm of tocols in the form of tocopherols and tocotrienols. These palm tocols have been isolated and analyzed in the past by various chromatographic techniques such as open column chromatography, high-performance liquid chromatography, as well as thin-layer chromatography. Supercritical fluid chromatography (SFC) has emerged as a more advanced chromatographic technique in recent years. The tocols present in palm oil are successfully isolated using SFC. Identification of these tocols is supported by various spectroscopic techniques such as 1H NMR, 13C NMR, and mass spectrometry.
In recent years, astaxanthin is claimed to have a 10 times higher antioxidant activity than that of other carotenoids such as lutein, zeaxanthin, canthaxanthin, and β-carotene; the antioxidant activity of astaxanthin is 100 times higher than that of α-tocopherol. Penaeus monodon (tiger shrimp) is the largest commercially available shrimp species and its waste is a rich source of carotenoids such as astaxanthin and its esters. The efficient and environment-friendly recovery of astaxanthins was accomplished by using a supercritical fluid extraction (SFE) technique. The effects of different co-solvents and their concentrations on the yield and composition of the extract were investigated. The following co-solvents were studied prior to the optimization of the SFE technique: ethanol, water, methanol, 50% (v/v) ethanol in water, 50% (v/v) methanol in water, 70% (v/v) ethanol in water, and 70% (v/v) methanol in water. The ethanol extract produced the highest carotenoid yield (84.02 ± 0.8 μg/g) dry weight (DW) with 97.1% recovery. The ethanol extract also produced the highest amount of the extracted astaxanthin complex (58.03 ± 0.1 μg/g DW) and the free astaxanthin content (12.25 ± 0.9 μg/g DW) in the extract. Lutein and β-carotene were the other carotenoids identified. Therefore, ethanol was chosen for further optimization studies.
Phytosterols provide important health benefits: in particular, the lowering of cholesterol. From environmental and commercial points of view, the most appropriate technique has been searched for extracting phytosterols from plant matrices. As a green technology, supercritical fluid extraction (SFE) using carbon dioxide (CO2) is widely used to extract bioactive compounds from different plant matrices. Several studies have been performed to extract phytosterols using supercritical CO2 (SC-CO2) and this technology has clearly offered potential advantages over conventional extraction methods. However, the efficiency of SFE technology fully relies on the processing parameters, chemistry of interest compounds, nature of the plant matrices and expertise of handling. This review covers SFE technology with particular reference to phytosterol extraction using SC-CO2. Moreover, the chemistry of phytosterols, properties of supercritical fluids (SFs) and the applied experimental designs have been discussed for better understanding of phytosterol solubility in SC-CO2.
Candlenut oil was extracted using supercritical CO(2) (SC-CO(2)) with an optimization of parameters, by the response surface methodology. The ground candlenut samples were treated in 2 different ways, that is, dried in either a heat oven (sample moisture content of 2.91%) or dried in a vacuum oven (sample moisture content of 1.98%), before extraction. An untreated sample (moisture content of 4.87%) was used as a control. The maximum percentage of oil was extracted from the heat-oven-dried sample (77.27%), followed by the vacuum-oven-dried sample (74.32%), and the untreated sample (70.12%). At an SC-CO(2) pressure of 48.26 Mpa and 60 min of extraction time, the optimal temperatures for extraction were found to be 76.4 °C, 73.9 °C, and 70.6 °C for the untreated, heat-oven-dried, and vacuum-oven-dried samples, respectively. The heat-oven-dried sample contains the highest percentage of linoleic acid, followed by the untreated and vacuum-oven-dried samples. The antiradical activity of candlenut oil corresponded to an IC(50) value of 30.37 mg/mL.
The novel biodiesel production technology using supercritical reactive extraction from Jatropha curcas L. oil seeds in this study has a promising role to fill as a more cost-effective processing technology. Compared to traditional biodiesel production method, supercritical reactive extraction can successfully carry out the extraction of oil and subsequent esterification/transesterification process to fatty acid methyl esters (FAME) simultaneously in a relatively short total operating time (45-80 min). Particle size of the seeds (0.5-2.0 mm) and reaction temperature/pressure (200-300 degrees C) are two primary factors being investigated. With 300 degrees C reaction temperature, 240 MPa operating pressure, 10.0 ml/g methanol to solid ratio and 2.5 ml/g of n-hexane to seed ratio, optimum oil extraction efficiency and FAME yield can reach up to 105.3% v/v and 103.5% w/w, respectively which exceeded theoretical yield calculated based on n-hexane Soxhlet extraction of Jatropha oil seeds.
Syzygium campanulatum Korth is a plant, which is a rich source of secondary metabolites (especially flavanones, chalcone, and triterpenoids). In our present study, three conventional solvent extraction (CSE) techniques and supercritical fluid extraction (SFE) techniques were performed to achieve a maximum recovery of two flavanones, chalcone, and two triterpenoids from S. campanulatum leaves. Furthermore, a Box-Behnken design was constructed for the SFE technique using pressure, temperature, and particle size as independent variables, and yields of crude extract, individual and total secondary metabolites as the dependent variables. In the CSE procedure, twenty extracts were produced using ten different solvents and three techniques (maceration, soxhletion, and reflux). An enriched extract of five secondary metabolites was collected using n-hexane:methanol (1:1) soxhletion. Using food-grade ethanol as a modifier, the SFE methods produced a higher recovery (25.5%‒84.9%) of selected secondary metabolites as compared to the CSE techniques (0.92%‒66.00%).
Mitragyna speciosa, a tropical plant indigenous to Southeast Asia, is well known for its psychoactive properties. Its leaves are traditionally chewed by Thai and Malaysian farmers and manual labourers as it causes a numbing, stimulating effect. The present study aims to evaluate alkaloid yield and composition in the leaf extracts. For this purpose we have compared several non-conventional extraction techniques with classic procedures (room temperature or under heating). Dried M. speciosa leaves belonging to three batches of different origin (from Thailand, Malaysia and Indonesia) were extracted using ultrasound-assisted extraction (UAE), microwave-assisted extraction (MAE) and supercritical carbon dioxide extraction SFE-CO(2), using methanol, ethanol, water and binary mixtures. The extracts were compared using an HPLC/ESI-MS analysis of mitragynine and four other related alkaloids which were present in the alkaloid fraction. The extraction technique influences both the raw product yield and the relative alkaloid content of M. speciosa leaves. Of the several methods tested, MAE in a closed vessel at 110 °C (60 W, methanol/water 1:1) gave the highest alkaloid fraction amount, while UAE with an immersion horn at 25 °C (21.4 kHz, 50 W, methanol) showed the best yield for mitragynine. This work may prove to be a useful contribution to forensic, toxicological and pharmacognosy studies. Although the potential applications of M. speciosa alkaloids clearly need further investigation, these results may facilitate the scaling-up of their extraction.
There are six tocol analogs present in palm oil, namely α-tocopherol (α-T), α-tocomonoenol (α-T₁), α-tocotrienol (α-T₃), γ-tocotrienol (γ-T₃), β-tocotrioenol (β-T₃) and δ-tocotrienol (δ-T₃). These analogs were difficult to separate chromatographically due to their similar structures, physical and chemical properties. This paper reports on the effect of pressure and injection solvent on the separation of the tocol analogs in palm oil. Supercritical CO₂ modified with ethanol was used as the mobile phase. Both total elution time and resolution of the tocol analogs decreased with increased pressure. Ethanol as an injection solvent resulted in peak broadening of the analogs within the entire pressure range studied. Solvents with an eluent strength of 3.4 or less were more suitable for use as injecting solvents.
High-quality fish oil for human consumption requires low levels of toxic elements. The aim of this study was to compare different oil extraction methods to identify the most efficient method for extracting fish oil of high quality with the least contamination. The methods used in this study were Soxhlet extraction, enzymatic extraction, wet reduction, and supercritical fluid extraction. The results showed that toxic elements in fish oil could be reduced using supercritical CO2 at a modest temperature (60°C) and pressure (35 MPa) with little reduction in the oil yield. There were significant reductions in mercury (85 to 100%), cadmium (97 to 100%), and lead (100%) content of the fish oil extracted using the supercritical fluid extraction method. The fish oil extracted using conventional methods contained toxic elements at levels much higher than the accepted limits of 0.1 μg/g.
A preliminary study was conducted to study the effects of different types and concentrations of co-solvents based on yield, composition and antioxidants capacity of extract prior to optimization studies of supercritical fluid extraction (SFE) of Labisia pumila (locally referred to as 'kacip fatimah'). The following co-solvents were studied prior to the optimization of supercritical carbon dioxide (SC-CO2) technique: ethanol, water, methanol, as well as aqueous solutions of ethanol-water and methanol-water (50% and 70% v/v). By using the selected co-solvents, identification of phenolic acids (gallic acid, methyl gallate and caffeic acid) was determined by using High-Performance Liquid Chromatography (HPLC). Then, the antioxidant capacity was evaluated by using three different assays: total phenolic content (TPC), ferric reducing/antioxidant power (FRAP) and free radical-scavenging capacity of 2,2-diphenyl-1-picrylhydrazyl (DPPH). SC-CO2 with 70% ethanol-water co-solvent was superior in terms of a higher combination of phenolic compounds extracted and antioxidants capacity. Overall, SC-CO2 with co-solvent 70% ethanol-water technique was efficient in extracting phenolic compounds from L. pumila, and thus the usage of this solvent system should be considered for further optimization studies.