IntechOpen

Home > Books > Carbon Dioxide Chemistry, Capture and Oil Recovery

Open access peer-reviewed chapter

Carbon Dioxide Use in High-Pressure Extraction Processes

Written By

Vânia Maria Borges Cunha, Marcilene Paiva da Silva, Wanessa Almeida da Costa, Mozaniel Santana de Oliveira, Fernanda Wariss Figueiredo Bezerra, Anselmo Castro de Melo, Rafael Henrique Holanda Pinto, Nelio Teixeira Machado, Marilena Emmi Araujo and Raul Nunes de Carvalho Junior

Submitted: 02 May 2017 Reviewed: 21 September 2017 Published: 16 August 2018

DOI: 10.5772/intechopen.71151

Carbon Dioxide Chemistry, Capture and Oil Recovery IntechOpen
Carbon Dioxide Chemistry, Capture and Oil Recovery Edited by Iyad Karamé

From the Edited Volume

Carbon Dioxide Chemistry, Capture and Oil Recovery

Edited by Iyad Karamé, Janah Shaya and Hassan Srour

Book Details Order Print

Chapter metrics overview

2,141 Chapter Downloads

View Full Metrics
Advertisement

Abstract

This chapter describes the use of carbon dioxide at high pressures as an alternative for the extraction of bioactive compounds in a more sustainable way, addressing some of its physicochemical properties, such as pressure, temperature, density, solvation, selectivity, and its interaction with the solute when modified by other solvents such as ethanol and water. This extraction process is considered chemically “green,” when compared to conventional extraction processes using toxic organic solvents.

Keywords

  • supercritical CO2
  • high pressure
  • density
  • vegetable matrix
  • bioactive compounds

1. Introduction

Separation technologies with fluids at high pressures are essentially vital to get new natural products of vegetable or marine origin that have biological activity, so-called bioactive extracts. Among the developed technologies, the supercritical fluid technology offers products free of residual solvent and that typically present high quality, when compared to products obtained by conventional techniques. The extracts of bioactive compounds can be obtained by extraction of solid matrices (leaves, seeds, pulps, etc.) or by extraction/fractionation of liquid mixtures (aqueous solutions, fish oils, microalgae oils, vegetable oil, deodorize distillates, etc.) [1, 2, 3, 4, 5]. In processes at high pressures, which are near or above the critical point (pressure and temperature), the solvent density increases drastically and this is the most important parameter associated to the solvent power. As illustrated in Figure 1, carbon dioxide, a non-toxic substance, acting as solvent, co-solvent, or anti-solvent, is the most important fluid used in the supercritical fluid technology in extraction, separation, fractionation, micronization, and encapsulation processes applied to obtain extracts concentrated with bioactive compounds for food, pharmaceutical, and cosmetic applications [6, 7, 8, 9].

Figure 1.

Carbon dioxide applications.

Carbon dioxide has a critical temperature near to room temperature, contributing to the operating conditions (pressure and temperature) to extract thermolabile substances, such as bioactive compounds. In addition, this substance is non-polar and to enlarge the application spectrum to extract bioactive compounds, ethanol, water, or both are usually used as co-solvents. Moreover, carbon dioxide acts as co-solvent when in the mixture it is used more than 60% of ethanol or water, and as anti-solvent, when the solute extract is not soluble in carbon dioxide during the depressurizing step.

The information accuracy related to the physical (pressure, temperature, and density) and transport properties (diffusivity, viscosity) and the accuracy of thermodynamic and mass transfer relations used for the solvent, co-solvent, and solute reach directly the costs of investment in extraction/separation units in supercritical conditions. The thermodynamic phase equilibrium determines the limits for the mass transfer among different phases, which are involved in various processes. The cubic equations of state are the most commonly applied models for the correlation and prediction of phase equilibrium at high pressures and are available in major commercial process simulators. In addition, they are used to calculate other thermodynamic properties, for both pure substances and mixtures, among which, the liquid and vapor phases density, enthalpy, and entropy.

This chapter intends to show the recent application scenarios of the carbon dioxide use at high pressures as solvent, to obtain natural extracts enriched with bioactive compounds, including the use of water as co-solvent to enhance the mixture solvating power. In this chapter, the description of the experimental strategy used for the supercritical carbon dioxide extraction of bioactive compounds from açaí berry pulp was emphasized. The primary properties of pure carbon dioxide were also described and calculated using equations of state.

Advertisement

2. Diagrams of pure substances

2.1. P-T diagram

The pressure versus temperature (P-T) diagram describes the different aggregation states of pure substances called solid, liquid, and vapor/gas.

Figure 2 is a schematic representation of the P-T diagrams for carbon dioxide and the substances most commonly employed as co-solvent, ethanol, and water, in high-pressure extraction processes of bioactive compounds. The curves represent the boundaries (phase transition or phase equilibrium) between the different states, known as saturation curves. The curve between the solid and liquid phases is called fusion; the curve between solid and vapor phases is called sublimation and that one between liquid and vapor phases is called vapor pressure (also known as boiling curve).

Figure 2.

Solid-liquid-gas-supercritical fluid phase diagram. TP = triple point. CP = critical point. Pc = critical pressure. Tc = critical temperature. Tt = triple point temperature. Pt = triple point pressure.

The behavior of the thermodynamic diagrams of pure substances culminates in the determination of the reference equilibrium points that has great importance in the development of thermodynamic models for different processes applications. In the P-T diagram, there are two points: the triple point, where the three phases are in equilibrium and the critical point, which is particularly of fundamental interest for applications in processes that use solvents at high pressures.

The critical point of a pure substance is the maximum thermodynamic state reached by the saturation curve between liquid and vapor phases. When the substance is in the state above the critical temperature (Tc) and the critical pressure (Pc), it is called supercritical fluid, and when the pressure is above Pc and the temperature below Tc, the thermodynamic state is called subcritical liquid. The technology with fluids at high pressures consists in the use of substances that act like solvent when they are in the thermodynamic state near or above the critical point. The triple point of carbon dioxide is at pressure of 5.18 bar and at temperature of 216.58 K (−56.57°C), and the critical point is at pressure of 73.7 bar and at temperature of 304.15 K (31°C) [10].

2.2. P-ρ-T diagram

Density (ρ) is the most important thermodynamic property to define the solvating power of a solvent at high pressures, increasing the density of the solvent increases its solvating power. To better understand the influence of density on the solvating power to increase or decrease the solubility of an extract within a solvent at high pressures, one needs information concerning the density as a function of system pressure and temperature.

Figure 3 shows the schematic representation of the density behavior (ρ = 1/V) of a pure substance with temperature and pressure variations, where V is the specific volume (volume per mass unit). In Figure 3, the density versus pressure isotherms are presented in descending order from T1 to T9. The red line represents the saturation curve between the liquid and vapor phases. The highest point of the saturation curve is the critical point. The dotted line within the saturation curve is the two-phase region. In the saturation curve, there is a sudden difference in the density between the liquid and vapor phases.

Figure 3.

Pressure-density (P-ρ) phase diagram for carbon dioxide. CP = critical point (Pc, Tc, and ρc). CP = critical point (Pc, Tc, and ρc).

The behavior of the P-ρ-T diagram shows that the density at constant temperature increases with the increasing pressure and at constant pressure increases with the decreasing temperature. In the region near the critical point, small variations of pressure and/or temperature cause great variations in density. For carbon dioxide, the critical point is at the pressure of 73.7 bar and at the temperature of 304.15 K (31°C); it makes carbon dioxide the most applied solvent to extract thermo-sensible substances.

Below the critical temperature, in the subcritical region, the isotherms present two types of behavior: for the vapor region, at constant pressure, the density increases with the decreasing temperature and for the liquid region, the density varies very little with the temperature.

Advertisement

3. Supercritical fluid extraction

The extraction/separation processes applied to solid matrix using carbon dioxide as solvent are the most studied supercritical processes in the search for new natural products that have biological activity, according to numerous applications described in the literature [1, 4, 5, 6, 11, 12, 13, 14, 15, 16, 17, 18].

3.1. General process steps

Generally, the supercritical fluid extraction applied to a natural solid matrix consists of three steps: the system supply of solvent/co-solvent, the extraction unit, and the extract separation system from solvent/co-solvent. Figure 4 presents a general scheme of the supercritical fluid extraction unit without solvent recycle. The system supply of solvent/co-solvent consists by a booster air-driven fluid pump, a cooling bath, a co-solvent recipient, a co-solvent pump, and a mixer. The extract separation system from solvent/co-solvent consists by a control valve for extraction pressure reduction and a separation vessel to collect the extract.

Figure 4.

Scheme of a supercritical fluid extraction plant applying solvent/co-solvent. CO2 cylinder (1); cooling bath (2); booster (CO2 pump-3 and Compressor-4); mixer (5); CO-solvent pump (6); co-solvent recipient (7); extraction unit (8); control valve (V-5); separation vessel (9); flow meter (10).

Regarding the extraction, the supercritical solvent continuously flows through a fixed bed of solid particles and dissolves the extractable components of the solid. The solvent is fed into the extractor and evenly distributed at the inlet of the fixed bed. The system solvent and soluble components leave the extractor and feed the precipitator/separator, where the solvent products are separated by expansion (depressurizing), since at low pressures the density of the solvent sharply decreases, therefore it decreases the solubilizing power of the solvent as well and the products precipitate.

The choice of the operating condition (P and T) is a determining factor that contributes to the maximization of the extracts solubility in the supercritical solvent, and consequently the extraction yields. Thus, increasing the density of the supercritical fluid, the solubility of the solvent maximizes. The solubility increasing can also occur when a co-solvent is added, which changes the solvent power and, in this way, the new solvent is a mixture [19, 20].

To design a high-pressure fluid extraction process of valuable compounds from new natural solid matrices, it is necessary to define the size of the extraction unit and some important parameters have to be determined to obtain the optimum process conditions for each application. Brunner [19] and Kiran et al. [21] described the most important parameters, and among the variables that determine the process, operating conditions (pressure and temperature), amount of solvent, conditions of solvent removal from extract (precipitation), pretreatment of solid matrix, and other mass transfer parameters can be highlighted.

In general, the parameters that define the behavior of the mass transfer at processes at high pressures are related to the configuration of the bed: particle size, height, and diameter, preparation of the raw material, solvent flow, among others, which contribute to define the shape of the kinetic extraction curves. The phenomenological discussions about supercritical fluid extraction mass transfer applied to solid matrices have been discussed in the literature [19, 22, 23, 24].

3.2. Supercritical carbon dioxide extraction of bioactive compounds: a case study

The experimental strategy used for the supercritical carbon dioxide extraction process of bioactive compounds is based on the previous results collected by our research group in obtaining açai extracts [25].

Açaí is a dark purple, berry-like fruit from typical Amazon palm tree Euterpe oleracea Mart., integrated in the daily dietary habit of the native people.

Recently, many studies have suggested its use as a functional food or food ingredient due to its antioxidant activity, explained by the high content of phenolic compounds, such as anthocyanins, specially cyanidin-3-glucoside and cyanidin-3-rutinoside, flavones, and phenolic acids [26, 27, 28]. Phenolic constituents are generally associated with health-promoting properties and prevention of diseases [29, 30, 31, 32, 33]. Anthocyanins constitute a group of pigments, also important in the food industry, for the replacement of artificial colors [34, 35, 36].

The supercritical extraction experiments of the lyophilized açaí pulp under development were carried out in a Spe-ed™ SFE commercial unit (Allentown, PA, USA: model 7071 from Applied Separations) which is coupled to the solvent + co-solvent delivery system of Laboratory of Supercritical Extraction (LABEX), Faculty of Food Engineering-UFPA. The schematic representation of the supercritical extraction system is shown in Figure 5.

Figure 5.

Experimental protocol for the bioactive compounds extraction.

The first step consisted of the extraction with supercritical CO2 (pure) to obtain extracts rich in fatty acids and byproducts of the residual solid matrix (defatted pulp). Analyses of the content of bioactive compounds (anthocyanins and total phenolic compounds) were performed. The second stage that is under development consists of the extraction with supercritical CO2 combined with water as co-solvent applied to the residual solid matrix to obtain extracts concentrated in anthocyanins.

In the first stage, Batista et al. [25] subjected samples of lyophilized açaí pulp to the supercritical carbon dioxide extraction process. Among the results, the study of the process variables (temperature, pressure, and solvent density) that maximize the extraction yield of açaí oil, the quantification of the total anthocyanins content and total phenolic compounds content, and the evaluation of the allelopathic potential of the extracts obtained can be highlighted.

Figure 6 shows the experimental results of the 50, 60, and 70°C isotherms on dry basis and their standard deviations. In this study, the highest global yield was equal to 45.4 ± 0.58%, obtained at 70°C and 490 bar, while the lowest global yield was equal to 9.07 ± 0.6%, obtained at 60°C and 190 bar. The density is related to the CO2 solubility and is directly influenced by temperature and pressure. Here, the most important parameter was the density, since when it increased (in all isotherms), the oil global yield also increased.

Figure 6.

Global yield on dry basis versus density of supercritical CO2 extraction of lyophilized açaí berry oil. () 50°C, () 60°C, and () 70°C isotherms [17].

The analysis of the phenolic compounds in the lyophilized açaí berry pulp showed an increase in its content comparing the samples before and after the extraction with supercritical CO2, in different conditions. Its highest content was equal to 7565 mg/100 g and was obtained in the condition of 70°C and 350 bar. The standard deviation for each condition was lower than 0.18% (Figure 7). Regarding anthocyanins, there was also an increase in its content. Before the extraction with supercritical CO2, the total concentration was equal to 96.58 ± 0.11 mg/100 g, and after the extraction, it reached up to 137.5 mg/100 g of sample in the condition of 50°C and 220 bar. The standard deviation was lower than 0.15%. Figure 8 shows the values obtained and their specific deviation. It can be inferred that since the extracts of the lyophilized acaí berry pulp obtained by supercritical CO2 are rich in phenolic compounds and anthocyanins, it presents great potential in nutraceutical applications.

Figure 7.

Total phenolic compounds content in lyophilized açaí berry pulp before and after extraction with supercritical CO2. () 50°C, () 60°C, and () 70°C isotherms [17].

Figure 8.

Total anthocyanins compounds content in lyophilized açaí berry pulp before and after extraction with supercritical CO2. () 50°C, () 60°C, and () 70°C isotherms [17].

The results of the fatty acid profile analysis of açaí extracts indicate a low saturated/unsaturated ratio except for the condition of 70°C and 320 bar. The SFA content reached 99.67% at the condition of 70°C and 320 bar.

Advertisement

4. High-pressure carbon dioxide properties

4.1. Thermodynamic properties

The influence of the density in the solvation power by the tunable operating conditions (P, T) is the most important thermodynamic effect in the high-pressure fluid processes.

Above the critical point, the supercritical extraction process can operate over a wide range of operating conditions (P, T) and the simplest density behavior can be obtained through an isotherm, being possible to select a wide range of operating pressures, as shown in Figure 3 of the item 2.2 for the isotherms T1 > T2 > T3 > T4 > T5.

The density is defined by the inverse of specific volume, and for practical purpose, could be calculated by volumetric properties (P-V-T) using equation of state.

4.1.1. P-V-T diagram calculation with equations of state

To describe the P-V-T diagram behavior, it is necessary to use precise equations of state (EOS) with specific parameters for pure substances. In the case of carbon dioxide, the equations of Bender [19] and Span and Wagner [37] are the most used. The Bender equation is presented below, where the parameters were determined from experimental PVT data of carbon dioxide. Table 1 shows the parameters of the Bender equation.

E1
iaiiai
10.22488558110.12115286
20.13717965 × 103120.10783386 × 10−3
30.14430214 × 105130.43962336 × 10−2
40.29630491 × 10714−0.36505545 × 108
50.20606039 × 109150.19490511 × 1011
60.45554393 × 10−116−0.29186718 × 1013
70.77042840 × 10−2170.24358627 × 108
80.40602371 × 10518−0.37546530 × 1011
90.40029509190.11898141 × 1014
10−0.39436077 × 10−3200.50000000 × 101

Table 1.

Bender equation constants for CO2 [19].

where

E2
E3
E4
E5
E6
E7
E8
E9

Figure 9 shows the calculation with Bender equation [19] of state for the P-V-T diagram isotherms and saturation curve, including an isotherm close to the critical temperature of the carbon dioxide. The calculations were performed using a Microsoft Excel spreadsheet. The equation presents accuracy in calculations when compared to data taken from IUPAC International Thermodynamic Table.

Figure 9.

P-V-T diagram of carbon dioxide calculated with Bender EOS and compared to IUPAC data (symbols).

However, for applications of supercritical technology, it is necessary to calculate other thermodynamic properties. The thermodynamic properties of the pure solvent (density, enthalpy, and entropy) and the thermodynamic properties of the solute/solvent mixture, among which the equilibrium compositions, enthalpies, and mixing entropies, must be calculated in the operating conditions throughout the process. The cubic equation of state, also called Van der Waals type equation, represents an alternative, since the Bender-type equation described above is complex. In these cases, the cubic equations of state of Peng-Robinson (PR) [38] and Soave Redlich-Kwong (SRK) [39] are presented as the most commonly applied options in process simulations (Table 2). These equations of state use various thermodynamic properties and the following physical properties of the pure substance: critical pressure, critical temperature, and the acentric factor, which are tabulated, in the case of carbon dioxide.

Table 2.

Cubic equations of state.

Table 3 shows the calculated values of the carbon dioxide densities for some isotherms above the critical point using the equations of Peng-Robinson [38] and Soave-Redlich-Kwong [39]. The computational package PE 2000 developed by Pfohl et al. [40] was used for calculations. The results are compared to data taken from IUPAC International Thermodynamic Table and from NIST Chemistry Webbook (NIST Standard Reference Database). The Peng-Robinson equation of state presented the best results for the carbon dioxide density calculation in the conditions of pressure and temperature of Table 3 when compared with different databases.

Pressure (bar)Temperature (°C/K)CO2 density (kg/m3)
PRSRKNISTIUPAC
10036.85/310617.3563.0683.4686.5
200847.8763.8855.5857.0
300941.1846.6921.5922.7
10046.85/320418.1390.6444.6449.4
200781.5707.9801.5803.1
250845.3763.8848.0849.5
300893.0805.9882.4883.7
400963.2868.2933.2934.4
10066.85/340260.5246.2258.1258.6
200643.2589.3678.7680.5
250731.7666.7751.9753.3
300794.4721.8800.6801.8
400882.9799.6866.7867.9

Table 3.

Carbon dioxide density calculated with different equations of state.

Figure 10 shows the calculation with Peng-Robinson [38] equation of state for P-V-T diagram isotherms and saturation curve, including an isotherm close to the critical temperature of the carbon dioxide. The Peng-Robinson equation of state was able to describe all the phases of the carbon dioxide P-V-T diagram for the isotherms studied when compared to data taken from IUPAC International Thermodynamic Table.

Figure 10.

PVT diagram of carbon dioxide calculated with Peng-Robinson EOS and compared to IUPAC data (symbols).

From a process point of view, the accuracy of the cubic equations of state was good, considering that the operating conditions commonly applied in CO2 extraction at high pressures are close to the values of temperature and pressure used in Table 3.

4.2. Other high-pressure carbon dioxide properties

The application of the high-pressure fluid extraction technologies in both laboratory and industrial scales requires not only the knowledge of the physical and thermodynamic properties of the solvent, but also requires the understanding of thermal and transport properties behavior. Among them, the most commonly cited are viscosity, diffusivity, thermal conductivity, and dielectric constant.

The dielectric constant describes the ability of a solvent to be polarized. The dielectric constant value is associated with the ability to dissolve electrolytes or polar compounds. The dielectric constant increases with temperature for most substances [41]. The dielectric constant of supercritical carbon dioxide with approximate value of a hydrocarbon alone does not characterize it as an important solvent; it only identifies it as a non-polar substance. Its solvation power is mainly related to the considerable increase of its density in the supercritical region with the properties as viscosity and diffusivity complementing the characteristics that makes supercritical carbon dioxide a differentiated solvent.

Under supercritical conditions, the thermal conductivity is influenced by both temperature and pressure and at constant pressure this property increases with increasing temperature, and on the other hand, at constant temperature, the thermal conductivity increases with pressure [42].

Carbon dioxide and other supercritical solvents have low viscosity and high diffusivity values. The viscosity and thermal conductivity of gases and liquids differ by one to two orders of magnitude, and the diffusivity values of gases and liquids differ by four orders of magnitude [41].

In the supercritical state, the substances have intermediate characteristics between the properties of a gas and a liquid, which contributes to more favorable hydrodynamic properties than the liquids, with diffusion coefficients close to those of a gas, which provides a fast and efficient mass transfer. Another feature of the supercritical fluid includes its low viscosity, which facilitates the penetration of the fluids into a solid matrix. Therefore, high diffusivity and low viscosity lead to a faster extraction time providing a dissolving power so that the supercritical fluid is considered a solvent.

Table 4 shows that supercritical fluids are characterized by transport properties (viscosity and diffusivity) between gases and liquids. The viscosity of a supercritical fluid is smaller than the viscosity of a gas and the diffusivity of the liquid is greater than the diffusivity of a supercritical fluid. In summary, the scheme of Figure 11 shows the basic properties of supercritical carbon dioxide, which become fundamental in high pressures extraction processes.

UnitGasSCFLiquid
ViscosityPa s10−510−4 to 10−510−3
Diffusivitycm2/s10−110−3 to 10−410−6

Table 4.

Order of magnitude of transport properties.

Figure 11.

Carbon dioxide properties.

Advertisement

5. High-pressure carbon dioxide applications

The most cited drawback of using supercritical carbon dioxide as solvent is the high investment cost for equipment acquisition and operation. However, the extraction with supercritical carbon dioxide presents a lower extraction time because of its diffusivity and low surface tension, greater selectivity in the compounds of interest and little or no consumption of organic solvents [43, 44, 45, 46].

5.1. Essential oil extraction

Essential oils have been used to prevent or treat human diseases for several centuries. The extraction of the volatile compounds present in edible or medicinal aromatic plants is generally carried out by hydrodistillation; however, the authors report that some compounds may undergo hydrolysis during the extraction period [47]. Although there are other techniques for isolating essential oils, the use of CO2 as supercritical fluid has been considered a “chemically green” unconventional extraction technique that does not alter or degrade the substances present in oils because it uses relatively low temperatures in the extraction process.

Guan et al. [48] performed a comparison between conventional extraction methods and extraction with supercritical CO2 and observed that the extraction using supercritical CO2 as solvent was less effective with recovery rate of 57.36% for eugenol compared to steam distillation with 58.2%, but it was more effective when compared to hydrodistillation with recovery rate of 48.82% and Soxhlet extraction with 57.24%. However, when compared with the extraction of eugenol acetate, the extraction with supercritical CO2 presented higher yields in relation to the other extraction methods.

Extraction of chemically active volatile molecules with supercritical CO2 is very widespread [49, 50, 51]. This is due to the possible applications as agents that promote biological activities [52], such as antioxidant activity [53], anti-inflammatory activity [54], insecticidal activity [55], and phytotoxic activity [56]. In Table 5, some studies in the literature on the extraction of essential oils with supercritical CO2 can be observed.

Aromatic plantBioactive compoundsReferences
Juniperus communis L.Germacrene D and 1-octadecene.[57]
Satureja hortensisγ-Terpinene, thymol, and carvacrol[58]
Myrtus communis L.Methyl eugenol, 1,8 cineole, and beta- caryophyllene[59]
Leptocarpha rivularisα-thujone, β-caryophyllene, and caryophyllene oxide[60]
Piper nigrum L.β-caryophyllene, limonene, sabinene, 3-carene, β-pinene, and α-pinene[53]
Camellia sinensis L.9-Thiabicyclo[3.3.1]non-7-en-2-ol, tricosane, heneicosane, tetracosane, and dibutyl phthalate[61]

Table 5.

Published studies on extraction of essential oils using CO2 as supercritical fluid.

As given above, it is observed that the process of extraction of essential oils using supercritical CO2 is ecologically a cleaner method than the conventional ones, and it has been seen as one of the most viable alternatives.

5.2. Phytosterols extraction

Phytosterols (plant sterols) are non-volatile triterpenes. The great majority of these compounds are formed by carbon with one or two carbon-carbon double bonds [62]. And the most common phytosterols found in plants are β-sitosterol, campesterol, and stigmasterol [63]. These compounds have various biological activities such as lowering the total serum or plasma cholesterol levels and the low-density lipoprotein cholesterol levels. In addition, they have antitumor activities inhibiting the development of colon cancer [64, 65].

For the extraction of these phytosterols, the supercritical CO2 has been shown to be an efficient technique for extraction of fixed oils from vegetable matrices. Studies report that this solvent may be superior to obtain oils in relation to the conventional extraction, exhibiting a recovery rate of phytosterols of 836.5 mg/100 g versus 30.5/100 g using a Soxhlet-type extraction apparatus [66]. A very important parameter for the extraction of phytosterols with supercritical CO2 is the increase of the pressure, because it favors the solvation power and consequently the solubilization of these compounds, with a recovery rate of up to 7262.80 mg.kg−1 [67]. Table 6 presents some articles published in the literature on the extraction of phytosterols using supercritical CO2.

PlantsPhytosterolsReferences
Cucurbita pepo convarDesmosterol, campesterol, stigmasterol, β-sitosterol, spinasterol, Δ7,22,25-stigmastatrienol, Δ7-stigmastenol, Δ7,25-stigmastadienol, and Δ7-avenasterol[68]
Brassica napusβ-sitosterol, campesterol and brassicasterol[69]
Hippophae rhamnoides L.β-sitosterol[70]
Sesamum indicum L.β-sitosterol + sitostanol, cholesterol, campesterol + campestanol +24-methylene cholesterol, Δ-5 avenasterol and stigmasterol, while lower levels of Δ-5,24 stigmastadienol, brassicasterol, clerosterol + Δ-5-23 stigmastadienol, Δ-7 avenasterol, eritrodiol and Δ-7 stigmasterol[71]

Table 6.

Phytosterols extracted using supercritical CO2.

5.3. Carotenoid extraction

Carotenoids are tetraterpenes present in plants that have several applications in food [72], cosmetic [73], and pharmaceutical [74] areas. Some of the benefits provided by these pigments are: antioxidant activity and strengthening of the immune system against degenerative diseases such as cancer, cardiovascular diseases, muscle degeneration, inflammation, hypertension, insulin resistance and obesity [75, 76].

Because of their hydrophobic characteristics, carotenoids are usually extracted using organic solvents such as hexane and petroleum ether. Carotenoids with hydrophilic characteristics can be obtained with more polar solvents such as acetone, ethanol, and ethyl acetate [77]. The techniques used to extract this compound may be maceration, Soxhlet, microwave-assisted extraction [78, 79], ultrasound-assisted extraction [80], pressurized liquid extraction [81, 82], and supercritical fluid technology using low temperature. The process is performed in a short time in relation to conventional processes and does not use toxic solvents to collect the compound of interest [83]. In Table 7, some published works that used supercritical CO2 to obtain carotenoids are shown.

Raw materialCarotenoidReferences
Tomato juiceLycopene and β-carotene[84]
Hemerocallis distichaLutein and zeaxanthin[85]
Dunaliella salina9-cis and trans-β-carotenes[86]
Undaria pinnatifida, Haematococcus pluvialis, and Chlorella vulgarisFucoxanthin, astaxanthin, lutein, and β-carotene[87]
Fucus serratus and Laminaria digitataXanthophyll and fucoxanthin[88]

Table 7.

Published studies about carotenoid extraction using CO2.

5.4. Fatty acids extraction

Fatty acids (FA) belong to the lipid class and differ according to the size of the C chain (2–80), the presence or absence of double bonds (saturated or unsaturated) or their radical function as the groups hydroxyl, epoxy, and halogen atoms [89]. Ingestion of FA is essential to have an adequate energy balance in the human organism in addition to reducing the risk of some diseases such as diabetes [90], hypertension [91], coronary diseases [92], and inflammation [93].

Some of its applications are in food, nutraceutical, and cosmetic industries, and in the production of lubricants, biodiesel, and glycerol [94, 95, 96]. Some of the extraction methods that can be used to obtain FA are mechanical extraction [97], extraction by supercritical fluids and organic solvent [98], microwave-assisted extraction [99], and supercritical CO2 extraction [98]. Table 8 shows some studies that used supercritical CO2 to obtain the main classes of the FA group.

Raw materialFatty acidReference
Cucurbita ficifolia, Bouchéω6-linoleic acid, palmitic acid, oleic acid[100]
Farfantepenaeus paulensisPalmitic acid, oleic acid, stearic acid, palmitoleic acid, and linoleic acid[101]
Cannabis sativa L.Linoleic acid and linolenic acid[102]
Chaetoceros muelleriMyristic acid, palmitic acid, and palmitoleic acid[103]
Saw PalmettoLauric acid, mystiric acid, and oleic acid[104]

Table 8.

Published studies about fatty acids extraction using CO2.

5.5. Extraction with supercritical CO2 modified with ethanol/water

The extraction with supercritical CO2 modified with water in different proportions is carried out to obtain bioactive compounds of high polarity, because as mentioned above, CO2 is an non-polar molecule and does not have “power” to solubilizate polar substances as is the case of the phenolic compounds (phenolic acids and flavonoids) [105, 106]. As previously mentioned, parameters of processes, such as temperature and pressure, can influence the extraction of bioactive compounds. Besides these two parameters, anthocyanins are also important for the extraction of phenolic compounds. Solvent flow rate, percentage of co-solvent, co-solvent type (ethanol or water), and extraction time are parameters that directly implicate the yield of these substances at the end of the extraction process [107].

Further examples of extraction of phenolic compounds using supercritical CO2 modified with co-solvents can be analyzed in the studies [106, 108, 109]. They extracted various flavonoids like quercetin, catechin, epicatechin from cranberry, blueberry, and raspberry. Table 9 presents some studies in which supercritical CO2 modified with ethanol/water were used to extract chemically active phenolic compounds.

Raw materialCompoundsReferences
Myrciaria caulifloraAnthocyanin[8]
Elderberry (Sambucus nigra)Anthocyanins[110]
Vitis vinifera var. Malvasia neraAnthocyanins[111]
Arrabidaea chicaAnthocyanins and luteolin[112]
Scutellaria lateriflora L.Baicalin, dihydrobaicalin, lateriflorin, ikonnikoside I, scutellarin, oroxylin A 7-O-glucuronide, oroxylin A, baicalein, wogonin[113]
Vaccinium myrtillus L.Delphinidin 3-O-galactoside, delphinidin 3-O-glucoside, cyanidin 3-O-galactoside, delphinidin 3-O-arabinoside, cyanidin 3-O-glucoside, petunidin 3-O-galactoside, cyanidin 3-O-arabinoside, petunidin 3-O-glucoside, peonidin 3-O-galactoside, petunidin 3-O-arabinoside, peonidin 3-O-glucoside, malvidin 3-O-galactoside, peonidin 3-O-arabinoside, malvidin 3-O-glucoside, malvidin 3-O-arabinoside and malvidin 3-O-xyloside[114]

Table 9.

Phenolic compounds extracted with supercritical CO2 modified with ethanol/water.

Advertisement

6. Conclusion

Carbon dioxide can be safely applied in high-pressure extraction processes due to its numerous advantageous characteristics. It is neither toxic nor inflammable, being able to act as solvent, co-solvent, or anti-solvent, which allows it to be used in natural products and foodstuff processing that require treatments intending to preserve their nutritional and sensory properties. Since it is a non-polar substance, it is suitable for extraction of non-polar bioactive compounds when used in pure form. When associated with a polar co-solvent, it can be used for extraction of polar compounds such as phenolic compounds and anthocyanins. Therefore, these characteristics make carbon dioxide the most important fluid used in high-pressure processes for extraction, separation, fractionation, micronization, and encapsulation, applied to obtain concentrated extracts with bioactive compounds for food, pharmaceutical, and cosmetic applications.

Advertisement

Acknowledgments

Costa W.A. (1427204/2014), Cunha V.M.B. (1566277/2015), Oliveira M.S. (1662230/2016), Silva M.P. (1636612/2016), Bezerra F.W.F. (1718822/2017), Pinto R.H.H. (1662902/2016) thank CAPES for the doctorate scholarship.

References

  1. 1. Sahena F, Zaidul ISM, Jinap S, Karim AA, Abbas KA, Norulaini NAN, Omar AKM. Application of supercritical CO2 in lipid extraction—A review. Journal of Food Engineering. 2009;95:240-253. DOI: 10.1016/j.jfoodeng.2009.06.026
  2. 2. Vardanega R, Prado JM, Meireles MAA. Adding value to agri-food residues by means of supercritical technology. Journal of Supercritical Fluids. 2015;96:217-227. DOI: 10.1016/j.supflu.2014.09.029
  3. 3. Fornari T, Vázquez L, Torres CF, Ibáñez E, Señoráns FJ, Reglero G. Countercurrent supercritical fluid extraction of different lipid-type materials: Experimental and thermodynamic modeling. Journal of Supercritical Fluids. 2008;45:206-212. DOI: 10.1016/j.supflu.2008.03.001
  4. 4. Rubio-Rodríguez N, Beltrán S, Jaime I, de Diego SM, Sanz MT, Carballido JR. Production of omega-3 polyunsaturated fatty acid concentrates: A review. Innovative Food Science & Emerging Technologies. 2010;11:1-12. DOI: 10.1016/j.ifset.2009.10.006
  5. 5. Herrero M, Ibáñez E. Green processes and sustainability: An overview on the extraction of high added-value products from seaweeds and microalgae. Journal of Supercritical Fluids. 2015;96:211-216. DOI: 10.1016/j.supflu.2014.09.006
  6. 6. Herrero M, Mendiola JA, Cifuentes A, Ibáñez E. Supercritical fluid extraction: Recent advances and applications. Journal of Chromatography. A. 2010;1217:2495-2511. DOI: 10.1016/j.chroma.2009.12.019
  7. 7. Beh CC, Mammucari R, Foster NR. Lipids-based drug carrier systems by dense gas technology: A review. Chemical Engineering Journal. 2012;188:1-14. DOI: 10.1016/j.cej.2012.01.129
  8. 8. Santos DT, Albarelli JQ, Beppu MM, Meireles MAA. Stabilization of anthocyanin extract from Jabuticaba skins by encapsulation using supercritical CO2 as solvent. Food Research International. 2013;50:617-624. DOI: 10.1016/j.foodres.2011.04.019
  9. 9. Keven Silva E, Meireles MAA. Encapsulation of food compounds using supercritical technologies: Applications of supercritical carbon dioxide as an antisolvent. Food and Public Health. 2014;4:247-258. DOI: 10.5923/j.fph.20140405.06
  10. 10. Smith R, Inomata H, Peters C. Introduction to supercritical fluids: A spreadsheet-based approach. Supercritical Fluid Science and Technology. 2013;4:55-119. DOI: 10.1016/B978-0-444-52215-3.00002-7
  11. 11. Casas L, Mantell C, Rodríguez M, Torres A, Macías FA, Martínez de la Ossa E. Effect of the addition of cosolvent on the supercritical fluid extraction of bioactive compounds from Helianthus annuus L. Journal of Supercritical Fluids. 2007;41:43-49. DOI: 10.1016/j.supflu.2006.09.001
  12. 12. Passos CP, Silva RM, Da Silva FA, Coimbra MA, Silva CM. Supercritical fluid extraction of grape seed (Vitis vinifera L.) oil. Effect of the operating conditions upon oil composition and antioxidant capacity. Chemical Engineering Journal. 2010;160:634-640. DOI: 10.1016/j.cej.2010.03.087
  13. 13. Pereira CG, Meireles MAA. Supercritical fluid extraction of bioactive compounds: Fundamentals, applications and economic perspectives. Food and Bioprocess Technology. 2010;3:340-372. DOI: 10.1007/s11947-009-0263-2
  14. 14. Moraes MN, Zabot GL, Prado JM, Meireles MAA. Obtaining antioxidants from botanic matrices applying novel extraction techniques. Food and Public Health. 2013;3:195-214. DOI: 10.5923/j.fph.20130304.04
  15. 15. Danh LT, Han LN, Triet NDA, Zhao J, Mammucari R, Foster N. Comparison of chemical composition, antioxidant and antimicrobial activity of lavender (Lavandula angustifolia L.) essential oils extracted by supercritical CO2, hexane and hydrodistillation. Food and Bioprocess Technology. 2013;6:3481-3489. DOI: 10.1007/s11947-012-1026-z
  16. 16. Rodrigues RB, Lichtenthäler R, Zimmermann BF, Papagiannopoulos M, Fabricius H, Marx F, Maia JGS, Almeida O. Total oxidant scavenging capacity of Euterpe oleracea Mart. (Açaí) seeds and identification of their polyphenolic compounds. Journal of Agricultural and Food Chemistry. 2006;54:4162-4167. DOI: 10.1021/jf058169p
  17. 17. Piras A, Rosa A, Marongiu B, Atzeri A, Dessì MA, Falconieri D, Porcedda S. Extraction and separation of volatile and fixed oils from seeds of Myristica fragrans by supercritical CO2: Chemical composition and cytotoxic activity on Caco-2 cancer cells. Journal of Food Science. 2012;77:C448-C453. DOI: 10.1111/j.1750-3841.2012.02618.x
  18. 18. de Oliveira MS, da Costa WA, Pereira DS, Botelho JRS, de Alencar Menezes TO, de Aguiar Andrade EH, da Silva SHM, da Silva Sousa Filho AP, de Carvalho RN. Chemical composition and phytotoxic activity of clove (Syzygium aromaticum) essential oil obtained with supercritical CO2. Journal of Supercritical Fluids. 2016;118:185-193. DOI: 10.1016/j.supflu.2016.08.010
  19. 19. Brunner G. Gas Extraction. Heidelberg: Steinkopff; 1994. DOI: 10.1007/978-3-662-07380-3
  20. 20. Kiran E, Brennecke JF. Current state of supercritical fluid science and technology. In: Comstock MJ, editor. Supercritical Fluid Engineering Science, Fundamentals and Applications. 514th ed. California: Los Angeles; 1992. pp. 1-8. DOI: 10.1021/bk-1992-0514.ch001
  21. 21. Kiran E, Debenedetti PG, Peters CJ. Supercritical Fluids. Fundamentals and Applications. Dordrecht: Springer Netherlands; 2000. DOI: 10.1007/978-94-011-3929-8
  22. 22. Meireles MAA. Extracting Bioactive Compounds for Food Products: Theory and Applications. 1st ed. London, New York: CRC Press Taylor & Francis Group Boca Raton; 2008
  23. 23. Jesus SP, Meireles MAA. Supercritical fluid extraction: A global perspective of the fundamental concepts of this eco-friendly extraction technique. In: Chemat F, Vian MA, editors. Green Chemistry and Sustainable Technology. Berlin, Heidelberg: Springer Berlin Heidelberg; 2014. pp. 39-72. DOI: 10.1007/978-3-662-43628-8_3
  24. 24. Sovová H, Stateva RP. Supercritical fluid extraction from vegetable materials. Reviews in Chemical Engineering. 2011;27:79-156. DOI: 10.1515/REVCE.2011.002
  25. 25. de Batista CCR, de Oliveira MS, Araújo ME, Rodrigues AMC, Botelho JRS, da Silva Souza Filho AP, Machado NT, Carvalho RN. Supercritical CO2 extraction of açaí (Euterpe oleracea) berry oil: Global yield, fatty acids, allelopathic activities, and determination of phenolic and anthocyanins total compounds in the residual pulp. Journal of Supercritical Fluids. 2016;107:364-369. DOI: 10.1016/j.supflu.2015.10.006
  26. 26. Dias ALS, Rozet E, Chataigné G, Oliveira AC, Rabelo CAS, Hubert P, Rogez H, Quetin-Leclercq J. A rapid validated UHPLC–PDA method for anthocyanins quantification from Euterpe oleracea fruits. Journal of Chromatography B. 2012;907:108-116. DOI: 10.1016/j.jchromb.2012.09.015
  27. 27. Gouvêa ACMS, De Araujo MCP, Schulz DF, Pacheco S, Godoy RLDO, Cabral LMC. Anthocyanins standards (cyanidin-3-O-glucoside and cyanidin-3-O-rutinoside) isolation from freeze-dried açaí (Euterpe oleraceae Mart.) by HPLC. Ciencia e Tecnologia de Alimentos. 2012;32:43-46. DOI: 10.1590/S0101-20612012005000001
  28. 28. Lichtenthäler R, Rodrigues RB, Maia JGS, Papagiannopoulos M, Fabricius H, Marx F. Total oxidant scavenging capacities of Euterpe oleracea Mart. (Açaí) fruits. International Journal of Food Sciences and Nutrition. 2005;56:53-64. DOI: 10.1080/09637480500082082
  29. 29. Kang J, Thakali KM, Xie C, Kondo M, Tong Y, Ou B, Jensen G, Medina MB, Schauss AG, Wu X. Bioactivities of açaí (Euterpe precatoria Mart.) fruit pulp, superior antioxidant and anti-inflammatory properties to Euterpe oleracea Mart. Food Chemistry. 2012;133:671-677. DOI: 10.1016/j.foodchem.2012.01.048
  30. 30. Gordon A, Cruz APG, Cabral LMC, de Freitas SC, Taxi CMAD, Donangelo CM, de Andrade Mattietto R, Friedrich M, da Matta VM, Marx F. Chemical characterization and evaluation of antioxidant properties of Açaí fruits (Euterpe oleraceae Mart.) during ripening. Food Chemistry. 2012;133:256-263. DOI: 10.1016/j.foodchem.2011.11.150
  31. 31. Vidigal MCTR, Minim VPR, Carvalho NB, Milagres MP, Gonçalves ACA. Effect of a health claim on consumer acceptance of exotic Brazilian fruit juices: Açaí (Euterpe oleracea Mart.), Camu-camu (Myrciaria dubia), Cajá (Spondias lutea L.) and Umbu (Spondias tuberosa Arruda). Food Research International. 2011;44:1988-1996. DOI: 10.1016/j.foodres.2010.11.028
  32. 32. Hogan S, Chung H, Zhang L, Li J, Lee Y, Dai Y, Zhou K. Antiproliferative and antioxidant properties of anthocyanin-rich extract from açai. Food Chemistry. 2010;118:208-214. DOI: 10.1016/j.foodchem.2009.04.099
  33. 33. Kang J, Li Z, Wu T, Jensen GS, Schauss AG, Wu X. Anti-oxidant capacities of flavonoid compounds isolated from acai pulp (Euterpe oleracea Mart.). Food Chemistry. 2010;122:610-617. DOI: 10.1016/j.foodchem.2010.03.020
  34. 34. Xu Z, Wu J, Zhang Y, Hu X, Liao X, Wang Z. Extraction of anthocyanins from red cabbage using high pressure CO2. Bioresource Technology. 2010;101:7151-7157. DOI: 10.1016/j.biortech.2010.04.004
  35. 35. Cerón IX, Higuita JC, Cardona CA. Design and analysis of antioxidant compounds from Andes berry fruits (Rubus glaucus Benth) using an enhanced-fluidity liquid extraction process with CO2 and ethanol. Journal of Supercritical Fluids. 2012;62:96-101. DOI: 10.1016/j.supflu.2011.12.007
  36. 36. Santos DT, Veggi PC, Meireles MAA. Optimization and economic evaluation of pressurized liquid extraction of phenolic compounds from Jabuticaba skins. Journal of Food Engineering. 2012;108:444-452. DOI: 10.1016/j.jfoodeng.2011.08.022
  37. 37. Span R, Wagner W. A new equation of state for carbon dioxide covering the fluid region from the triple-point temperature to 1100 K at pressures up to 800 MPa. Journal of Physical and Chemical Reference Data. 1996;25:1509-1596. DOI: 10.1063/1.555991
  38. 38. Peng D-Y, Robinson DB. A new two-constant equation of state. Industrial and Engineering Chemistry Fundamentals. 1976;15:59-64. DOI: 10.1021/i160057a011
  39. 39. Soave G. Equilibrium constants from a modified Redlich-Kwong equation of state. Chemical Engineering Science. 1972;27:1197-1203. DOI: 10.1016/0009-2509(72)80096-4
  40. 40. Pfohl O, Petkov S, Brunner G. “PE” quickly makes available the newest equations of state via the internet. Industrial and Engineering Chemistry Research. 2000;39:4439-4440. DOI: 10.1021/ie000778t
  41. 41. Brunner G. Hydrothermal and Supercritical Water Processes. Amsterdam: Supercritical fluid science and technology; 2014. DOI: 10.1016/B978-0-444-59413-6.00009-1
  42. 42. Bertucco A, Vetter G. High Pressure Process Technology: Fundamentals and Applications. United Kingdom: Elsevier Science & Technology; 2001. DOI: 10.1016/S0926-9614(01)80016-2
  43. 43. Bimakr M, Rahman RA, Taip FS, Ganjloo A, Salleh LM, Selamat J, Hamid A, Zaidul ISM. Comparison of different extraction methods for the extraction of major bioactive flavonoid compounds from spearmint (Mentha spicata L.) leaves. Food and Bioproducts Processing. 2011;89:67-72. DOI: 10.1016/j.fbp.2010.03.002
  44. 44. Eller FJ, Cermak SC, Taylor SL. Supercritical carbon dioxide extraction of cuphea seed oil. Industrial Crops and Products. 2011;33:554-557. DOI: 10.1016/j.indcrop.2010.12.017
  45. 45. Ruttarattanamongkol K, Siebenhandl-Ehn S, Schreiner M, Petrasch AM. Pilot-scale supercritical carbon dioxide extraction, physico-chemical properties and profile characterization of Moringa oleifera seed oil in comparison with conventional extraction methods. Industrial Crops and Products. 2014;58:68-77. DOI: 10.1016/j.indcrop.2014.03.020
  46. 46. Ledesma-Hernandez B, Herrero M. Bioactive Compounds from Marine Foods. Chichester, UK: John Wiley & Sons Ltd; 2013. DOI: 10.1002/9781118412893
  47. 47. Jiao J, Fu Y-J, Zu Y-G, Luo M, Wang W, Zhang L, Li J. Enzyme-assisted microwave hydro-distillation essential oil from Fructus forsythia, chemical constituents, and its antimicrobial and antioxidant activities. Food Chemistry. 2012;134:235-243. DOI: 10.1016/j.foodchem.2012.02.114
  48. 48. Guan W, Li S, Yan R, Tang S, Quan C. Comparison of essential oils of clove buds extracted with supercritical carbon dioxide and other three traditional extraction methods. Food Chemistry. 2007;101:1558-1564. DOI: 10.1016/j.foodchem.2006.04.009
  49. 49. Conde-Hernández LA, Espinosa-Victoria JR, Trejo A, Guerrero-Beltrán JÁ. CO2-supercritical extraction, hydrodistillation and steam distillation of essential oil of rosemary (Rosmarinus officinalis). Journal of Food Engineering. 2017;200:81-86. DOI: 10.1016/j.jfoodeng.2016.12.022
  50. 50. Shahsavarpour M, Lashkarbolooki M, Eftekhari MJ, Esmaeilzadeh F. Extraction of essential oils from Mentha spicata L. (Labiatae) via optimized supercritical carbon dioxide process. Journal of Supercritical Fluids. 2016:2-9. DOI: 10.1016/j.supflu.2017.02.004
  51. 51. Abbas A, Anwar F, Ahmad N. Variation in physico-chemical composition and biological attributes of common basil essential oils produced by hydro-distillation and super critical fluid extraction. Journal of Essential Oil-Bearing Plants. 2017;20:95-109. DOI: 10.1080/0972060X.2017.1280418
  52. 52. Vági E, Simándi B, Suhajda Á, Héthelyi É. Essential oil composition and antimicrobial activity of Origanum majorana L. extracts obtained with ethyl alcohol and supercritical carbon dioxide. Food Research International. 2005;38:51-57. DOI: 10.1016/j.foodres.2004.07.006
  53. 53. Bagheri H, Bin Abdul Manap MY, Solati Z. Antioxidant activity of Piper nigrum L. essential oil extracted by supercritical CO2 extraction and hydro-distillation. Talanta. 2014;121:220-228. DOI: 10.1016/j.talanta.2014.01.007
  54. 54. Ocaña-Fuentes A, Arranz-Gutiérrez E, Señorans FJ, Reglero G. Supercritical fluid extraction of oregano (Origanum vulgare) essentials oils: Anti-inflammatory properties based on cytokine response on THP-1 macrophages. Food and Chemical Toxicology. 2010;48:1568-1575. DOI: 10.1016/j.fct.2010.03.026
  55. 55. Pavela R, Sajfrtová M, Sovová H, Bárnet M, Karban J. The insecticidal activity of Tanacetum parthenium (L.) Schultz Bip. extracts obtained by supercritical fluid extraction and hydrodistillation. Industrial Crops and Products. 2010;31:449-454. DOI: 10.1016/j.indcrop.2010.01.003
  56. 56. Oliveira MS, da Costa WA, Pereira DS, Botelho JRS, de Alencar Menezes TO, de Aguiar Andrade EH, da Silva SHM, da Silva Sousa Filho AP, de Carvalho RN. Chemical composition and phytotoxic activity of clove (Syzygium aromaticum) essential oil obtained with supercritical CO2. Journal of Supercritical Fluids. 2016;118:185-193. DOI: 10.1016/j.supflu.2016.08.010
  57. 57. Larkeche O, Zermane a, Meniai a-H, Crampon C, Badens E. Supercritical extraction of essential oil from Juniperus communis L. needles: Application of response surface methodology. Journal of Supercritical Fluids. 2015;99:8-14. DOI: 10.1016/j.supflu.2015.01.026
  58. 58. Khajeh M. Optimization of process variables for essential oil components from Satureja hortensis by supercritical fluid extraction using Box-Behnken experimental design. Journal of Supercritical Fluids. 2011;55:944-948. DOI: 10.1016/j.supflu.2010.10.017
  59. 59. Zermane A, Larkeche O, Meniai A-H, Crampon C, Badens E. Optimization of essential oil supercritical extraction from Algerian Myrtus communis L. leaves using response surface methodology. Journal of Supercritical Fluids. 2014;85:89-94. DOI: 10.1016/j.supflu.2013.11.002
  60. 60. Uquiche E, Cirano N, Millao S. Supercritical fluid extraction of essential oil from Leptocarpha rivularis using CO2. Industrial Crops and Products. 2015;77:307-314. DOI: 10.1016/j.indcrop.2015.09.001
  61. 61. Chen Z, Mei X, Jin Y, Kim E-H, Yang Z, Tu Y. Optimisation of supercritical carbon dioxide extraction of essential oil of flowers of tea (Camellia sinensis L.) plants and its antioxidative activity. Journal of the Science of Food and Agriculture. 2014;94:316-321. DOI: 10.1002/jsfa.6260
  62. 62. Moreau RA, Whitaker BD, Hicks KB. Phytosterols, phytostanols, and their conjugates in foods: Structural diversity, quantitative analysis, and health-promoting uses. Progress in Lipid Research. 2002;41:457-500. DOI: 10.1016/S0163-7827(02)00006-1
  63. 63. Awad AB, Fink CS. Phytosterols as anticancer dietary components: Evidence and mechanism of action. The Journal of Nutrition. 2000;130:2127-2130. http://jn.nutrition.org/content/130/9/2127.long
  64. 64. Ling WH, Jones PJH. Dietary phytosterols: A review of metabolism, benefits and side effects. Life Sciences. 1995;57:195-206. DOI: 10.1016/0024-3205(95)00263-6
  65. 65. Ostlund RE. Phytosterols inhumannutrition. Annual Review of Nutrition. 2002;22:533-549. DOI: 10.1146/annurev.nutr.22.020702.075220
  66. 66. Nyam KL, Tan CP, Lai OM, Long K, Man YBC. Optimization of supercritical CO2 extraction of phytosterol-enriched oil from Kalahari melon seeds. Food and Bioprocess Technology. 2011;4:1432-1441. DOI: 10.1007/s11947-009-0253-4
  67. 67. Nyam KL, Tan CP, Lai OM, Long K, Che Man YB. Optimization of supercritical fluid extraction of phytosterol from roselle seeds with a central composite design model. Food and Bioproducts Processing. 2010;88:239-246. DOI: 10.1016/j.fbp.2009.11.002
  68. 68. Hrabovski N, Sinadinović-Fišer S, Nikolovski B, Sovilj M, Borota O. Phytosterols in pumpkin seed oil extracted by organic solvents and supercritical CO2. European Journal of Lipid Science and Technology. 2012;114:1204-1211. DOI: 10.1002/ejlt.201200009
  69. 69. Uquiche E, Romero V, Ortíz J, Del Valle JM. Extraction of oil and minor lipids from cold-press rapeseed cake with supercritical CO2. Brazilian Journal of Chemical Engineering. 2012;29:585-597. DOI: 10.1590/S0104-66322012000300016
  70. 70. Sajfrtová M, Ličková I, Wimmerová M, Sovová H, Wimmer Z. β-Sitosterol: Supercritical carbon dioxide extraction from sea buckthorn (Hippophae rhamnoides L.) seeds. International Journal of Molecular Sciences. 2010;11:1842-1850. DOI: 10.3390/ijms11041842
  71. 71. Botelho JRS, Medeiros NG, Rodrigues AMC, Araújo ME, Machado NT, Guimarães Santos A, Santos IR, Gomes-Leal W, Carvalho RN. Black sesame (Sesamum indicum L.) seeds extracts by CO2 supercritical fluid extraction: Isotherms of global yield, kinetics data, total fatty acids, phytosterols and neuroprotective effects. Journal of Supercritical Fluids. 2014;93:49-55. DOI: 10.1016/j.supflu.2014.02.008
  72. 72. Wang H, Yang A, Zhang G, Ma B, Meng F, Peng M, Wang H. Enhancement of carotenoid and bacteriochlorophyll by high salinity stress in photosynthetic bacteria. International Biodeterioration and Biodegradation. 2017;121:91-96. DOI: 10.1016/j.ibiod.2017.03.028
  73. 73. Martins N, Ferreira ICFR. Wastes and by-products: Upcoming sources of carotenoids for biotechnological purposes and health-related applications. Trends in Food Science and Technology. 2017;62:33-48. DOI: 10.1016/j.tifs.2017.01.014
  74. 74. Huang JJ, Lin S, Xu W, Cheung PCK. Occurrence and biosynthesis of carotenoids in phytoplankton. Biotechnology Advances. 2017;35:597-618. DOI: 10.1016/j.biotechadv.2017.05.001
  75. 75. Riccioni G, D’Orazio N, Franceschelli S, Speranza L. Marine carotenoids and cardiovascular risk markers. Marine Drugs. 2011;9:1166-1175. DOI: 10.3390/md9071166
  76. 76. Gammone MA, Riccioni G, D’Orazio N. Carotenoids: Potential allies of cardiovascular health? Food & Nutrition Research. 2015;59:1-11. DOI: 10.3402/fnr.v59.26762
  77. 77. Saini RK, Keum Y-S. Carotenoid extraction methods: A review of recent developments. Food Chemistry. 2018;240:90-103. DOI: 10.1016/j.foodchem.2017.07.099
  78. 78. Figueira JA, Pereira JAM, Porto-Figueira P, Câmara JS. Ultrasound-assisted liquid-liquid extraction followed by ultrahigh pressure liquid chromatography for the quantification of major carotenoids in tomato. Journal of Food Composition and Analysis. 2017;57:87-93. DOI: 10.1016/j.jfca.2016.12.022
  79. 79. Hiranvarachat B, Devahastin S. Enhancement of microwave-assisted extraction via intermittent radiation: Extraction of carotenoids from carrot peels. Journal of Food Engineering. 2014;126:17-26. DOI: 10.1016/j.jfoodeng.2013.10.024
  80. 80. Goula AM, Ververi M, Adamopoulou A, Kaderides K. Green ultrasound-assisted extraction of carotenoids from pomegranate wastes using vegetable oils. Ultrasonics Sonochemistry. 2017;34:821-830. DOI: 10.1016/j.ultsonch.2016.07.022
  81. 81. Kwang HC, Lee HJ, Koo SY, Song DG, Lee DU, Pan CH. Optimization of pressurized liquid extraction of carotenoids and chlorophylls from Chlorella vulgaris. Journal of Agricultural and Food Chemistry. 2010;58:793-797. DOI: 10.1021/jf902628j
  82. 82. Damergi E, Schwitzguébel JP, Refardt D, Sharma S, Holliger C, Ludwig C. Extraction of carotenoids from Chlorella vulgaris using green solvents and syngas production from residual biomass. Algal Research. 2017;25:488-495. DOI: 10.1016/j.algal.2017.05.003
  83. 83. Millao S, Uquiche E. Extraction of oil and carotenoids from pelletized microalgae using supercritical carbon dioxide. Journal of Supercritical Fluids. 2016;116:223-231. DOI: 10.1016/j.supflu.2016.05.049
  84. 84. Egydio JA, Moraes ÂM, Rosa PTV. Supercritical fluid extraction of lycopene from tomato juice and characterization of its antioxidation activity. Journal of Supercritical Fluids. 2010;54:159-164. DOI: 10.1016/j.supflu.2010.04.009
  85. 85. Hsu YW, Tsai CF, Chen WK, Ho YC, Lu FJ. Determination of lutein and zeaxanthin and antioxidant capacity of supercritical carbon dioxide extract from daylily (Hemerocallis disticha). Food Chemistry. 2011;129:1813-1818. DOI: 10.1016/j.foodchem.2011.05.116
  86. 86. Chen J-R, Wu J-J, Lin JC-T, Wang Y-C, Young C-C, Shieh C-J, Hsu S-L, Chang C-MJ. Low density supercritical fluids precipitation of 9-cis and all trans-β-carotenes enriched particulates from Dunaliella salina. Journal of Chromatography. A. 2013;1299:1-9. DOI: 10.1016/j.chroma.2013.05.022
  87. 87. Goto M, Kanda H, Wahyudiono SM. Extraction of carotenoids and lipids from algae by supercritical CO2 and subcritical dimethyl ether. Journal of Supercritical Fluids. 2015;96:245-251. DOI: 10.1016/j.supflu.2014.10.003
  88. 88. Heffernan N, Smyth TJ, FitzGerald RJ, Vila-Soler A, Mendiola J, Ibáñez E, Brunton NP. Comparison of extraction methods for selected carotenoids from macroalgae and the assessment of their seasonal/spatial variation. Innovative Food Science & Emerging Technologies. 2016;37:221-228. DOI: 10.1016/j.ifset.2016.06.004
  89. 89. Gunstone D, Norris FA. Lipids in Foods: Chemistry, Biochemistry and Technology. Oxford: Elsevier; 1983
  90. 90. Stirban A, Nandrean S, Go C, Tamler R, Pop A, Negrean M, Gawlowski T. Effects of n-3 fatty acids on macro- and microvascular function in subjects with type 2 diabetes mellitus 1–3. The American Journal of Clinical Nutrition. 2010;91:808-813. DOI: 10.3945/ajcn.2009.28374.1
  91. 91. Begg DP, Sinclair AJ, a Stahl L, Premaratna SD, Hafandi A, Jois M, Weisinger RS. Hypertension induced by omega-3 polyunsaturated fatty acid deficiency is alleviated by alpha-linolenic acid regardless of dietary source. Hypertension Research. 2010;33:808-813. DOI: 10.1038/hr.2010.84
  92. 92. De CR. N-3 fatty acids in cardiovascular disease. The New England Journal of Medicine. 2011;364:2439-2450
  93. 93. Oh DY, Talukdar S, Bae EJ, Imamura T, Morinaga H, Fan W, Li P, Lu WJ, Watkins SM, Olefsky JM. GPR120 is an Omega-3 fatty acid receptor mediating potent anti-inflammatory and insulin-sensitizing effects. Cell. 2010;142:687-698. DOI: 10.1016/j.cell.2010.07.041
  94. 94. Issariyakul T, Dalai AK. Biodiesel from vegetable oils. Renewable and Sustainable Energy Reviews. 2014;31:446-471
  95. 95. Hafis SM, Ridzuan MJM, Rahayu A, Farahana RN, Nor Fatin B, Syahrullail S. Properties of palm pressed fibre for metal forming lubricant applications. Procedia Engineering. 2013;68:130-137
  96. 96. Pádua MS, Paiva LV, Labory CRG, Alves E, Stein VC. Induction and characterization of oil palm (Elaeis guineensis Jacq.) pro-embryogenic masses. Anais da Academia Brasileira de Ciências. 2013;85:1545-1556. DOI: 10.1590/0001-37652013107912
  97. 97. Ezeh O, Gordon MH, Niranjan K. Enhancing the recovery of tiger nut (Cyperus esculentus) oil by mechanical pressing: Moisture content, particle size, high pressure and enzymatic pre-treatment effects. Food Chemistry. 2016;194:354-361. DOI: 10.1016/j.foodchem.2015.07.151
  98. 98. Koubaa M, Mhemdi H, Vorobiev E. Influence of canola seed dehulling on the oil recovery by cold pressing and supercritical CO2 extraction. Journal of Food Engineering. 2016;182:18-25. DOI: 10.1016/j.jfoodeng.2016.02.021
  99. 99. Hu B, Li C, Zhang Z, Zhao Q, Zhu Y, Su Z, Chen Y. Microwave-assisted extraction of silkworm pupal oil and evaluation of its fatty acid composition, physicochemical properties and antioxidant activities. Food Chemistry. 2017;231:348-355. DOI: 10.1016/j.foodchem.2017.03.152
  100. 100. Bernardo-Gil MG, Casquilho M, Esquível MM, Ribeiro MA. Supercritical fluid extraction of fig leaf gourd seeds oil: Fatty acids composition and extraction kinetics. Journal of Supercritical Fluids. 2009;49:32-36. DOI: 10.1016/j.supflu.2008.12.004
  101. 101. Sánchez-Camargo AP, Martinez-Correa HA, Paviani LC, Cabral FA. Supercritical CO2 extraction of lipids and astaxanthin from Brazilian redspotted shrimp waste (Farfantepenaeus paulensis). Journal of Supercritical Fluids. 2011;56:164-173. DOI: 10.1016/j.supflu.2010.12.009
  102. 102. Tomita K, Machmudah S, Quitain AT, Sasaki M, Fukuzato R, Goto M. Extraction and solubility evaluation of functional seed oil in supercritical carbon dioxide. Journal of Supercritical Fluids. 2013;79:109-113. DOI: 10.1016/j.supflu.2013.02.011
  103. 103. Wang XW, Liang JR, Luo CS, Chen CP, Gao YH. Biomass, total lipid production, and fatty acid composition of the marine diatom Chaetoceros muelleri in response to different CO2 levels. Bioresource Technology. 2014;161:124-130. DOI: 10.1016/j.biortech.2014.03.012
  104. 104. Bartolomé Ortega A, Calvo Garcia A, Szekely E, Škerget M, Knez Ž. Supercritical fluid extraction from saw palmetto berries at a pressure range between 300 bar and 450 bar. Journal of Supercritical Fluids. 2017;120:132-139. DOI: 10.1016/j.supflu.2016.11.003
  105. 105. De Melo MMR, Silvestre AJD, Silva CM. Supercritical fluid extraction of vegetable matrices: Applications, trends and future perspectives of a convincing green technology. Journal of Supercritical Fluids. 2014;92:115-176. DOI: 10.1016/j.supflu.2014.04.007
  106. 106. Vatai T, Škerget M, Knez Ž. Extraction of phenolic compounds from elder berry and different grape marc varieties using organic solvents and/or supercritical carbon dioxide. Journal of Food Engineering. 2009;90:246-254. DOI: 10.1016/j.jfoodeng.2008.06.028
  107. 107. Mantell C, Rodríguez M, Martínez de la Ossa E. A screening analysis of the high-pressure extraction of anthocyanins from red grape pomace with carbon dioxide and cosolvent. Engineering in Life Sciences. 2003;3:38-42. DOI: 10.1002/elsc.200390004
  108. 108. Ghafoor K, AL-Juhaimi FY, Choi YH. Supercritical fluid extraction of phenolic compounds and antioxidants from grape (Vitis labrusca B.) seeds. Plant Foods for Human Nutrition. 2012;67:407-414. DOI: 10.1007/s11130-012-0313-1
  109. 109. L.E. Laroze, B. Díaz-Reinoso, A. Moure, M.E. Zúñiga, H. Domínguez, Extraction of antioxidants from several berries pressing wastes using conventional and supercritical solvents, European Food Research and Technology 231 (2010) 669-677. doi:10.1007/s00217-010-1320-9
  110. 110. Seabra IJ, Braga MEM, Batista MTP, de Sousa HC. Fractioned high pressure extraction of anthocyanins from elderberry (Sambucus nigra L.) pomace. Food and Bioprocess Technology. 2010;3:674-683. DOI: 10.1007/s11947-008-0134-2
  111. 111. Bleve M, Ciurlia L, Erroi E, Lionetto G, Longo L, Rescio L, Schettino T, Vasapollo G. An innovative method for the purification of anthocyanins from grape skin extracts by using liquid and sub-critical carbon dioxide. Separation and Purification Technology. 2008;64:192-197. DOI: 10.1016/j.seppur.2008.10.012
  112. 112. Paula JT, Paviani LC, Foglio MA, Sousa IMO, Duarte GHB, Jorge MP, Eberlin MN, Cabral FA. Extraction of anthocyanins and luteolin from Arrabidaea chica by sequential extraction in fixed bed using supercritical CO2, ethanol and water as solvents. Journal of Supercritical Fluids. 2014;86:100-107. DOI: 10.1016/j.supflu.2013.12.008
  113. 113. Bergeron C, Gafner S, Clausen E, Carrier DJ. Comparison of the chemical composition of extracts from Scutellaria lateriflora using accelerated solvent extraction and supercritical fluid extraction versus standard hot water or 70% ethanol extraction. Journal of Agricultural and Food Chemistry. 2005;53:3076-3080. DOI: 10.1021/jf048408t
  114. 114. Paes J, Dotta R, Barbero GF, Martínez J. Extraction of phenolic compounds and anthocyanins from blueberry (Vaccinium myrtillus L.) residues using supercritical CO2 and pressurized liquids. Journal of Supercritical Fluids. 2014;95:8-16. DOI: 10.1016/j.supflu.2014.07.025

Written By

Vânia Maria Borges Cunha, Marcilene Paiva da Silva, Wanessa Almeida da Costa, Mozaniel Santana de Oliveira, Fernanda Wariss Figueiredo Bezerra, Anselmo Castro de Melo, Rafael Henrique Holanda Pinto, Nelio Teixeira Machado, Marilena Emmi Araujo and Raul Nunes de Carvalho Junior

Submitted: 02 May 2017 Reviewed: 21 September 2017 Published: 16 August 2018

© 2018 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms of the Creative Commons Attribution 3.0 License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

Continue reading from the same book

View All
Chapter 12 A Review on the Application of Enhanced Oil/Gas Re...

By Abdelmalek Atia and Kamal Mohammedi

1967 downloads

Chapter 1 Introductory Chapter: An Outline of Carbon Dioxide...

By Janah Shaya, Hassan Srour and Iyad Karamé

1970 downloads

Chapter 2 Electrochemical/Photochemical CO2 Reduction Cataly...

By Hitoshi Ishida

2315 downloads