C H A P T E R
7.7
Supercritical Fluid Applications in the
Food Industry
Michel Perrut, Vincent Perrut
Atelier Fluides Supercritiques, Nyons, France
7.7.1 INTRODUCTION:
SUPERCRITICAL FLUID
TECHNOLOGY AS A “GREEN”
ALTERNATIVE FOR NATURAL
PRODUCT PROCESSING
After three decades of development, at least
400 plants are now using a supercritical fluid
(SCF) at the commercial scale, mainly dedicated
to extraction/fractionation of natural products.
First of all, as it is harmless (nonflammable
and nontoxic), abundant, and very inexpensive
(except on special locations such as islands or
remote sites, or specific applications requiring
high-purity gas), CO2 must be considered as the
SCF. From the very beginning of industrial appli-
cations of supercritical fluid technology, it has
been asserted that it is definitely a “green” tech-
nology, as a perfect example of processes com-
patible with sustainable development. In fact,
as CO2 used as SCF represents only a very small
part of the CO2 available from petrochemical
sources where it is a fatal byproduct (mainly in
ammonia synthesis plants), it is true that emis-
sions from SCF plants do not contribute to global
warming, as this gas would have been released
Gases in Agro-food Processes
https://doi.org/10.1016/B978-0-12-812465-9.00020-7
anyway to the atmosphere. Moreover, using
CO2 instead of organic solvents leads to a drastic
reduction of VOC emissions, even when a cosol-
vent is used to modify fluid polarity. Moreover,
CO2-processed products are not contaminated
with solvent residues that may be deleterious
to consumers and the environment.
The most promising applications of natural
product processing can be classified into the fol-
lowing areas:
- Extraction (SFE): Most large-scale units are
operated worldwide for extraction of solid
natural materials, mainly for food ingredients
and phytopharmaceuticals/nutraceuticals.
- Fractionation (SFF): Industrial applications
are designed to profit from the very high
selectivity of supercritical fluids: Aroma
production from fermented and distilled
beverages, lipid fractionation (especially
polyunsaturated fatty acids and polar lipids),
active compounds from fermentation
broth, etc.
- Reactions (SFR): Supercritical fluids are very
promising media for many chemical and
biochemical reactions leading to higher
483 # 2019 Elsevier Inc. All rights reserved.
484 7.7. SUPERCRITICAL FLUID APPLICATIONS IN THE FOOD INDUSTRY
selectivity and reaction rates than in liquid
solvents.
- Formulation (SFFO): Considerable effort has
been undertaken to dry and formulate
ingredients by carrier impregnation and particle
“engineering,” mainly for designing drug-
delivery systems but also for preparing novel
food, cosmetics, and nutraceutical products.
- Sterilization and biological applications
(Biotech): The unique biocide properties of
supercritical fluids, and especially of CO2
possibly added with various additives, open
new opportunities for pest elimination,
sterilization, and virus inactivation in “mild”
conditions (near room temperature)
preserving substrate quality.
7.7.2 PRINCIPLES OF
SUPERCRITICAL FLUID PROCESSES
7.7.2.1 What Is a Supercritical Fluid?
All pure compounds can be found in three
states: solid, liquid, and vapor (or gas). On the
(pressure, temperature) diagram as shown in
Fig. 7.7.1, the three regions corresponding to
these three states are separated by curves that
meet at the triple point. Surprisingly, the vapor-
ization/liquefaction curve presents an end point
FIG. 7.7.1 General pressure-temperature diagram for
pure compounds.
7. FOOD PROCESSING: ALL THE FOOD INDUSTRY SECTORS
called the critical point (Pc
Tc). Beyond this point
(P > Pc et T > Tc), only one phase exists, called
supercritical fluid (SCF) while the liquid phase
pressurized beyond the critical pressure (P > Pc
et T < Tc) is called subcritical liquid (SCL).
Most compounds exhibit a critical pressure in
the range of 3–8 MPa, except highly polar mole-
cules such as water and ammonia. The critical
temperature increases with the complexity of
the molecule and very few “current” compounds
exhibit a critical temperature between 0°C and
50°C (ethane, ethylene, CO2, N2O, CHF3).
Mixtures behave in a more complex way,
depending on their composition, but “critical”
phenomena are also observed.
Obviously, CO2 (PC ¼ 7.38 MPa; TC ¼ 31°C) is
the most attractive supercritical fluid for many
reasons:
• Very inexpensive and abundant in pure form
(food grade) worldwide.
• Not flammable, not toxic, and
environmentally friendly.
• Critical temperature 31°C, permitting
operations at near-ambient temperature.
As shown in Fig. 7.7.2, CO2 density varies in a
wide range versus pressure and temperature,
especially around the critical point, but the fluid
becomes almost incompressible at pressure
beyond 50 MPa.
Although they do not present the advantages
of carbon dioxide, other types of fluids are con-
sidered for specific applications:
• Light hydrocarbons, especially liquefied
propane (PC ¼ 4.25 MPa; TC ¼ 96.7°C), appear
to be much stronger solvents than carbon
dioxide vis-à-vis lipids, but they present a
high explosion hazard.
• Hydrofluorocarbons (HFCs) are
environmentally acceptable at the present
time but very expensive; neither toxic nor
flammable, they may decompose in highly
toxic gases when submitted to a flame.
• Dimethyl ether, used as liquefied gas,
behaves as a “polar” solvent and is able to
 7.7.2 PRINCIPLES OF SUPERCRITICAL FLUID PROCESSES 485

FIG. 7.7.2 Carbon dioxide density versus pressure at different temperatures. From NIST http://webbook.nist.gov/chemistry/
fluid/.

dissolve a very wide range of compounds,
including many polymers (Lemert and De
Simone, 1991).
• Nitrous oxide (N2O) exhibits similar critical
properties as CO2; although it is commonly
used in anesthesia, it should be considered as
an oxidant that may lead to explosion when it
contacts flammable solutes.
• Water exhibits very attractive properties at
subcritical or supercritical conditions that are
in a completely different range (PC ¼ 22.1 MPa,
TC ¼ 374°C). Great variation of its dielectric
constant results in polarity and solvent
properties varying from the exceptionally
high polarity of common liquid water to a
nonpolar fluid dissolving organics and
precipitating salts in supercritical conditions.
7.7.2.2 Solubility in Supercritical
Solvents
Most applications of supercritical fluids (and
subcritical liquids) are related to their “tunable”
properties that can be easily changed by
monitoring pressure and temperature, particu-
larly on the possibility of varying their solvent
power over a wide range.
Carbon dioxide always behaves as a rather
weak nonpolar solvent that selectively dissolves
lipids such as vegetable oils, butter, fats, hydro-
carbons, and essential oils, but has a weak affinity
with oxygenated or hydroxylated molecules. It
does not dissolve any hydrophilic compound
such as sugars and proteins or mineral species
such as salts or metals. However, CO2 solvent
power and polarity can be significantly increased
by adding a polar cosolvent that is generally cho-
sen between short-chain alcohols, esters, or
ketones. For obvious reasons, ethanol is often pre-
ferred as it is abundant and cheap in pure forms
(food grade, pharmacopeia grade) while being
nonhazardous to the environment and not very
toxic. Moreover, it is to be noticed that although
water is only slightly soluble in supercritical CO2
(1–3 g/kg), it plays a very important role as a
“cosolvent” for many polar molecules; in fact,
water is present in most applications, especially
when natural products are processed.

7. FOOD PROCESSING: ALL THE FOOD INDUSTRY SECTORS

486 7.7. SUPERCRITICAL FLUID APPLICATIONS IN THE FOOD INDUSTRY

Fluid phase equilibria of mixtures are very com-
plex, and many types of phase diagrams can be
found. After the basic work of FRANCIS in 1954
(Francis, 1954, 1955), who measured solubilities
in liquid CO2 of hundreds of components and
phase equilibria of tens of ternary systems
including liquid CO2, thousands of articles have
dealt with high-pressure fluid phase equilibria,
covering a very wide range of compounds and
operating conditions. The reader could start on
books focusing on natural products (Stahl
et al., 1987; King and Bott, 1993; Rizvi, 1994;
McHugh and Krukonis, 1994; King and List,
1996) and symposium proceedings (ISASF,
1988–2016). Recent progress in thermodynamic
modeling permits predicting the behavior of
many mixtures; however, some measurements
that are difficult to perform are yet required to
set interaction parameters that cannot be calcu-
lated, especially for polar liquids (for example
in the case of strong hydrogen bonding). But
happily, it is not always necessary to handle
detailed thermodynamic data of the processed
mixtures to design SCF processes.
For “simple” systems and relatively low solu-
bility, the empirical correlation proposed by
Chrastil (Chrastil, 1982) can be used to interpret
experimental results with a good reliability that
satisfactorily fits the solubility data of 104
different organic compounds (Billoni et al.,
1988) without any complicated calculations:
C5ρk : exp ½a=T + b (7.7.1)
where C is the solute concentration and a, b, and
k the empirical constants. In fact, this simple
equation shows that:
• Solubility is strongly dependent on the fluid
specific gravity ρ as k is always positive and
in the range of several units; it drastically
decreases when the fluid is depressurized at
constant temperature below its critical
pressure, with a solubility variation of several
orders of magnitude permitting fluid-solute
separation.
• Solubility increases with pressure at constant
temperature but solubility may increase or
decrease when temperature is raised at
constant pressure. In fact, experimental
values on various substances show that
below a certain “inversion” pressure,
solubility decreases when temperature is
increased while beyond this pressure,
solubility increases with temperature. For
example, vanillin solubility curves versus
pressure at various temperatures intersect at
an “inversion” pressure of 140 bar
(Fig. 7.7.3); meanwhile, the inversion

VANILLIN solubility
10
Mass fraction (g/kg)

4 42°C
51°C
2
56°C
0
60 80 100 120 140 160 180 200 220
Pressure (bar)
FIG. 7.7.3 Vanillin solubility in CO2. Data from Billoni, N., Jose, J., Merlin, J.C. 1998. Solubility of heavy components in super-
critical CO2 using directly coupled supercritical fluid extraction-HPLC. In: Perrut, M. (Eds.), Proceedings of International Symposium on
Supercritical Fluids, Nice, France, ISBN 2-905267-13-5, Tome 1, pp. 373–380.

7. FOOD PROCESSING: ALL THE FOOD INDUSTRY SECTORS

 7.7.2 PRINCIPLES OF SUPERCRITICAL FLUID PROCESSES
pressure for triglycerides is in the range of
280–300 bar, depending on the oil source
(Stahl et al., 1987).
Moreover, it has to be emphasized that one of
the main interests of SCFs is related to the ability
to set very precisely their solvent power vis-à-vis
different compounds by tuning pressure, tem-
perature, and cosolvent content. This allows per-
forming very selective fractionation of complex
mixtures that cannot be resolved with classical
organic solvents or by any other process. This
is used either for sorting compounds belonging
to the same chemical family but differing by
their carbon numbers (i.e., fatty acids or oligo-
mers/polymers), or of similar molecular mass
487
but with slightly different polarities (i.e., neutral
and polar lipids).
Due to its nonpolar character, supercritical
CO2 is also used as an “antisolvent” in polar
organic solvents in which it readily dissolves,
leading to a significant decrease of their polar
character and causing precipitation of com-
pounds previously dissolved in these solvents.
7.7.2.3 Transport Properties of
Supercritical Fluids
SCFs are dense as liquids but “mobile” like gas,
as presented in Table 7.7.1: Very low viscosity
(Fig. 7.7.4), intermediate diffusivity. So, mass

TABLE 7.7.1 Comparison of Average Properties of Gases, Liquids, and SCF

Supercritical Gas
Property Liquid T Tc & P1 to 4 Pc (at Room T et P)

Specific Gravity ρ (kg m
3) 600–1600 100–900 0.6–2

–3
5
Viscosity η (Pa s) 10 10 –10 -4
10–5
Diffusivity D (m2 s
1) 10–9 10–8 10–5

FIG. 7.7.4 CO2 viscosity versus pressure at different temperatures. From NIST http://webbook.nist.gov/chemistry/fluid/.

7. FOOD PROCESSING: ALL THE FOOD INDUSTRY SECTORS

488 7.7. SUPERCRITICAL FLUID APPLICATIONS IN THE FOOD INDUSTRY
transfer (and similarly heat transfer) is fast in SCF
in comparison with liquid solvents or water.
Moreover, SCF rapidly diffuses into porous
media, easing either extraction from solid mate-
rials or impregnation of solutes (NIST, n.d.;
ISASF, 1988–2016; Reid et al., 1986; Brunner, 1994).
Another important property of SCF solvents is
related to the drastic viscosity reduction of a liquid
phase contacted with a SCF solvent that partly
dissolves in the liquid, even at a pressure below
critical. This is of use for fluidifying viscous oils
and waxes in order to ease processing (filtering,
reaction, extraction). Similarly, many polymers
are “swollen” and “plasticized” by compressed
carbon dioxide, with a decrease of the glass tran-
sition temperature by several tens of degrees Cel-
sius, permitting an easy processing (forming and
atomizing, mixing, grafting, foaming), as shown
in Fig. 7.7.5 for PEG6000 (Deschamps, n.d.).
7.7.3 SUPERCRITICAL FLUID
EXTRACTION (SFE)
7.7.3.1 SFE Concept
The drastic variation of solvent power of
supercritical fluids with pressure and tempera-
ture permits designing extraction processes
based on the following concepts:
65
Binary system
Melting point (°C)
55 PEG 6000 / CO2
45
35
0 40 80 120
Pressure (bar)
FIG. 7.7.5 Melting point decrease of PEG6000 in presence
of pressurized CO2 (Deschamps, n.d.).
7. FOOD PROCESSING: ALL THE FOOD INDUSTRY SECTORS
• Extraction of nonpolar or low-polarity
compounds present in the raw materials in
conditions where the fluid is a powerful
solvent (supercritical or subcritical with a high
specific gravity); for solid raw materials, this is
operated in batch mode as there are no means
available to introduce and withdraw solid
materials to and from a high-pressure vessel
(except in the very special case of coffee
beans). In very large-scale plants, feed loading
and spent material unloading are operated by
pneumatic transport; in lab, pilot, and
medium-scale plants, feed is introduced in a
“basket” consisting of a cylinder closed by
two filters that is installed in the pressure
extractor.
• Fluid-extract separation in conditions where
the fluid is a weak solvent, by
depressurization and heating to operate
almost isothermally, avoiding formation of
liquid CO2, or, in some rare cases, by
heating or fluid scrubbing at constant
pressure.
• Fluid recycle either by gas liquefaction, liquid
pumping and heating to extraction
temperature, or by gas compression and
cooling to extraction temperature. In very
large plants, the second cycle is preferred
while the first one is operated in most
lab, pilot, and medium-scale extraction
plants.
This batch mode imposes costly operation of
pressure cycling and material handling, what-
ever the effort to reduce both cycle duration
and manpower by automation. Cycle duration,
energy consumption, and CO2 losses are to be
optimized on a case-by-case basis on the basis
of experimental data gathered at the pilot scale.
160 7.7.3.2 Extraction Kinetics
Thousands of works on thousands of differ-
ent materials, mostly natural products, have
been published with or without modeling
 7.7.3 SUPERCRITICAL FLUID EXTRACTION (SFE)
(ISASF, 1988–2016; Brunner, 1994; Sovova, 2012;
Pardo-Castanez et al., 2015). It is not in the scope
of this chapter to cite and discuss this back-
ground, and we would prefer to present a sim-
ple pragmatic view based on our own
experimental results and long-term experience.
7.7.3.2.1 Simple Model
Most extraction kinetics confirm that batch
extraction of dry solid material can be repre-
sented by the curve in Fig. 7.7.6: Extract mass
yield y (kg extract/kg feed) or the relative yield
y/yT where yT is the maximum extractable solute
mass percentage in feed versus extraction time,
or better, versus the solvent ratio S (CO2 mass/
feed mass); two zones clearly appear.
- At first, a straight line corresponding to
saturation of the exiting CO2 by extract,
Relative yield (%)
100
80
60 Diffusion-controlled extraction
40
20 Solubility-controlled extraction
0 Time or
solvent ratio
FIG. 7.7.6 General shape of extraction curves of dry
material.
Yield (Weight % of the feed)
3 1: Us = 10 kg/h
2 2 : Us = 15 kg/h
1 Solubility :
y/yT = a. S
10 20 30
FIG. 7.7.7 Oil extraction from sunflower seeds with pure CO2 at various fluid flow rates (Perrut et al., 1997).
7. FOOD PROCESSING: ALL THE FOOD INDUSTRY SECTORS
489
showing that no mass transfer limitation
hinders the extraction rate due to “easy”
access to the solute.
- Then, an asymptotic line showing mass
transfer limitation related to diffusion inside
the solid material preventing CO2 saturation.
These limitations depend on material
pretreatment (milling, sieving) and bed
porosity (packing technique).
However, some other factors—often ignored
at the lab or pilot scale—may play an important
role at the large scale: Material agglomeration,
fluid channeling, and dead zones inside the
material bed may drastically degrade extraction
performances that have been expected from
small-scale experiments.
This mechanism is confirmed by the fact that,
when modifying the fluid flow rate and conse-
quently the contact time, the first part of the
extraction curve is not changed while the second
part of the curve is significantly altered with a
decreasing efficiency of each kg of CO2 when
the flow rate is increased, as shown in
Fig. 7.7.7 (Perrut et al., 1997).
So, it can be said that:
- In the saturation zone, the yield y is directly
proportional to the solvent ratio S and to
solute solubility s (kg solute/kg CO2) in the
fluid at the operating conditions, and the
advancement of extraction, until yield reaches
a value ysat, can be written as:
Diffusion
3 : Us = 30 kg/h
40 50 60 Solvent ratio (kg CO2/ kg feed)
490 7.7. SUPERCRITICAL FLUID APPLICATIONS IN THE FOOD INDUSTRY
y ¼ s:S
It is also common to introduce a 5 s/yT
y=yT ¼ a:S
- In the diffusion zone, the main parameter is no
longer solubility but contact time τC that can
be defined as:
τC ¼ ε:ðMF =ρF Þ=ðQS =ρS Þ
where ε is the bed porosity, MF and ρF the mass
and specific gravity of the feed material, and QS
and ρS the mass fluid flow rate and specific grav-
ity. For a given case, τC is proportional to the
inverse of fluid specific velocity defined as
uS 5QS/MF that can be considered as the key
parameter to describe the kinetics in this zone.
Very useful in practice, this “model” permits
an easy scale up, but it must be used with pru-
dence as it globalizes the extract as a unique
product. Meanwhile, the extract composition
100
80
Yield/Total yield ratio (%)
60
40
20
0
0 100
FIG. 7.7.8 Spices extraction with supercritical CO2 (250–300 bar; 40–60°C).
7. FOOD PROCESSING: ALL THE FOOD INDUSTRY SECTORS
also varies along extraction time and also
depends on pressure and temperature, all the
more when the natural feed contains more
moisture.
7.7.3.2.2 Dry Feeds
Among many experimental results available
in the literature that clearly support this simple
kinetic description, we propose the following
ones related to dry ground spice extraction by
supercritical CO2.
According to Fig. 7.7.8, the extraction kinetics
of seven spices lead to a quasiunique curve in
the “saturation” phase when we represent y/yT
versus a.S with a 5 s/yT.
It can be seen that the yield ysat corresponding
to the limit of the saturation zone varies signifi-
cantly from one species to the other, depending
on the species’ nature and particle size: 90% for
pimento but only 30% for black pepper for
which grinding was not correctly operated
(too coarse particles). The same grinding issue
is also shown in Fig. 7.7.9 on another spice spe-
cies. So, this very simple kinetic description
Spices
caraway, a = 3
curcuma, a = 35
paprika, a = 4
pimento, a = 4
black pepper, a = 8
coriander, a = 7
nutmeg, a = 6
200 300 400 500
S *a (kg/kg)
 7.7.3 SUPERCRITICAL FLUID EXTRACTION (SFE) 491
Piper cubeba
10

Mass yield (%)

6

0
0 5 10 15 20
Solvent/feed ratio (kg/kg)

FIG. 7.7.9 Extraction of Piper cubeba by pure CO2 (90 bar; 40°C; 3.86 kg CO2/kg feed/h).

teaches valuable information related to feed when the extract is readily soluble in water like
preparation that is of major importance for scal- caffeine or vanillin.
ing up to commercial scale (see Section 7.7.3.3). In several processes operated at a very large
scale for long periods, the feed must be hydrated
before processing. Coffee beans are saturated in
7.7.3.2.3 Humid Feeds water prior to supercritical CO2 decaffeination;
But, another parameter can modify the extrac- similarly, cork is humidified before treatment
tion curve shape: The moisture content in the in order to remove trichloroanisole to make
processed material. In fact, most “dry” natural “safe” wine stoppers and ginseng powder is trea-
products always contain some moisture. This ted for pesticide elimination.
water has a positive effect on extraction kinetics, This effect is illustrated in Fig. 7.7.10, where
as shown by many works, when its concentration we compare extraction curves of “crude” and
is limited (generally below 10% m/m), moreso humidified vanilla powder.

Vanilla powder FIG. 7.7.10 Extraction of vanilla Bourbon pow-

100% der by pure CO2 with or without water addition
(240 bar; 40°C; 13–15 kg CO2/kg feed/h).
80%
Vanillin yield (%)

60%

40%
Powder
Powder + water
20%

0%
0 20 40 60 80 100 120
Solvent ratio (kg CO2/kg feed)

7. FOOD PROCESSING: ALL THE FOOD INDUSTRY SECTORS

492 7.7. SUPERCRITICAL FLUID APPLICATIONS IN THE FOOD INDUSTRY

Black-current
25

20

Mass yield (%)

15

10
Seeds 1 700 µm
5 Seeds 2 700 µm
Seeds 1 1,500 µm
0
0 50 100 150 200 250
Solvent ratio (kg CO2/kg feed)

FIG. 7.7.11 Total extract of black-current seeds by pure CO2 (200 bar; 55°C; 10–14 kg CO2/kg feed/h).

Black-current oil
But, water is also extracted by supercritical 100
CO2 as, at the difference with hexane to which

Relative oil yield (%)

supercritical CO2 is often assimilated, water is
significantly soluble in CO2. In classical condi-
tions of extraction of natural products (300 bar
and 50°C), water loading is 3 g/kg. So, when pro-
cessing natural stuff, even dry (generally down to
8% m/m moisture), some water is extracted by
supercritical CO2 and extracts are often found
as emulsions, moreso when fresh plants (30%–
60% dry matter) are processed, of course.
This can be illustrated by two examples:
• Black-current seeds
Extraction curves of two different lots of dry
milled black-current seeds by pure CO2 in
“mild” conditions are presented: Total extract
(Fig. 7.7.11) and oil after water separation
(Fig. 7.7.12). It appears that oil extraction is
almost completed at a solvent ratio of 70 and
extract is essentially composed of water for
higher solvent ratios. As black-current seeds
are very difficult to break, it is also to be noted
that a coarse milling leads (seeds 1–1500 μm) to
a very low yield in comparison with milling in
dry ice (Seeds 1–700 μm). Knowing that the oil
content is not the same in the two different seed
lots, Fig. 7.7.12 shows that the representation of
the relative yield is pertinent to compare extrac-
tion conditions.
80
60
40 Seeds 1
20 Seeds 2
0
0 50 100 150 200 250
Solvent ratio (kg CO2/kg feed)
FIG. 7.7.12 Relative oil yield of black-current seeds by
pure CO2 (200 bar; 55°C; 10–14 kg CO2/kg feed/h).
• Fresh aromatic herbs: Lavenders
Everybody can easily observe the difference
in odor of fresh and dry herbs: A very fine smell
in nature or when freshly cut, but some “hay”
odor appearing when they are dried and kept
for weeks or months. So, it is a challenge to
see if the extraction of fresh herbs with supercrit-
ical CO2 does lead to a complete extract deliver-
ing a nature-like fragrance.
We present extraction curves of large lots of
freshly cut lavender Maillette (Fig. 7.7.13) and a
lot of dry lavender Matherone (Fig. 7.7.14). In
Fig. 7.7.13, the vegetal variability clearly appears
from one lot to the other. More interestingly,
water extraction is very important: The continu-
ous line corresponding to the water saturation of

7. FOOD PROCESSING: ALL THE FOOD INDUSTRY SECTORS

 7.7.3 SUPERCRITICAL FLUID EXTRACTION (SFE) 493
Lavander Maillette FIG. 7.7.13 Extraction of fresh flowers of lav-
6.0 ender Maillette (39% dry matter) by pure CO2
(- - - -) and water extraction at saturation ()
5.0 (280 bar; 45°C; 6–7 kg CO2/kg feed/ h).
Mass yield (%)

4.0

3.0

2.0

1.0

0.0
0 2 4 6 8 10 12 14
Solvent ratio (kg CO2/kg feed)

Lavander Matherone FIG. 7.7.14 Extraction of dry flowers of laven-

6.0 der Matherone (63% dry matter) by pure CO2
(280 bar; 45°C; 7 kg CO2/kg feed/ h).
5.0
Mass yield (%)

4.0

3.0

2.0

1.0

0.0
0 2 4 6 8
Solvent ratio (kg CO2/kg feed)

CO2 is exactly parallel to the extraction curve • Rosemary

after completion of the terpenic extract of laven-
der. This water extraction is much less impor-
tant when the moisture content is lower, as
shown on Fig. 7.7.14 on which is also repre-
sented the precedent extraction curve of laven-
der Maillette.
From these results, it clearly appears that
extraction must be stopped for a solvent ratio
of 4, as proceeding further will essentially
extract water that shall be separated later from
the valuable terpenic extract, causing useless
expenses and extract losses.
Lots of fresh and dry plants of rosemary—a
native plant in Provence grown for food and fla-
vor applications—were extracted. In order to
obtain reliable kinetic curves instead of erratic
results due to great variations of dry matter con-
tent (varying from 36% m/m for a freshly cut
plant to 86% m/m after storage for 1 week),
the extract yield—calculated on dry matter in
feed mass—is represented versus the solvent
ratio, which is also calculated on dry matter in
feed mass, in Fig. 7.7.15, leading to a unique

7. FOOD PROCESSING: ALL THE FOOD INDUSTRY SECTORS

494 7.7. SUPERCRITICAL FLUID APPLICATIONS IN THE FOOD INDUSTRY

Rosemary relatively low pressure (#120 bar) followed by

6 a high-pressure (>400 bar) step leading to a
5 flavor-free wax presenting strong antioxidant
Mass yield/Dry (%)

4
properties.
Moreover, a polarity modifier could be added
3 after this step-wise extraction with pure CO2,
2 DM 67% leading to higher-polarity compounds, as exem-
DM 32% plified in the extraction/fractionation of Ortho-
1
siphon (Java tea) presented in Fig. 7.7.16. The
0 first step is at 120 bar and the second step at
0 5 10 15 20 25
280 bar with pure CO2, followed by a third step
Solvent ratio (kg CO2/kg dry matter)
at 280 bar with the addition of ethanol, leading to
FIG. 7.7.15 Extraction of rosemary by pure CO2 (300 bar; three different fractions of growing polarity.
44°C; 13.3 kg CO2/kg dry matter/h).

7.7.3.3 Extract Fractionation and

kinetic curve. This clearly demonstrates the
need to take into account moisture content as a
Recovery
key parameter. Although often considered an “easy” opera-
tion based on a drastic reduction of fluid solvent
7.7.3.2.4 Multistep Extraction power, extract recovery from solvent exiting the
Although difficult to implement at the com- extractor(s) and collection are always very
mercial scale, it was often shown that CO2 important and difficult operations that might
extraction can lead to several fractions of extract jeopardize extraction performance, especially
by step-wise pressure extraction. For example, when the extract yield is very small as in herb
rosemary terpenic flavor can be obtained at or flower processing.

Orthosiphon stamineus
4.0

3.5 120 bar

280 bar
3.0
280 bar + EtOH
Mass yield (%)

2.5

2.0

1.5

1.0

0.5

0.0
0 5 10 15 20 25 30 35
Solvent ratio (kg CO2/kg feed)

FIG. 7.7.16 Extraction of Java tea leaves (Orthosiphon stamineus) (120 bar then 280 bar then 280 bar +9.5% EtOH; 40°C;
3–3.5 kg CO2/kg feed/h).

7. FOOD PROCESSING: ALL THE FOOD INDUSTRY SECTORS

 7.7.3 SUPERCRITICAL FLUID EXTRACTION (SFE)
7.7.3.3.1 Extract Recovery Methods
In fact, extract collection can be operated in
several ways or combinations thereof:
• Taking profit of solvent power variation, extract
is precipitated from the fluid solution by
isothermal depressurization toward the CO2
recycle pressure (generally 50 bar). Although
the thermodynamic principle is “obvious,” its
implementation is often very complicated
due to the following issues:
• Heat supply after depressurization needs a
high-duty exchanger that may be plugged
by viscous extract.
• Formation of mist of extract droplets
carried by the fluid that may be entrained
out of separators; this is why cyclonic
chambers are recommended in order to
supply a much better collection than
classical gravity decanters.
• Extract withdrawal from separators
operating at a rather high pressure with
risk of emission of extract mist and
correlated losses and hazards; this can be
avoided by using pressure locks
permitting a smooth depressurization and
avoiding extract and CO2 losses.
• Natural extracts often appear as emulsion
oil-in-water or water-in-oil that must be
reprocessed to eliminate water and reach a
“clear” extract (Section 7.7.3.2.2).
• Crude extracts are often very viscous and
withdrawal is difficult; moreover,
equipment cleaning between different plant
processings is a very tiresome operation.
• Moreover, when flowers and herbs are
processed for perfumes and cosmetics,
reprocessing the crude extract is required
to reach an absolute soluble in ethanol-
water mixture (see Section 7.7.3.2.2).
• But, the unique properties of supercritical
fluids could also be exploited to fractionate the
extract:
• By a step-wise depressurization from
extraction pressure to recycle pressure.
This is commonly used in food ingredient
7. FOOD PROCESSING: ALL THE FOOD INDUSTRY SECTORS
495
processing: Rosemary (separation of
antioxidant wax and flavor) and spices
(carotenoids from capsaicin from chilly or
piperin from pepper flavor).
• By a variation of temperature after
depressurization at recycle pressure: In a
first separator, waxes are precipitated from
liquid CO2 that is further vaporized for
dewaxed extract collection.
• Scrubbing the fluid with an adequate solvent
at constant pressure: This is operated for
coffee decaffeination where CO2 is scrubbed
with water prior to recycling, leading to dry
caffeine powder after water evaporation in a
spray dryer and to low-energy consumption
with such a CO2 cycle. The collection solvent
may be also an oily excipient in which the
extract dissolves (i.e., aromatized edible oil or
a cosmetic ingredient).
• Adsorption onto a porous material, like
activated charcoal, when the extract cannot be
completely recovered by depressurization
and decantation, either when the extract is
not to be recovered during adsorbent
regeneration (caffeine in some tea and coffee
decaffeination plants or odorous compounds,
as in cork treatment or in pesticide
elimination), or be recovered by adsorbent
reextraction by CO2 (light aromatic fractions).
In a variant, water adsorption can be operated
on 3A zeolite at an extractor exit prior to
depressurization to recover a “dry” extract.
7.7.3.3.2 Extract Reprocessing
A main concern of SFE operation is related to
extract composition and aspect. In most cases
when herbs are processed, the “total” extract—
when not fractionated as described before—
appears as a viscous “honey” in which water is
emulsified like mayonnaise, as illustrated by Lin-
alool Thyme (Thymus vulgaris linaloliferum) extract
obtained at 280 bar, 45°C, and 12 kg CO2/kg.
Obviously, these extracts must be reprocessed
to eliminate water, often by centrifugation
(Fig. 7.7.17A) and/or to eliminate the viscous
“waxes” (by ethanol/water reextraction and
496 7.7. SUPERCRITICAL FLUID APPLICATIONS IN THE FOOD INDUSTRY

(A)

(B)
FIG. 7.7.17 (A) Linalool Thyme: Total extract (left) before and after water decantation by centrifugation. (B) Linalool
Thyme: Total extract (left) leads to wax powder (center) and aroma oil (right) after ethanol/water reprocessing.

filtering at low temperature). The sticking crude
extract (“concrète”) with a yield of 4% leads to a
wax powder with a yield of 1.8% and an aromatic
oil with a yield of 1.5%; water and losses repre-
sent the complement (Fig. 7.7.17B).
Another typical example is presented in
Fig. 7.7.18, which shows vanilla bean extract
after decantation of the three phases: an oil
phase on top and an intermediate aqueous
phase rich in vanillin.
slow rate, and at 280 bar leading to an unpleas-
ant smelling dark extract. But, by fractionating
the extract through a two-step separation
(65 bar—20°C and 55 bar—40°C), a viscous and
unpleasant-smelling fraction is obtained in the
first separator and an extract very similar to
the first one is collected in the second separator
at a much higher rate than at 100-bar extraction
(intermediate curve). By this way, a much lower
amount of fluid is required.

7.7.3.3.3 Example: Fragrance Extraction and

Fractionation From Hemp
As presented in Fig. 7.7.19, extraction curves
of hemp (the dry entire plant) clearly illustrate
the classical shape at 100 bar with the collection
of a clear, pleasant-smelling extract at a very
7.7.3.4 Optimization and Scale Up
Few documents are available for engineering
plants for natural products SFE (Perrut et al.,
1997; Del Valle et al., 2014; Nunez and Del
Valle, 2014; Del Valle, 2015). In fact, SFE is only

7. FOOD PROCESSING: ALL THE FOOD INDUSTRY SECTORS

 7.7.3 SUPERCRITICAL FLUID EXTRACTION (SFE) 497

FIG. 7.7.18 Vanilla beans extract decantation.

Hemp
4.5

4.0 100 bar

3.5 280 bar

3.0
Mass yield (%)

280 bar
(fractionation)
2.5

2.0

1.5

1.0

0.5

0.0
0 5 10 15 20 25 30 35
Solvent ratio (kg CO2/kg of feed)

FIG. 7.7.19 Extraction of hemp by pure CO2 with or without extract fractionation (120 and 280 bar–40°C: 6–10 kg CO2/kg
feed/h).

seldom operated in a unique extractor at the com-
mercial scale, as it is far from optimum except in
very special high-value product processing. In
most cases, several extractors are operated in
series in order to minimize CO2 losses and pro-
cess cycle duration. At least three extractors
(Del Valle et al., 2014; Nunez and Del Valle,
2014; Del Valle, 2015) are employed, two or more
ones being in extraction while one is in the
depressurization (spent feed unloading; fresh
feed loading) and recompression (Fig. 7.7.20).
In order to reduce the quantity of CO2 needed
for a given feed mass, it is valuable to simulate a
countercurrent flow between feed and fluid.
Supposing that three extractors are implemen-
ted. CO2 is first contacted with a partially
extracted feed and then is saturated by percola-
tion through the “fresh” feed extractor.

7. FOOD PROCESSING: ALL THE FOOD INDUSTRY SECTORS

498 7.7. SUPERCRITICAL FLUID APPLICATIONS IN THE FOOD INDUSTRY
Extractors
Condensor
CO2
CO2 reservoir
Heater
CO2 pump
Co-solvent
FIG. 7.7.20 Supercritical fluid extraction.
Then, when the first extractor feed is exhausted,
this extractor is depressurized and unloaded.
Meanwhile, the second one becomes the first to
be percolated and the newly loaded third one
becomes the second to be contacted. By this
way, the fluid exiting the extractor battery is
almost always saturated in extract and, conse-
quently, is “optimally” used. Of course, with four
or five extractors, this countercurrent implementa-
tion is facilitated, but global cost suffers of supple-
mentary investment (Del Valle et al., 2014; Nunez
and Del Valle, 2014; Del Valle, 2015).
The following points must also be empha-
sized when scale up is to be implemented:
• Feed preparation is of key importance as feed
agglomeration and fluid channeling may
jeopardize an operation that could appear
7. FOOD PROCESSING: ALL THE FOOD INDUSTRY SECTORS
Separators
Extract
pump
profitable in light of pilot-scale kinetics.
In fact, many natural products must be
pretreated before SFE. To avoid “caking,”
hops are pelletized while waxy and oil-rich
feeds often need to be mixed with an inert
packing such as food-grade cellulose
fibers. Great care must also be taken to
avoid the formation of very fine particles
during raw material milling. Dust may
be responsible of filter blockage, leading
to safety issues during basket
depressurization, filter collapse entraining
transport of feed powder throughout the
plant, or basket deformation requiring a
costly maintenance.
• Pilot-scale optimization is of key importance
with the analysis of extraction kinetic curves
and extract composition in various conditions
 7.7.4 SUPERCRITICAL FLUID FRACTIONATION (SFF)
(P, T, uS), but also material pretreatment and
extract composition shall not be
underestimated. Moreover, experience shows
that the first large-scale extractions may not
lead to a valuable product, but are used to
finalize the process and product
optimization.
• Extract posttreatment needs great attention as
shown before. Centrifugation, cold filtering,
and, in certain cases, molecular distillation
are implemented in order to obtain a clear oil,
an ethanol-soluble fragrance, or a
concentrated aroma by eliminating
emulsified water and viscous waxes.
7.7.3.5 Potential and Limitations
After decades of stop-and-go strategies, and
although final costs remain too high for many
applications, especially when limited amounts
of products are to be processed, the technology
has become more and more accepted in most com-
panies, many of which are now considering SFE as
a “necessary” tool that must be implemented to fit
new marketing and regulatory requirements.
At the present time, hundreds of industrial
SFE plants are operating worldwide on natural
products, with extractor capacity ranging from
20 L for fine perfumes, aromas, colorants, and
phytopharmaceuticals to 10–20 m3 for food
(hops, coffee, tea, rice, specialty edible oils, egg
yolk defatting) and cork processing.
However, it is honest to say that SFE cannot
substitute for all solvent extraction processes as
CO2 is a nonpolar fluid of limited solvent power,
even if ethanol addition can increase fluid polar-
ity (but entraining a retreatment step of the
extract). Along with technology improvement,
a trend to increase service pressure (up to
1000 bar) has been observed in order to increase
fluid polarity (avoiding the addition of ethanol)
and to reduce extraction duration (and conse-
quently, amortization, energy, and manpower
savings) (King, 2013). This very high pressure
equipment permits producing many compounds
that cannot be extracted in “classical” conditions
7. FOOD PROCESSING: ALL THE FOOD INDUSTRY SECTORS
499
(300 bar). However, it is underlined that the
extract composition is always significantly mod-
ified when the extraction pressure is increased, as
stated in Section 7.7.3.2.3 and illustrated in
Fig. 7.7.21 on carotenoid extraction from sea
buckthorn (Hippophae rhamnoides) (Clavier et al.,
2014); this can have adverse consequences on
extract color, composition, and global properties.
7.7.4 SUPERCRITICAL FLUID
FRACTIONATION (SFF)
7.7.4.1 Concept and Efficiency
SFF is founded on the high and “tunable” selec-
tivity of supercritical fluids combined with the
efficiency of multistage countercurrent processes
with reflux, as currently used in distillation or
liquid-liquid extraction. Fundamentals can be
found in Brunner (Brunner, 1994). As said earlier,
supercritical CO2 solvent power is very depen-
dent on its specific gravity and it is therefore pos-
sible to tune this solvent power so as to very
selectively separate feed components, even if they
are very close to each other. The SFF process is
implemented according to the flow sheet in
Fig. 7.7.22 and is operated in continuous mode.
The liquid feed is pumped at an intermediate level
into the column while supercritical CO2 is intro-
duced at the column bottom. Due to the density
difference, CO2 percolates to the top of the column
while the liquid phase flows down in the counter-
current. Contact between the two phases is
ensured by packing (structured or random) ele-
ments. The feed fraction dissolved in CO2 is col-
lected on top of the column as extract through
several separators in series while the liquid phase
is collected at the bottom of the column as raffi-
nate through two-step decompression vessels.
The fluid loop is similar to the one used in SFE
plants described earlier: Extract separation by
(possible multistep) depressurization and heat-
ing, fluid purification (when needed) on an adsor-
bent bed, and fluid recycling by CO2 liquefaction,
pumping, and reheating. Cosolvent addition is
 % of Carotenoid in the extract
1.60%

1.40%

1.20%

1.00%
% carotenoid

0.80% P = 900 bar

P = 600 bar
0.60% P = 300 bar

0.40%

0.20%

0.00%
0 20 40 60 80 100
Solvent ratio

FIG. 7.7.21 Sea buckthorn (Hippophae rhamnoides) extraction: carotenoid content in extract by pure CO2 (Clavier et al.,
2014).

FIG. 7.7.22 Supercritical fluid fractionation.

 7.7.4 SUPERCRITICAL FLUID FRACTIONATION (SFF)
possible although seldom implemented, as selec-
tivity requires a rather “weak” solvent power of
the fluid.
However, some specific implementations are
required in SFF:
- As for all countercurrent systems, fluid and
liquid flow rates must be set below the
flooding zone that depends on flow rates,
phase density difference, interfacial tension,
and liquid viscosity related to pressure and
temperature. As there is no reliable correlation
to predict flooding, experimental work at the
pilot scale is required on the real phases to
avoid liquid entrainment by the fluid.
Moreover, in certain conditions, liquid
foaming may appear and lead to rapid,
unpredictable flooding.
- Due to a faster mass transfer rate, it is better to
work in “trickle” flow, with the continuous
phase being CO2 while the liquid phase is
dispersed. This means that the fluid-liquid
interface is preferably located in the bottom
head of the column and liquid withdrawal is
operated by level control. This level control is
rather difficult to operate with high reliability
in many cases, especially with foaming
liquids, and the sensor shall be chosen on a
case-by-case basis (optoelectronic,
conductivity, pressure, etc.).
- Liquid phase withdrawal has to be tuned very
precisely so as to avoid a strong perturbation
of pressure inside the column. This is why a
two-step depressurization is recommended,
with a first vessel in which pressure is
maintained rather close to the column one
while the second vessel is used as a pressure
lock for an easy liquid recovery. Moreover,
CO2 being significantly soluble in most feeds,
the liquid phase exiting the column bottom is
loaded with CO2 that can be partly recovered
from the first vessel.
- Extract reflux is very important to increase
fractionation performances. It requires a
degassing vessel, a pump, and a heat
7. FOOD PROCESSING: ALL THE FOOD INDUSTRY SECTORS
501
exchanger of significant cost. So, in small-scale
columns (up to 10-cm diameter), the reflux is
caused by a thermal gradient along the
column by heating different sections of the
jacket at increasing temperatures from bottom
to top. For most feeds, the component
solubilities decrease when temperature
increases at constant pressure, causing partial
demixion of dissolved compounds from the
fluid as it flows up, causing internal liquid
reflux. But for large columns, an external
reflux is required as the heating power
through demixion jacket is limited and may
cause radial temperature gradients
deleterious to selectivity.
7.7.4.2 Examples of Applications
It is rather surprising that SFF of liquid mix-
tures has been paid much less attention than
the “classical” SFE of solids, although this pro-
cess could lead to much lower operating costs
as it is basically a continuous process that can
be totally automated. Meanwhile, solid treat-
ment requires a batch process with a significant
manpower requirement. Some developments
have been dedicated to fractionation of bever-
ages (juices, alcoholic beverages), citrus
essences, aromas and natural colorants, polyun-
saturated oils, and phospholipids/glycolipids.
These applications are very demonstrative as
they permit fully taking profit of supercritical
fluid carbon dioxide possibilities as nontoxic,
“natural” solvents with high selectivity at rela-
tively low temperature preventing alteration of
thermolabile products.
7.7.4.2.1 Fractionation of Lipid Mixtures
Fractionation of lipid mixtures from plants
(edible oils) (Brunner, 1994), animals (eggs,
milk) (Perrut et al., 2007), and various marine
sources (mostly fish, but also krill and microal-
gae) has demonstrated the great selectivity of
SFF since 1985. Various applications were
explored, including oil and fatty acid
502 7.7. SUPERCRITICAL FLUID APPLICATIONS IN THE FOOD INDUSTRY
deodorization and decoloration; polyunsatu-
rated fatty acid ester fractionation to obtain
enriched cuts of ω3-esters (essentially EPA or/
and DHA); mono-, di-, and tri-glyceride frac-
tionation; phospholipid and glycol-lipid purifi-
cation; concentration of squalene and
tocopherols; etc. (Brunner, 1994; Riha and
Brunner, 2000; Fiori et al., 2014; Perrut et al.,
2007). From these numerous works, it appears
that SFF of oils is very selective, either based
on fatty acid chain length (but not at all on the
unsaturation number) or on polarity differences
(for minor polar molecules concentration) as for
isolation of pure fractions of digalactosyl-
diglycerides from wheat gluten lipids (Perrut
et al., 2007).
7.7.4.2.2 Alcoholic Beverage Fractionation
Alcoholic beverage fractionation is of high
economical interest, as the manufacture of
low-alcohol beverages is of increasing interest
for ethical, religious, and/or dietetic motiva-
tions, and improving their quality will lead to
growing profitable markets. Alcoholic bever-
ages contain mainly water and ethanol (3–
10 wt% for fermented ones and 40–60 wt% for
distilled ones). Meanwhile, aromas are present
at a total concentration between 500 and
5000 ppm comprising hundreds of components
at the trace level, with the main ones being very
similar to ethanol (ethyl acetate, other alcohols).
Hydrophilic components are also present
(sugars, proteins, colorants) that often cause liq-
uid foaming.
• Process concept
In fact, such fractionation represents a very
difficult challenge as ethanol increases the fluid
solvent power, reducing its selectively vis-à-vis
water and aroma products. High selectivity
between ethanol and aroma extract requires a
high reflux in very “mild” conditions (low fluid
density and solvent power). Moreover, aroma
collection is extremely complex (high dilution
and high volatility). Classical mechanical
7. FOOD PROCESSING: ALL THE FOOD INDUSTRY SECTORS
separations are not at all efficient enough in this
case, even with high performance cyclonic sep-
arators; adsorption of the organics carried by
gaseous CO2 appears to be the most convenient
process, even if it requires a periodic system for
aroma recovery by desorption with supercritical
CO2.
Schultz and Randall (1970), Schultz et al.
(1974) founded the basic knowledge of selective
fractionation of aroma compounds from alco-
holic aqueous mixtures, using liquid CO2. They
established simple relations between the carbon
numbers of the alcohols or esters and their dis-
tribution coefficient between water and liquid
CO2 (Francis, 1954). In the late 1970s and the
1980s, numerous investigators worked on etha-
nol extraction from fermentation broth in order
to obtain “dry” ethanol to be used as fuel in
motors. However, it rapidly appeared that
CO2 is not selective enough to “break” the azeo-
trope, which ruins any interest in this process.
Concerning aroma-ethanol separation, attrac-
tive data (Di Giacomo et al., 1991) evaluate phase
equilibria at various pressures and temperatures
between CO2, water, ethanol, and a few aro-
matic compounds that are present at significant
concentrations in wine and beer (Table 7.7.2),
showing that, as expected, selectivity (defined
as α ¼ ðaroma wt=ethanol wtÞ in extract
ðaroma wt=ethanol wtÞ in feed ) decreases when
ethanol concentrations in the liquid phase and
optimal conditions can be found for “mild” con-
ditions (100 bar, 40°C), although selectivity
seems maximum with liquid CO2 (60 bar, 20°C).
Wine and wine must (Perrut and Nunes da
Ponte, 1997; Ruiz-Rodriguez et al., 2010, 2012;
Macedo et al., 2007), beer (Perrut and Nunes
da Ponte, 1997), and cider (Medina and
Martinez, 1997) dealcoholization have been
investigated for many years.
• Wine fractionation
SFF was proved to be a valuable process to
fractionate wine, leading to a tasteless raffinate
and a global extract yield near 0.6 wt%
 7.7.4 SUPERCRITICAL FLUID FRACTIONATION (SFF) 503

TABLE 7.7.2 Liquid and Supercritical CO2 Selectivity

T (°C) P bar Acetaldehyde n-Propanol Ethyl Acetate Isobutanol Isoamylalcohol

20 60 11.8 14.9 3.1 7.9 13.9

40 100 5.4 8.2 2.0 4.2 7.5

40 150 5.6 9.7 2.5 4.1 9.8

60 200 2.1 2.5 2.0 3.9 2.3

From Di Giacomo, G., Brandini, V., Del Re, G., Martinez de la Ossa, E. On the feasibility of dense carbon dioxide based extraction-recovery process for alcohol-
reduced beer and wine production. In: Perrut, M. (Ed.), Actes du 2ème Colloque sur les Fluides supercritiques, Paris, France, 1991, ISBN 2-905267-17-8,
pp. 63–68.

comprising a first pink ethanol-rich fraction
smelling wine, and an aromatic-rich extract frac-
tion concentrated in heavy components with a
much smaller yield of 1 to 3.10
4. As tested by
a panel of wine experts, the organoleptic quality
of these aromatic extracts is strongly dependent
on the recovery process used and is very satis-
factory when optimized (Perrut and Nunes da
Ponte, 1997).
• Beer dealcoholization
For a long time, most ethanol-free beer (<0.5
or 1% vol. ethanol) has been considered of poor
organoleptic quality. So, selective fractionation
of beer aromas is of key interest, either for rein-
corporation in the aroma-free raffinate after
ethanol depletion (distillation, reverse osmo-
sis, or pervaporation) or for aroma reinforce-
ment of low-alcohol beers. The best aroma
concentrates obtained by SFF correspond to α
values as high as 30. However, extraction effi-
ciency varies for the different aroma com-
pounds and the global aroma profile might
be different from the original beer one
(Perrut and Nunes da Ponte, 1997).
• Fractionation of distilled beverages
The aroma of distilled beverages has been
currently extracted by hazardous organic sol-
vents (pentane and dichloromethane). Mean-
while, SFF in mild conditions (120–140 bar,
30–50°C) leads to a very high extract yield and
a tasteless raffinate. This process was validated
at the semiindustrial scale (several tens of tons
of feed) on different feeds: 0.12 yield on cognac
(53 wt% ethanol), 0.7% yield on whiskey (58 wt%
ethanol), and 1.65% yield on Rum (49 wt% etha-
nol). Extracts are considered as excellent by a
taste panel and either comparable or better than
those obtained by dichloromethane extraction,
especially for rum where the aromatic power
and spectrum are judged as exceptional
(Perrut and Nunes da Ponte, 1997).
7.7.4.2.3 Essence and Concrete
Fractionation
For 30 years, citrus peel oil deterpenation
has received wide attention as it requires a
very selective process due to the fact that lim-
onene is readily soluble in CO2. Also, this mix-
ture is a very strong solvent from which it is
difficult to separate the oxygenated terpenes
selectively (Stahl et al., 1987). For the separa-
tion of such hydrocarbon-oxygenated com-
pounds, a combination of SFF and
adsorption (frontal chromatography) is very
efficient (Barth et al., 1994).
SFF is also efficient for flower concrete repro-
cessing in order to obtain a high-value extract,
similar to an absolue by selective elimination of
waxy compounds widely extracted by organic
solvents such as hexane. This process was
described on model molecules consisting of lim-
onene and canola oil (Yasumoto et al., 2014).

7. FOOD PROCESSING: ALL THE FOOD INDUSTRY SECTORS

504 7.7. SUPERCRITICAL FLUID APPLICATIONS IN THE FOOD INDUSTRY
7.7.4.3 Optimization and Scale-Up
Very little data are available on SFF scale up
until now, as very few industrial applications
have yet been disclosed and no details have been
published.
There is no doubt that any application shall be
subjected to a detailed optimization of all oper-
ating parameters at the pilot scale, although
internal reflux is difficult to evaluate. Optimiza-
tion of the fluid recycle loop is similar as for SFE
and does not raise any difficulty. Similarly, sep-
arator and raffinate vessels can be easily
designed. The sole difficulty lies in column
dimensioning.
- When enough thermodynamic data on phase
equilibria are available, it is highly
recommended to use a chemical engineering
model to fit pilot-scale results and then to use
it for large-scale parameter optimization
(Brunner, 1994; Riha and Brunner, 2000; Fiori
et al., 2014; Ruiz-Rodriguez et al., 2010). This
shall save a lot of time and money, moreso
because reaching process stabilization needs
many hours at large scale, as we have recently
experienced on the fractionation of fish oil
ethyl esters on a 126 mm diameter column.
- The external reflux rate shall be fixed only on
real tests at large scale.
- Column diameter can be determined from
pilot column diameter by homothetic scale up
to maintain the same specific fluid and liquid
flow rates, the liquid flow rate taking into
account the extract reflux rate.
- Column height is very complicated to
determine, as it is necessary to “guess” the
influence of diameter on the height of a
transfer unit (or equivalent to a theoretical
plate). Upon our knowledge, there is no
validated method available for such
evaluations for SFF. However, it is possible to
use results gathered on liquid-liquid or gas-
liquid contactors to predict that increasing the
column diameter will significantly increase
the height of the transfer unit due to axial
dispersion and possible bad liquid
7. FOOD PROCESSING: ALL THE FOOD INDUSTRY SECTORS
distribution inside the column section. To
limit this efficiency loss, liquid phase
redistributors shall be installed every 1.5–2 m
of packing.
7.7.4.4 Potential and Limitations
As said earlier, SFF has as yet been used in a
limited number of applications, in spite of its
great potential in terms of low processing cost
(automatized continuous mode) and high selec-
tivity (multistage countercurrent with extract
reflux) for such a “green” process. This is prob-
ably due to several factors:
- Rather few labs are operating SFF equipment.
- Process modeling is much more complex
than SFE.
- Process control requires a fluid-liquid level
control system that is difficult to select in
order to reach a reliable operation.
However, we recently demonstrated that frac-
tionation of fish oil ethyl esters was correctly
described by incorporating the binary solubility
data of each of the main components (Riha and
Brunner, 2000) in general process engineering soft-
ware (PRO-II). This shows that SFF modeling of
complex mixtures is no longer an impossible
target.
7.7.5 SUPERCRITICAL FLUID
REACTIONS (SFR)
For a long time, polymerizations have been
operated in supercritical monomers at very
large scale (polyethylene, PVDF). Also, many
types of chemical reactions in supercritical
media are being investigated, especially in the
field of “green chemistry,” in order to avoid
toxic solvents. Moreover, reaction rate and selec-
tivity are often much higher than in classical
solvents.
 7.7.6 SUPERCRITICAL FLUID FORMULATION (SFR)
7.7.5.1 Chemical Reactions:
Hydrogenation of Fats
Regarding natural product processing,
hydrogenation of unsaturated fats in supercriti-
cal propane (or possibly CO2) is very interesting,
as this catalytic reaction is operated in a unique
fluid phase. The kinetics are much faster and the
formation of trans-isomers is considerably
reduced. However, this process is not yet devel-
oped at the commercial scale.
7.7.5.2 Biochemical Reactions
In spite of the possible denaturation of pH-
sensitive enzymes, biochemical reactions are
also investigated. For example, operating ester-
ification of fats and oils in a nonpolar solvent
such as CO2 avoids the limitations observed in
aqueous media.
7.7.5.3 Pest Elimination in Food Products
Pressurized CO2 at 10–50 bar is efficient to kill
insect eggs, larva,or beetles after exposure of 10–
20 min; this strong effect may be connected with
gas action as a respiratory analeptic (Stahl et al.,
1987). For example, most common insects and
their eggs present in rice (Sitophilus oryzae L.
and Oryzaephilus surinamensis L.) are completely
eradicated by CO2 in relatively low-pressure
conditions (25 bar) (Capilla et al., 2003).
This process is presently used at a very large
scale with medium-pressure CO2 to treat huge
amounts of the overseas supply of food products
(like rice) and medicinal plants that are often
contaminated by insects.
7.7.5.4 Microorganism Inactivation in
Food Products
Regarding biological properties of SCF sol-
vents, CO2 exhibits biocide properties and is
very active on fungi, bacteria and viruses so that
all processed materials are decontaminated, or
7. FOOD PROCESSING: ALL THE FOOD INDUSTRY SECTORS
505
even sterilized, depending on the process condi-
tions and raw material contaminants. So, super-
critical CO2 treatment looks attractive as it
avoids heat processing or irradiation, which
are deleterious to product quality in a number
of cases. Much work has been done on this dur-
ing the three last decades, as reviewed in
(Perrut, 2012). Even if it is difficult to raise firm
conclusions, the main results can be summa-
rized as follows:
• Liquid foodstuff pasteurization is operative
and near being employed at the
commercial scale.
• Bacteria and fungi vegetative cells are
inactivated by high-pressure CO2 near room
temperature (<60°C) in the presence of water,
but additives (generally peroxides) are
required for spore inactivation; development
for injectable drug sterilization is now
ongoing.
• Virus inactivation needs important further
work to reach acceptance as a safe alternative
to present techniques, especially when
injectable products containing fragile
biomolecules are concerned.
• Supercritical fluid sterilization of biomedical
items (such as implants, prostheses, or
medical instruments) is of special interest at a
moment when nosocomial diseases are
spreading worldwide.
7.7.6 SUPERCRITICAL FLUID
FORMULATION (SFR)
7.7.6.1 Impregnation
As CO2 is a good carrier with high diffusiv-
ity, a porous matrix can be impregnated by a
solute previously dissolved in it. Online
impregnation downward extraction of natural
products (Majewski and Perrut, 2000) is oper-
ated as the CO2 loaded with extract exiting
the extractor is dried to eliminate water onto
a specific adsorbent. It is then partly liquefied
506 7.7. SUPERCRITICAL FLUID APPLICATIONS IN THE FOOD INDUSTRY
FIG. 7.7.23 Kava-Kava root (left), CO2 extract (center) and impregnated powder (right) (Majewski & Perrut, 2000).
in a stirred vessel in which the extract is depos-
ited into a porous excipient. This permits avoid-
ing the handling of a very viscous and sticky
extract and readily obtaining a free-flowing
powder that is easy to handle for commerciali-
zation (Fig. 7.7.23).
Other applications were also reported
with impregnation of polymers by APIs (i.e.,
antibiotics in soft lens), colorants in polycarbon-
ate view glasses, or perfumes in beauty
accessories.
7.7.6.2 Foodstuff Drying
Although CO2 is a weak solvent of water, it
can be used to dry natural products at the condi-
tion that a high solvent/feed rate is acceptable
and the fluid itself is dried after contacting the
product. According to a recent patent (Agterof
et al., 2007), a demonstration plant is now operat-
ing to dry a food product by CO2 in an innovative
pressure vessel incorporating a high flow-rate
turbine pump. The water-loaded fluid is perco-
lated through a specific adsorbent bed (i.e., 3A-
zeolite) prior to being recirculated. This process
is claimed to lead to high-quality dried products
with better preservation of valuable compounds
that are often destroyed by heat in spray drying,
and with less energy consumption.
7. FOOD PROCESSING: ALL THE FOOD INDUSTRY SECTORS
7.7.6.3 Particle Design Using
Supercritical Fluids
Many processes are being developed for
manufacturing various types of particles for
applications such as drug-delivery systems, per-
fumes and cosmetics, or aromas in food prod-
ucts. Supercritical fluids (mainly CO2) are used
in different ways, leading either to nano- or
microparticles with the possibility of tuning
their crystal polymorphism or to complex
microparticles or capsules ( Jung and Perrut,
2001). To summarize, we can cite the basic
concepts:
- Solvent power modulation: The substance is
dissolved in fluid at high pressure and
depressurized though a nozzle for very fine
particle precipitation according to RESS (rapid
expansion of supercritical solutions). There
are two main issues at the commercial scale:
Heating the fluid to avoid liquid CO2
formation and microparticle collection for
which innovative systems are proposed such
as deep filtration of microparticle-loaded CO2
through a bed of excipient macroparticles, as
shown in Fig. 7.7.24 (Perrut et al., 2005).
- Antisolvent: The substance is dissolved in a
polar solvent (particles, organic, or water) that
is pulverized into a stream of CO2 (possibly
 7.7.7 PRESENT AND FUTURE INDUSTRIAL DEVELOPMENT
FIG. 7.7.24 Capture of microparticles (right) of lovastatin generated by RESS in CO2 onto lactose particles (left) (Perrut
et al., 2005).
added with ethanol) that dissolves into the
solvent and diminishes its polarity so as to
precipitate the substance while the solvent is
carried out by the fluid. Solvent elimination
from the processed solid is often very difficult,
particularly when “heavy” solvents are used
(such as DMSO, DMF, or NMP).
- Plasticizer agent: CO2 dissolves in lipids and
various polymers and “plasticized” these
decreasing their viscosity and their melting
points, even at moderate pressures (40 to 80 bar)
as shown earlier in Fig. 7.7.16. The innovative
processes known as PGSS (particles from gas-
saturated suspensions) or FAME (fluid-assisted
microencapsulation) rely on this phenomenon:
Dispersion of an active-ingredient powder in an
excipient liquefied by CO2 saturation followed
by rapid depressurization through a nozzle
down to atmospheric pressure, leading to core-
shell microcapsules.
7.7.7 PRESENT AND FUTURE
INDUSTRIAL DEVELOPMENT
7.7.7.1 Hundreds of Plants Now Operate
in the World, Mainly for Food
Applications
As many as 400–500 large-scale plants are
now operating worldwide, mainly in Europe,
Asia (China, South Korea, and Japan) and the
7. FOOD PROCESSING: ALL THE FOOD INDUSTRY SECTORS
507
United States. Most of them are processing
natural raw materials for food ingredients,
nutraceuticals, pharmaceuticals, and cos-
metics. This number is now increasing follow-
ing the demand boost for organic ingredients
manufactured by “sustainable” techniques.
7.7.7.2 New Trends for New
Applications
Increasing extraction pressure appears as
a major trend for SFE development, although
this possibility to increase fluid solvent
power is not always a plus. It is to be empha-
sized that optimization of the global processing
chain, including material pretreatment,
extraction, and final extract processing, is the
key for reaching high-value, easy-to-use
products.
SFF presents great potential for several food
fractionation challenges concerning dairy prod-
ucts, various oils, polar lipids, flower concretes,
alcoholic beverages, etc.
Moreover, the combination of SFE or SFF with
online formulation of active ingredients is also
of major industrial interest. Meanwhile, pest
elimination and “CO2 pasteurization” are now
considered favorably as green alternatives to
“classical” treatments.
508 7.7. SUPERCRITICAL FLUID APPLICATIONS IN THE FOOD INDUSTRY
Acknowledgments
The authors are grateful to the Chambre de Commerce et
d’Industrie de la Dr^
ome, the Rh^one-Alpes Region, and the
European Union (FEDER) for financing the EXTRALIANS
platform where most of the experiments presented in this
paper were performed. The authors also thank Distillerie
Bleu-Provence (Nyons-France) and his manager M. Philippe
SOGUEL for cooperation on several extraction works
presented here.
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Further Reading
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using empirical equations. J. Supercrit. Fluids 24: 19–35,
2002.