Supercritical Fluid Extraction

SUPERCRITICAL FLUID EXTRACTION
CONTENTS
1. Introduction
2. Fundamentals
3. Equipment
4. Technological factors
5. Use in food industry
Van Viet Man Le (Ho Chi Minh City

University of Technology) 1

1. Introduction
History
 1879: Increased solubility of inorganic salts in
supercritical fluid (Hannay and Hogarth)
 1950: Starting research on supercritical fluid extraction
(Russia and Germany)
 1960: First patent on supercritical fluid extraction
(Germany)
 1990: Concept “green processing”
 Current application of supercritical fluid in the industry
(USA, Germany, Japan, UK, France)


1. Introduction
Industrial application of supercritical fluid extraction
Manufacturers Country
Flavex, Hermsen, HGV Barth, Kaffe HAG, SKW Germany
Trostberg
General foods, John Haas, Praxair, Yakima USA
Chief
Carlton United Breweries, English Hops UK
Fuji Flavor, Kobe, Mori Oil Mills, Ogawa, Japan
Takasago, Takeda
Cultor, Hitex France
1
1. Introduction
Advantages
 Mass transfer
 Selectivity
 By-reactions
 Purity
 Energy consumption
 Regulation
Disadvantages
 Investment
 Working pressure Van Viet Man Le (Ho Chi Minh City

1. Introduction
Application


2. Fundamentals
Extraction
 Definition
 Material for extraction
 Driving force

2
2. Fundamentals
Solvent
 Solute solubility
 Inertness
 Safety
 Recovery
 Cost


2. Fundamentals
Pressure – temperature diagram


2. Fundamentals
Supercritical Fluid (SCF)
 Properties of SCF
 Near-Critical Fluid (NCF)

3
2. Fundamentals
SCF – Critical constants
Concepts
 Reduced pressure:
Pr=P/Pc
 Reduced
temperature: Tr=T/Tc
 Reduced specific
gravity: ρr=ρ/ρc


2. Fundamentals
SCF – Physico-chemical properties


2. Fundamentals
SCF specific
gravity

4
2. Fundamentals
SCF viscosity


2. Fundamentals
SCF diffusivity


2. Fundamentals
SCF extraction and

mass transfer

5
2. Fundamentals
Co-solvent/ entrainer
 Objective
 Mechanism
 Solute
 Specific gravity
 Examples
 Use ratio


2. Fundamentals
Solute separation and solvent recovery

 Solute
 Pressure change
 Adsorption
 Molecular filtration
 Solvent
 Recovery
 Treatment


2. Fundamentals
Criteria for solvent selection

 Critical constants
 Other criteria

6
2. Fundamentals
Supercritical CO2
 Polarity
 Solvent power
C = ρk * exp(a/T +b)
C: Solute concentration
T: Temperature
ρ: Specific gravity of supercritical fluid
a, b, k: Experimental constants


2. Fundamentals
Supercritical CO2
CO2 + H2O ↔ H2CO3

H2CO3 + H2O ↔ H3O+ + HCO3-
HCO3- + H2O ↔ H3O+ + CO32-
pH value


2. Fundamentals
Supercritical CO2
 Advantages:
- Cost
- Safety
- Tc=31.06oC
- Pc=73.8bar
 Disadvantages: non-polar property

7
2. Fundamentals
Supercritical CO2
Tc=31.06oC
Pc=73.8bar
Application:
 Simple extraction
 Total extraction
 Fractionation
 Deodorisation

3. Equipment


8


SCF
 Chemical nature
 Properties
Material
 Size
 Structure
 Chemical composition

Technological parameters
 Temperature
 Pressure
→ Pressure diagram
 Flow-rate of the solvent
 Time
 Other parameters

9
 Essential oil extraction

 Alkaloid extraction
 Oil extraction
 Cholesterol removal
 Colorant extraction
 Other application


5.1. Hop products
 Hop extract
 Alpha acids and essential oil
 Note


10
5.2. Alkaloids
 Definition
 Properties
 Source: Papaveraceae (poppy and opium), Papilonaceae

(lupins), Ranunculaceae (aconitum), Solanaceae
(tobacco)…
 Example: caffeine, cocaine, nicotine, morphine, quinine,

codeine, emetine, pilocarpine…


5.2. Alkaloids
 Purine alkaloids: caffeine, theobromine, theophylline…


5.2. Alkaloids Coffee decaffeination
 Coffee beans: 3% caffeine

 Objective
 Treatment operation
 Conventional procedure: Coffee beans  Swelling 

Caffeine extraction  Solvent removal  Drying 
Product

11
 Solvent
 Benzene
 Ethyl acetate, methylene chloride, methyl acetate,
ethylmethylketone, trichloroethane
 Water
 SCF


 Procedure 1:
 Extraction at 16-22MPa, 70-90oC
→ Product: 0.02% caffeine
 Water washing tower for caffeine separation
 Procedure 2:
 Similar parameters as those in procedure 1
 Bed of activated carbon for caffeine separation


 Procedure 3:
 Moistened green coffee beans and activated carbon
pellets
 Extraction at 22MPa, 90oC
 Separation by vibrating sieves

12
 Other procedures
 2 extractors in 1 production line  SCF
 SCF: NO2, NH3, CHF3
 Co-solvent: acetone, methanol, ethanol  Working
pressure and extraction yield
 Ion-exchange resins for activated carbon
replacement


 Procedure for roasted coffee beans

 Objective
 Application



13
 Advantages
 Decaffeinated coffee
 Sugars and amino acids  Flavoring compounds
 Other components
 Caffeine product
 Natural treatment
 Energy consumption
 Economic efficiency

 Disadvantages
 Investment
 Production management
 Safety


5.2. Alkaloids Tea decaffeination

14
 Tea: 2.0-3.5% caffeine

 Objective
 Conventional method
(methylene chloride or ethyl acetate)


 Procedure: Black tea  Separation of flavoring

compounds  Moistening and decaffeination  Drying 
Addition of flavoring compounds  Product
 Separation of flavoring compounds: SC-CO2 at
25MPa, 50oC
 Decaffeination: 25.5-35MPa, 50-80oC
 Vacuum drying: 50oC
 Manufacturers: SKW/Trostberg, Meunschmeunster
(Germany)

 Decaffeinated instant tea

 Procedure
 Development tendency

15
5.2. Alkaloids Theobromine extraction from
Theobroma cacao
 Theobroma cacao: 1-2% theobromine and 0.1% caffeine
 Cocoa fermentation: alkaloids  grain peel
 Mass balance: 150.000t cocoa beans  13.000t bean

shell  30t theobromine

Components Cocoa bean (% w/w) Shell (% w/w)

Moisture 5 4.5
Lipid 54 1.5
Theobromine 1.2 1.4
Caffeine 0.2 -
Polyhydroxyphenols 6 -
Total protein 11.5 10.9
Mono/oligosaccharide 1 0.1
Starch 6 -
Pentosans 1.5 7
Cellulose 9 26.5
Carboxylic acids 1.5 -
Ash 2.6 8
Other compounds 0.5 -


5.2. Alkaloids Theobromine extraction from
Theobroma cacao
 Theobromine extraction
 Water
 SC CO2: 30MPa, 90oC
 Co-solvent:
 Water: Caffeine showed better solubility than
theobromine
 Ethanol 10%, 20MPa, 70oC  Theobromine yield:
89%
 Increase in extraction temperature
16
5.2. Alkaloids
Other alkaloids
 Monocrotaline (Crotalaria spectabilis): anticancer activity
 SC CO2 and ethanol/ water, Ion exchange resin for
purification
 Nicotine (Nicotiana): insecticide  SC CO2 and water
 Morphine and its derivatives: analgesics (160t/ year)


5.3. Lipid extraction
 Cocoa butter extraction (Tan et al., 2008)
 Parameters: 45 MPa, 75oC and 12h
 Cocoa liquor (74 μm) → 40.4%; Ground cocoa nibs
(0.85–1 mm) → 29.3%, Crushed cocoa nins (4–6 mm) →
14.1%
 Composition:
 1,3-Dipalmitoyl-2-oleoyl-glycerol (POP) → > 30%
 1-palmitoyl-2-oleoyl-3-stearoyl-glycerol (POS)
 1,3-distearoyl-2-oleoyl-glycerol (SOS)

5.3. Lipid extraction
 Extraction of lipid with high PUFA level

Ex: By-product from Merluccius capensis – Merluccius
paradoxus (Rubio-Rodríguez et al., 2008)
 Pretreatment: milling → freezing
 Parameters: t=40oC, P=25 MPa, 10 kg CO2/h, 3h
 Yield: 96%
 Composition: omega-3/omega-6 (7%); EPA (6%); DHA
(14%)

17
5.4. Removal of cholesterol from foods


 Cholesterol: precursor for synthesis of steroid hormones,

bile acids and sexual hormones
 For human: cholesterol synthesis, absorption (intestine)
and transport (liver)
 Cholesterol in blood
 LDL  “bad cholesterol”
 HDL  “good cholesterol”
 Daily diet: max 300mg


 Cholesterol removal: SC-CO2, P=10-25MPa, T=40-80oC
 Hydrocarbon: solvent or co-solvent

 SC ethane: Tc, Pc
 Mixture of ethane-propane, ethane-CO2
 Increase in solubility by 3-15 times

18


Food P (MPa) T(oC) Yield References

(%)
Dried egg yolk 16.5-37.8 40-55 65.8 Froning et al, 1998
Dried egg yolk 24.1-37.8 45-55 98.0 Bohac, 1998
Dehydrated beef 23.4-38.6 45-55 87.8 Lim, 1992
Dried chicken 30.6-37.6 45-55 90.0 Froning et al, 1994
meat
Pork (cooked) 7.3-34.4 50-150 70.1 Lin et al, 1999
Milk fat 10.1-36.4 40-70 91.5 Neves, 1996
Milk fat 8.0-24.0 40-70 93.4 Mohamed et al, 2000

5.5. Other applications
 Colorant extraction
 Bioactive compound extraction
 Lecithin separation
 Cooking oil purification

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SUPERCRITICAL FLUID EXTRACTION

Van Viet Man Le (Ho Chi Minh City