Extraction of natural compounds

using supercritical CO2: Going from

the laboratory to the industrial
application

Jose M. del Valle

U.C. de Chile

Contents

Introduction

Previous work

Predictive Modelling: Extraction of vegetable oil

Estimation of production costs

Study case

Conclusions

Introduction

scCO2 extraction processes have well established commercial applications:

Bitter flavor from hops

Decaffeinated coffee beans

High value compounds of herbs, species, vegetables etc.

Wrong misconception that scCO2 extraction processes is not fully competitive

There is lack of a predictive model for simulating this processes

Accurate cost estimates would reduce risk on investing in commercial

applications

Previous Work
Extraction
Author
Vessels

Krner

Novak
and
Robey

Fiori

Volume
[L]

300

974

800

Mass
Flow
Rate CO2
[kg/h]

2000

4550

2000

Operating
Pressure
[bar]

Substrate

300

Spices
(Aroma and
Oleoresin)

Production cost comparable to that of a

conventional plant
Equivalent fractionation process in a single
process

300

Herbs and
Spices
(Aroma and
Flavor
Compounds)

Estimated cost of larger SFE plants using

equipment-specific scaling factors
Increasing the SFE plant size by a factor of four
decreased production cost from USD 1,1/kg to
USD 0,50/kg

550

Grape Seeds
(Oil
extraction)

Development of a mathematical model that

predicted the extraction process in simulated
countercurrent mode.

Conclusions/contribution

Previous Work
Author

Conclusions

Proposal of a three-stage CO2 recovery system that dramatically reduces the

energy requirement for the CO2 recompression

Rosa and
Meireles

Development of a simple method to determine the Cost of Production (CoM)

CoM can be compared to the actual price of the extract in the market.

Del Valle

Experimental determination of the cumulative extraction curve

The cumulative extraction curve is a key parameter for the determination
of CoM and cost optimization.

Optimization of extraction time by computer simulation rather than

experimentally

Bravi

Clavier

Predictive modeling: Extraction of vegetable oils

Extraction time critically affects

SFE costs

Process conditions (d, T, P, U) may

be optimized in the laboratory

Relationship between extraction

yield and process time depends on
scale-specific variables

Cumulative Extraction Curve

OBJECTIVE: To develop a predictive model which provides the relationship

between oil yield and extraction time
optimize time by computer simulation using a mass transfer model

Predictive modeling: Extraction of vegetable oils

Prepressed oilseed: network of interconnected open pores filled with oil

Shrinking Core (SC) mass transfer model based on effective diffusivity

Csat: solubility of oil in scCO2
(solute partition between the
soulte core and intraparticle
scCO2)
De: effective diffusivity of the
solute in the soild
kf: external mass transfer
coefficient
DL: axial dispersion coefficient
(transport in the scCO2 phase)
7

Predictive modeling: Extraction of vegetable oils

Physical properties of solvent are estimated as function of T and P

Funazukuri equation for Infinite dilution binary diffusion coefficient (D 12)

Solubility of oil in scCO2 Csat

Axial dispersion DL

Predictive modeling: Extraction of vegetable oils

Film mass transfer coefficient kf in a packed bed operating with SCF

Effective diffusivity of oil in the prepressed substrate (De)

Fm: pre-treatment dependent
microestructural factor
9

Estimation of production cost

Unitary production cost per year investment + operational costs

Include extraction vessels, cascade depressurization, system for vessel

reconditioning and auxiliaries

10

Estimation of production cost

Solvent cycle

Extraccion vessels
with on-off valves

Vessel
reconditioning cycle11

Estimation of production cost

Investment cost: function of mass flow rate of CO2 (Q), volume and number
of extraction vessels. Expressed as annuity (CI).

Ir: reference cost;

:cost corresponding to
solvent; f(H/D) correction
factor for each vessel

Annual cost of labor

Unitary energy cost of the solvent cycle

12

Estimation of production cost

Solvent cycle in a supercritical fluid extraction plant

13

Estimation of production cost

Total unitary production cost

Annual cost of investment

Labor

Energy expend in the solvent cycle, depressurization and repressurization

Prepressed oilseeds

CO2 vented from extraction vessels or lost with the recovered oil

Estimate the unitary production cost as a function of

extraction computer simulation!

14

Study Case: Minimization of production cost

60C
8 MPa

40C
30 Mpa
V=1 m3

25C
6,43 MPa

Q= 12 t/h of CO2

Extraction of oil from prepressed oilseed particles using a simulated

countercurrent process.

15

Study Case: Minimization of production cost

Cumulative Extraction Yield and Plant Productivity

Increasing Oil Yield decreases Oil Production

After the constant extraction-rate period limitations

in mass transfer occurs which preclude scCO 2 leaving
the vessel without reaching saturation.

The initial extraction rate is controlled by the

solubility of the oil in scCO2.

16

Study Case: Minimization of production cost

Production Cost as a Function of Extraction Time

The minimum extraction cost is just after the constant extraction-rate period finishes

As the Oil Yield increases the contribution of substrate and CO 2 (Variable Cost) decreases

As the Oil Yield increases the contribution of fixed cost increases

17

Study Case: Minimization of production cost

Effect of particle diameter on the production of cost

As the particle diameter increases the

internal mass transfer is more difficult

As the particle size decreases the mass

transfer is controlled externally

18

Study Case: Minimization of production cost

Effect of particle diameter and superficial velocity

It advantageous to use smaller particle sizes and

higher superficial velocities

The limit is the fluidization velocity

Fluidization of the bed is undesirable because it

can clog the screen of the extraction baskets and
induce channeling phenomena

19

Study Case: Minimization of production cost

Effect on the number of extraction vessels

As the number of vessels increases the

extraction time increases due to the
decrease of extraction in the initial
stages

Increasing the number of vessels

improves the solvent power of scCO2
that is because the CO2 is closer to
saturation

20

Conclusions
Perspectives and Future Directions

For decreasing the production costs it is desirable to:

Decrease particle size

Increase CO2 mass flow rate

Increase of extraction pressure (Increase of oil solubility)

Increasing the plant size

Reconditioning time may be large when:

Extraction pressure is high

Free volume of the vessel is high

When H/D ratio is small due to limitation in heat transfer

21

Conclusions
Perspectives and Future Directions

Pretreatments:

Are useful to:

Release solutes from the cells

Ease solvent flow through the packed bed

Increase extraction vessel load

Size-reduction

Breaks superficial cells

Increases the specific surface of the substrate

Small particles are inconvenient due to: agglomeration, low packing density and channeling

High-Shear-Stress proceses

Examples: Pressing, Pelletization

Destroys cell walls and barriers without reducing particle size

Increases the vessel load capacity

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Thank you for your attention!

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