Types

Author

Title

Review paper (Institute of Food Technologists) Journal (J. of Supercritical Fluid)

Rozzi, N.L. Supercritical fluids and and Singh, the food industry R.K. (2002)

Raw material/ products Natural Products

Solubility parameter Solubility Parameter (equation of state) Process modeling (mass balance) Flow rate Temperature Pressure

Rodrigues Coumarin solubility and Emburana et al.(2008) extraction from emburana seeds (Torresea cearensis) seeds with supercritical carbon dioxide

Solubility Parameter

The solubility parameter is the solvating capability of compressed gas as described by Hildebrand Solubility Parameter, which is rough measure of the ability of solvent to dissolve a solute. Equation 1 relates the solubility parameter to the density of both the gas and the liquid by (Rizvi et al., 1994):

Where:

When

As the pressure increases, the solubility parameter increases, with great changes taking place as is reached. This solubility parameter is not applicable for esters, ketones, alcohols and other polar liquids.

Another equation regarding solubility parameter is proposed by Allada (1984). The concept used is internal energy of the gas relative to isothermally expanded ideal gas state as the cohesive energy of gases.

The values for Z and

can be calculated as equations below or can be obtained from the

book, Chemical Process Principles, Part Two, Thermodynamics, by Hougen and Watson (1947).

This equation works well for prediction of the solubility of a substance in different SC fluids at different P but not for T changes.

Another equation to describe the behavior of solutes being dissolved in SC fluids is PengRobinson Equation of State. Pure species:

Mixture:

Specified form:

Mixing rule:

X=mole fraction in the liquid or SC fluid phase

Another mixing rule which can be take into account in order to improve the fit of the data for some solutes (Mc Hugh, 1994) as follows:

Process Modeling The process of extracting natural products by supercritical fluid extraction can be modeled using the model developed by Sovova (1994). This model is based on the following assumptions: (1) The solvent flows axially through a bed of raw material in a cylindrical extractor. (2) The solvent is solute-free upon entering the extractor. (3) The solute is partially exposed to the solvent due to previous milling

The mass balance for the process is described below:

(14)

(15) Where:

The curves describing the extraction process can be determined by the following:

(16) Where:

e (t) = Mass extracted relative to the mass of the solute-free solid phase xo H = Concentration related to the solute-free solid phase = Height of the bed

x(t,h) = Concentration related to the solute-free solid phase as a function of time (t) and height (h).

This modeling system can be used to describe the extraction of natural products using supercritical CO2 (Sovova, 1994).

Solubility experiments The design of SFE processes are mainly dependant on the solubility of the solute in the supercritical fluid. There are some parameter that need to be considered depending on raw materials used.

Types Review Paper

Author Lijun Wang and Curtis L.Weller

Title Recent advances in extraction of nutraceuticals from plants

Raw material/product Santolina insularis essential oil

Parameter Temperature and density

Nonacosan-10ol,-amyrin acetate,squalene and stigmasterol Chilean hop (Humulus lupulus) ecotypes

Temperature and density

Pressure and temperature

Santolina insularis essential oil

Extraction time

Foeniculum vulgare volatile oil

CO2 flow rate

High extraction yield of the desire compound in a supercritical fluid are affected by the temperature and density as stated by Chercie et al., 2001.The temperature and density of the fluid will influence the solubility of the Santolina insularis essential oil where they become soluble in the fluid so that the extraction of other compounds can be minimized. Due to that reason, it is highly recommended to choose the proper density of a supercritical fluid such as CO2 because this property can influence the extract composition, solvent power and selectivity. Choi et al., 1997 also report the same result where supercritical CO2 extraction of squalene from the entire plant of spirodela polyrhiza gives better relative extraction yield compare to the stigmasterol extraction at 10 MPa and 50 or 600C.The extraction of squalene are comparable with n-hexane extract but the stigmasterol was not detected under this condition. Their result revealed that SFE could selectively extract substances from the plant by adjusting the temperature and density. For supercritical CO2 extraction of Chilean hop (Humulus lupulus) ecotypes, del Valle et al., 2003 found that the extraction rate increased minimally when applying pressure > 20 MPa at the temperature of 400C because increase in pressure will also increase the co-extraction of undesirable compounds. Cherci et al., 2001 reported that the extraction time also affect the extract composition. Lower molecular weight and less polar compound are more readily extracted during supercritical CO2 extraction since the mechanism is usually controlled by internal diffusion. Therefore, the extract composition varies with the extraction time. However, Coelho et al., 2003 claimed that the increase of CO2 flow rate did not affect the composition of Foeniculum vulgare volatile oil although it increased the extraction rate.