EXTRACTION TECHNOLOGIES FOR MEDICINAL AND AROMATIC PLANTS

1 An Overview of Extraction Techniques

for Medicinal and Aromatic Plants
S. S. Handa

Abstract
A wide range of technologies is available for the extraction of active components and
essential oils from medicinal and aromatic plants. The choice depends on the eco-
nomic feasibility and suitability of the process to the particular situation. The various
processes of production of medicinal plant extracts and essential oils are reviewed in
this paper.

1.1 Introduction

Asia is the largest continent and has 60% of the world’s popu-
lation. It has abundant medicinal and aromatic plant species, well docu-
mented traditional knowledge, a long-standing practice of traditional medi-
cine, and the potential for social and economic development of medicinal
and aromatic plants (MAPs). Asia is one of the largest biodiversity regions
in the world, containing some of the richest countries in plant resources.
The continent has diverse plant flora but species richness is concentrated
mainly in tropical and subtropical regions. Six of the world’s 18 biodiversity
hot spots, namely eastern Himalaya, North Borneo, Peninsular Malaysia,
Sri Lanka, Philippines and the Western Ghats of South India, lie in Asia.
The countries of the region have large flora: China has 30,000 species of
higher plants; Indonesia, 20,000; India, 17,000; Myanmar, 14,000; Malay-
sia, 12,000; and Thailand, 12,000. The total numbers of plant species and
the endemics in the region are given below:

Region Species Endemics

South East Asia 42-50,000 40,000
China and East Asia 45,000 18,650
Indian Subcontinent 25,000 12,000
South West Asia 23,000 7,100

Sustainable industrial exploitation of such a valuable biore-

source, through use of appropriate technologies, can substantially contrib-
ute to the socio-economic growth of Asian countries. The International Cen-
tre for Science and High Technology (ICS-UNIDO) has thus organized this
regional workshop on “extraction technologies for medicinal and aromatic
plants” for South East Asian countries.

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1 AN OVERVIEW OF EXTRACTION TECHNIQUES FOR MEDICINAL AND AROMATIC PLANTS

1.2 Medicinal Plant Extracts

Extraction, as the term is used pharmaceutically, involves the

separation of medicinally active portions of plant or animal tissues from
the inactive or inert components by using selective solvents in standard
extraction procedures. The products so obtained from plants are relatively
impure liquids, semisolids or powders intended only for oral or external use.
These include classes of preparations known as decoctions, infusions, fluid
extracts, tinctures, pilular (semisolid) extracts and powdered extracts. Such
preparations popularly have been called galenicals, named after Galen, the
second century Greek physician.

The purposes of standardized extraction procedures for crude

drugs are to attain the therapeutically desired portion and to eliminate the
inert material by treatment with a selective solvent known as menstruum.
The extract thus obtained may be ready for use as a medicinal agent in the
form of tinctures and fluid extracts, it may be further processed to be incor-
porated in any dosage form such as tablets or capsules, or it may be frac-
tionated to isolate individual chemical entities such as ajmalicine, hyoscine
and vincristine, which are modem drugs. Thus, standardization of extraction
procedures contributes significantly to the final quality of the herbal drug.

1.2.1 General Methods of Extraction of Medicinal Plants

[Link] Maceration

In this process, the whole or coarsely powdered crude drug is

placed in a stoppered container with the solvent and allowed to stand at
room temperature for a period of at least 3 days with frequent agitation until
the soluble matter has dissolved. The mixture then is strained, the marc
(the damp solid material) is pressed, and the combined liquids are clarified
by filtration or decantation after standing.

[Link] Infusion

Fresh infusions are prepared by macerating the crude drug for

a short period of time with cold or boiling water. These are dilute solutions
of the readily soluble constituents of crude drugs.

[Link] Digestion

This is a form of maceration in which gentle heat is used during

the process of extraction. It is used when moderately elevated temperature
is not objectionable. The solvent efficiency of the menstruum is thereby
increased.

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 EXTRACTION TECHNOLOGIES FOR MEDICINAL AND AROMATIC PLANTS

[Link] Decoction

In this process, the crude drug is boiled in a specified volume

of water for a defined time; it is then cooled and strained or filtered. This
procedure is suitable for extracting water-soluble, heat-stable constituents.
This process is typically used in preparation of Ayurvedic extracts called
“quath” or “kawath”. The starting ratio of crude drug to water is fixed, e.g.
1:4 or 1:16; the volume is then brought down to one-fourth its original vol-
ume by boiling during the extraction procedure. Then, the concentrated ex-
tract is filtered and used as such or processed further.

[Link] Percolation

This is the procedure used most frequently to extract active

ingredients in the preparation of tinctures and fluid extracts. A percolator
(a narrow, cone-shaped vessel open at both ends) is generally used (Figure
1). The solid ingredients are moistened with an appropriate amount of the
specified menstruum and allowed to stand for approximately 4 h in a well-
closed container, after which the mass is packed and the top of the percola-
tor is closed. Additional menstruum is added to form a shallow layer above
the mass, and the mixture is allowed to macerate in the closed percolator
for 24 h. The outlet of the percolator then is opened and the liquid contained
therein is allowed to drip slowly. Additional menstruum is added as required,
until the percolate measures about three-quarters of the required volume
of the finished product. The marc is then pressed and the expressed liquid
is added to the percolate. Sufficient menstruum is added to produce the
required volume, and the mixed liquid is clarified by filtration or by standing
followed by decanting.

Figure 1: Percolator

[Link] Hot Continuous Extraction (Soxhlet)

In this method, the finely ground crude drug is placed in a porous

bag or “thimble” made of strong filter paper, which is placed in chamber E of
the Soxhlet apparatus (Figure 2). The extracting solvent in flask A is heated,

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1 AN OVERVIEW OF EXTRACTION TECHNIQUES FOR MEDICINAL AND AROMATIC PLANTS

and its vapors condense in condenser D. The condensed extractant drips

into the thimble containing the crude drug, and extracts it by contact. When
the level of liquid in chamber E rises to the top of siphon tube C, the liquid
contents of chamber E siphon into flask A. This process is continuous and is
carried out until a drop of solvent from the siphon tube does not leave residue
when evaporated. The advantage of this method, compared to previously de-
scribed methods, is that large amounts of drug can be extracted with a much
smaller quantity of solvent. This effects tremendous economy in terms of
time, energy and consequently financial inputs. At small scale, it is employed
as a batch process only, but it becomes much more economical and viable
when converted into a continuous extraction procedure on medium or large
scale.

Figure 2: Soxhlet apparatus

[Link] Aqueous Alcoholic Extraction by Fermentation

Some medicinal preparations of Ayurveda (like asava and arista)

adopt the technique of fermentation for extracting the active principles. The
extraction procedure involves soaking the crude drug, in the form of either a
powder or a decoction (kasaya), for a specified period of time, during which
it undergoes fermentation and generates alcohol in situ; this facilitates the
extraction of the active constituents contained in the plant material. The al-
cohol thus generated also serves as a preservative. If the fermentation is to
be carried out in an earthen vessel, it should not be new: water should first
be boiled in the vessel. In large-scale manufacture, wooden vats, porcelain
jars or metal vessels are used in place of earthen vessels. Some examples
of such preparations are karpurasava, kanakasava, dasmularista. In Ayurveda,
this method is not yet standardized but, with the extraordinarily high degree of

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 EXTRACTION TECHNOLOGIES FOR MEDICINAL AND AROMATIC PLANTS

advancement in fermentation technology, it should not be difficult to standard-

ize this technique of extraction for the production of herbal drug extracts.

[Link] Counter-current Extraction

In counter-current extraction (CCE), wet raw material is pulverized

using toothed disc disintegrators to produce a fine slurry. In this process, the
material to be extracted is moved in one direction (generally in the form of a
fine slurry) within a cylindrical extractor where it comes in contact with extrac-
tion solvent. The further the starting material moves, the more concentrated the
extract becomes. Complete extraction is thus possible when the quantities of
solvent and material and their flow rates are optimized. The process is highly
efficient, requiring little time and posing no risk from high temperature. Finally,
sufficiently concentrated extract comes out at one end of the extractor while the
marc (practically free of visible solvent) falls out from the other end.
This extraction process has significant advantages:
i) A unit quantity of the plant material can be extracted with
much smaller volume of solvent as compared to other meth-
ods like maceration, decoction, percolation.
ii) CCE is commonly done at room temperature, which spares
the thermolabile constituents from exposure to heat which
is employed in most other techniques.
iii) As the pulverization of the drug is done under wet condi-
tions, the heat generated during comminution is neutralized
by water. This again spares the thermolabile constituents
from exposure to heat.
iv) The extraction procedure has been rated to be more effi-
cient and effective than continuous hot extraction.

[Link] Ultrasound Extraction (Sonication)

The procedure involves the use of ultrasound with frequencies

ranging from 20 kHz to 2000 kHz; this increases the permeability of cell
walls and produces cavitation. Although the process is useful in some cas-
es, like extraction of rauwolfia root, its large-scale application is limited due
to the higher costs. One disadvantage of the procedure is the occasional but
known deleterious effect of ultrasound energy (more than 20 kHz) on the ac-
tive constituents of medicinal plants through formation of free radicals and
consequently undesirable changes in the drug molecules.

[Link] Supercritical Fluid Extraction

Supercritical fluid extraction (SFE) is an alternative sample prep-

aration method with general goals of reduced use of organic solvents and
increased sample throughput. The factors to consider include temperature,
pressure, sample volume, analyte collection, modifier (cosolvent) addition,

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1 AN OVERVIEW OF EXTRACTION TECHNIQUES FOR MEDICINAL AND AROMATIC PLANTS

flow and pressure control, and restrictors. Generally, cylindrical extraction

vessels are used for SFE and their performance is good beyond any doubt.
The collection of the extracted analyte following SFE is another important
step: significant analyte loss can occur during this step, leading the analyst
to believe that the actual efficiency was poor.

There are many advantages to the use of CO2 as the extract-

ing fluid. In addition to its favorable physical properties, carbon dioxide is
inexpensive, safe and abundant. But while carbon dioxide is the preferred
fluid for SFE, it possesses several polarity limitations. Solvent polarity is
important when extracting polar solutes and when strong analyte-matrix in-
teractions are present. Organic solvents are frequently added to the carbon
dioxide extracting fluid to alleviate the polarity limitations. Of late, instead
of carbon dioxide, argon is being used because it is inexpensive and more
inert. The component recovery rates generally increase with increasing pres-
sure or temperature: the highest recovery rates in case of argon are ob-
tained at 500 atm and 150° C.

The extraction procedure possesses distinct advantages:

i) The extraction of constituents at low temperature, which
strictly avoids damage from heat and some organic sol-
vents.
ii) No solvent residues.
iii) Environmentally friendly extraction procedure.

The largest area of growth in the development of SFE has been

the rapid expansion of its applications. SFE finds extensive application in
the extraction of pesticides, environmental samples, foods and fragrances,
essential oils, polymers and natural products. The major deterrent in the
commercial application of the extraction process is its prohibitive capital
investment.

[Link] Phytonics Process

A new solvent based on hydrofluorocarbon-134a and a new

technology to optimize its remarkable properties in the extraction of plant
materials offer significant environmental advantages and health and safety
benefits over traditional processes for the production of high quality natural
fragrant oils, flavors and biological extracts.

Advanced Phytonics Limited (Manchester, UK) has developed

this patented technology termed “phytonics process”. The products mostly
extracted by this process are fragrant components of essential oils and bio-
logical or phytopharmacological extracts which can be used directly without
further physical or chemical treatment.

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 EXTRACTION TECHNOLOGIES FOR MEDICINAL AND AROMATIC PLANTS

The properties of the new generation of fluorocarbon solvents

have been applied to the extraction of plant materials. The core of the sol-
vent is 1,1,2,2-tetrafluoroethane, better known as hydrofluorocarbon-134a
(HFC-134a). This product was developed as a replacement for chlorofluoro-
carbons. The boiling point of this solvent is -25° C. It is not flammable or
toxic. Unlike chlorofluorocarbons, it does not deplete the ozone layer. It has
a vapor pressure of 5.6 bar at ambient temperature. By most standards this
is a poor solvent. For example, it does not mix with mineral oils or triglycer-
ides and it does not dissolve plant wastes.

The process is advantageous in that the solvents can be cus-

tomized: by using modified solvents with HFC-134a, the process can be
made highly selective in extracting a specific class of phytoconstituents.
Similarly, other modified solvents can be used to extract a broader spectrum
of components. The biological products made by this process have extreme-
ly low residual solvent. The residuals are invariably less than 20 parts per
billion and are frequently below levels of detection. These solvents are nei-
ther acidic nor alkaline and, therefore, have only minimal potential reaction
effects on the botanical materials. The processing plant is totally sealed
so that the solvents are continually recycled and fully recovered at the end
of each production cycle. The only utility needed to operate these systems
is electricity and, even then, they do no consume much energy. There is no
scope for the escape of the solvents. Even if some solvents do escape, they
contain no chlorine and therefore pose no threat to the ozone layer. The
waste biomass from these plants is dry and “ecofriendly” to handle.

[Link].1 Advantages of the Process

• Unlike other processes that employ high temperatures, the

phytonics process is cool and gentle and its products are
never damaged by exposure to temperatures in excess of
ambient.
• No vacuum stripping is needed which, in other processes,
leads to the loss of precious volatiles.
• The process is carried out entirely at neutral pH and, in the
absence of oxygen, the products never suffer acid hydrolysis
damage or oxidation.
• The technique is highly selective, offering a choice of operat-
ing conditions and hence a choice of end products.
• It is less threatening to the environment.
• It requires a minimum amount of electrical energy.
• It releases no harmful emissions into the atmosphere and
the resultant waste products (spent biomass) are innocuous
and pose no effluent disposal problems.
• The solvents used in the technique are not flammable, toxic
or ozone depleting.
• The solvents are completely recycled within the system.

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[Link].2 Applications

The phytonics process can be used for extraction in biotechnol-

ogy (e.g for the production of antibiotics), in the herbal drug industry, in the
food, essential oil and flavor industries, and in the production of other phar-
macologically active products. In particular, it is used in the production of top-
quality pharmaceutical-grade extracts, pharmacologically active intermediates,
antibiotic extracts and phytopharmaceuticals. However, the fact that it is used
in all these areas in no way prevents its use in other areas. The technique is
being used in the extraction of high-quality essential oils, oleoresins, natural
food colors, flavors and aromatic oils from all manner of plant materials. The
technique is also used in refining crude products obtained from other extrac-
tion processes. It provides extraction without waxes or other contaminants. It
helps remove many biocides from contaminated biomass.

[Link] Parameters for Selecting an Appropriate Extraction Method

i) Authentication of plant material should be done before per-

forming extraction. Any foreign matter should be completely
eliminated.
ii) Use the right plant part and, for quality control purposes, record
the age of plant and the time, season and place of collection.
iii) Conditions used for drying the plant material largely depend
on the nature of its chemical constituents. Hot or cold blow-
ing air flow for drying is generally preferred. If a crude drug
with high moisture content is to be used for extraction, suit-
able weight corrections should be incorporated.
iv) Grinding methods should be specified and techniques that
generate heat should be avoided as much as possible.
v) Powdered plant material should be passed through suitable
sieves to get the required particles of uniform size.
vi) Nature of constituents:
a) If the therapeutic value lies in non-polar constituents, a
non-polar solvent may be used. For example, lupeol is the
active constituent of Crataeva nurvala and, for its extrac-
tion, hexane is generally used. Likewise, for plants like
Bacopa monnieri and Centella asiatica, the active con-
stituents are glycosides and hence a polar solvent like
aqueous methanol may be used.
b) If the constituents are thermolabile, extraction methods
like cold maceration, percolation and CCE are preferred.
For thermostable constituents, Soxhlet extraction (if non-
aqueous solvents are used) and decoction (if water is the
menstruum) are useful.
c) Suitable precautions should be taken when dealing with
constituents that degrade while being kept in organic sol-
vents, e.g. flavonoids and phenyl propanoids.

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 EXTRACTION TECHNOLOGIES FOR MEDICINAL AND AROMATIC PLANTS

d) In case of hot extraction, higher than required tempera-

ture should be avoided. Some glycosides are likely to
break upon continuous exposure to higher temperature.
e) Standardization of time of extraction is important, as:
• Insufficient time means incomplete extraction.
• If the extraction time is longer, unwanted constituents
may also be extracted. For example, if tea is boiled
for too long, tannins are extracted which impart astrin-
gency to the final preparation.
f) The number of extractions required for complete extrac-
tion is as important as the duration of each extraction.
vii) The quality of water or menstruum used should be specified
and controlled.
viii) Concentration and drying procedures should ensure the safety
and stability of the active constituents. Drying under reduced
pressure (e.g. using a Rotavapor) is widely used. Lyophiliza-
tion, although expensive, is increasingly employed.
ix) The design and material of fabrication of the extractor are
also to be taken into consideration.
x) Analytical parameters of the final extract, such as TLC and
HPLC fingerprints, should be documented to monitor the
quality of different batches of the extracts.

1.2.2 Steps Involved in the Extraction of Medicinal Plants

In order to extract medicinal ingredients from plant material,

the following sequential steps are involved:
1. Size reduction
2. Extraction
3. Filtration
4. Concentration
5. Drying

[Link] Size Reduction

The dried plant material is disintegrated by feeding it into a

hammer mill or a disc pulverizer which has built-in sieves. The particle size
is controlled by varying the speed of the rotor clearance between the ham-
mers and the lining of the grinder and also by varying the opening of the
discharge of the mill. Usually, the plant material is reduced to a size be-
tween 30 and 40 mesh, but this can be changed if the need arises. The
objective for powdering the plant material is to rupture its organ, tissue and
cell structures so that its medicinal ingredients are exposed to the extrac-
tion solvent. Furthermore, size reduction maximizes the surface area, which
in turn enhances the mass transfer of active principle from plant material
to the solvent. The 30-40 mesh size is optimal, while smaller particles may
become slimy during extraction and create difficulty during filtration.

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[Link] Extraction

Extraction of the plant material is carried out in three ways:

i) Cold aqueous percolation
ii) Hot aqueous extraction (decoction)
iii) Solvent extraction (cold or hot)

[Link].1 Cold Aqueous Percolation

The powdered material is macerated with water and then

poured into a tall column. Cold water is added until the powdered material
is completely immersed. It is allowed to stand for 24 h so that water-soluble
ingredients attain equilibrium in the water. The enriched aqueous extract is
concentrated in multiple-effect evaporators to a particular concentration.
Some diluents and excipients are added to this concentrated extract, which
is then ready for medicinal use.

[Link].2 Hot Aqueous Extraction (Decoction)

This is done in an open-type extractor. The extractor is a cylin-

drical vessel made from type 316 stainless steel and has a diameter (D)
greater than the height (H), i.e. the H/D ratio is approximately 0.5. The bot-
tom of the vessel is welded to the dished end and is provided with an inside
false bottom with a filter cloth. The outside vessel has a steam jacket and a
discharge valve at the bottom.

One part powdered plant material and sixteen parts deminer-

alized water are fed into the extractor. Heating is done by injecting steam
into the jacket. The material is allowed to boil until the volume of water is
reduced to one-fourth its original volume. By this time the medicinal ingredi-
ents present in the plant material have been extracted out.

[Link].3 Filtration

The extract so obtained is separated out from the marc (ex-

hausted plant material) by allowing it to trickle into a holding tank through
the built-in false bottom of the extractor, which is covered with a filter cloth.
The marc is retained at the false bottom, and the extract is received in the
holding tank. From the holding tank, the extract is pumped into a sparkler
filter to remove fine or colloidal particles from the extract.

[Link].4 Spray Drying

The filtered extract is subjected to spray drying with a high

pressure pump at a controlled feed rate and temperature, to get dry powder.
The desired particle size of the product is obtained by controlling the inside

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 EXTRACTION TECHNOLOGIES FOR MEDICINAL AND AROMATIC PLANTS

temperature of the chamber and by varying the pressure of the pump. The
dry powder is mixed with suitable diluents or excipients and blended in a
double cone mixer to obtain a homogeneous powder that can be straighta-
way used, for example, for filling in capsules or making tablets.

[Link] Solvent Extraction

The principle of solid-liquid extraction is that when a solid material

comes in contact with a solvent, the soluble components in the solid material
move to the solvent. Thus, solvent extraction of plant material results in the
mass transfer of soluble active principle (medicinal ingredient) to the solvent,
and this takes place in a concentration gradient. The rate of mass transfer de-
creases as the concentration of active principle in the solvent increases, until
equilibrium is reached, i.e. the concentrations of active principle in the solid ma-
terial and the solvent are the same. Thereafter, there will no longer be a mass
transfer of the active principle from plant material to the solvent.

Since mass transfer of the active principle also depends on its

solubility in the solvent, heating the solvent can enhances the mass transfer.
Moreover, if the solvent in equilibrium with the plant material is replaced with
fresh solvent, the concentration gradient is changed. This gives rise to differ-
ent types of extractions: cold percolation, hot percolation and concentration.

[Link].1 Cold Percolation

The extraction of plant material is carried out in a percolator

which is a tall cylindrical vessel with a conical bottom and a built-in false
bottom with a filter cloth. The percolator is connected to a condenser and a
receiver for stripping solvent from the marc.

The powdered material is fed into the percolator along with a

suitable solvent (ethyl alcohol or another non-polar solvent). The material
is left in contact with the solvent until equilibrium of the active principle is
achieved. The solvent extract, known as miscella, is taken out from the bot-
tom discharge valve of the percolator. Fresh solvent is added into the per-
colator and the miscella is drained out after acquiring equilibrium. Overall,
the plant material is washed four to five times until it gets exhausted. All
washes from the percolator are pooled and concentrated.

The solvent in the marc is stripped out by passing steam from

the bottom of the percolator. The solvent and steam vapors rise and are con-
densed in a tubular condenser. The condensate, which is a mixture of alcohol
and water, is collected in a receiver and then subjected to fractional distillation
to get 95% pure ethyl alcohol which is again used as a fresh solvent.

This type of percolation is not efficient as it takes a long time

to reach equilibrium due to the slow mass transfer rate. The mass transfer

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rate can be enhanced if some sort of movement is created between the

particles and the solvent.

This can be achieved either by providing inside agitation with a

mechanical stirrer or by repeated circulation of the extract back to the per-
colator. The first method is cumbersome and power intensive whereas the
latter has been successful. A circulation pump that continuously circulates
the miscella back to the top of the percolator gives a better mass transfer
rate and reduces the equilibrium time considerably. Still, this type of percola-
tion is energy-consuming as large amounts of miscella from multiple washes
must be concentrated to remove the solvent.

To overcome this problem, a battery of percolators can be con-

nected in series. If three washes are required for completion of the extrac-
tion, four percolators are connected in series with their respective miscella
storage tanks.

At a particular time, one percolator is out of circuit, for charging

and discharging the material and also for stripping solvent from the marc,
whereas the other three percolators are in operation. Material is fed into
all the percolators and the solvent is fed into the first percolator. When the
equilibrium in the first percolator is reached, the extract from the first perco-
lator is sent to the second percolator. The first percolator is again filled with
fresh solvent. The extract of second percolator is transferred to the third,
the extract of first is transferred to second, and fresh solvent is added to the
first. The extract of the third percolator is transfered to the fourth percolator.
After attaining equilibrium, the extract from the fourth percolator is drained
off. The extract of the third percolator goes to fourth, the extract of second
goes to third, and the extract of first goes to second percolator. The mate-
rial of the first percolator, which has received three washes, is completely
exhausted. This percolator is taken out of the system for stripping the sol-
vent and discharging the extracted marc. This is again filled with fresh plant
material and the sequence is repeated with other percolators. In this way,
solvent of each percolator comes in contact three times with solid material
and gets fully enriched with active principle. The enriched extract is sent for
solvent recovery and concentration. Thus, instead of concentrating three vol-
umes of solvent, only one volume has to be concentrated; this saves energy
and the process is efficient.

[Link].2 Hot Percolation

Increasing the temperature of the solvent increases the solu-

bility of the active principle, which increases the concentration gradient and
therefore enhances the mass transfer of active principle from solid material
to the solvent, provided the active principle is not heat sensitive. This is
achieved by incorporating a heat exchanger between the circulation pump
and the feed inlet of the percolator. The extract is continuously pumped into

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a tubular heat exchanger which is heated by steam. The temperature of the

extract in the percolator is controlled by a steam solenoid valve through a
temperature indicator controller. This sort of arrangement can be incorpo-
rated in single percolators or in a battery of percolators as needed.

The percolators that are tall cylindrical towers must be housed

in sheds of relatively great height. Tall towers are difficult to operate, espe-
cially when charging material and discharging the marc from the top and bot-
tom manholes, which are time-consuming and labor-intensive procedures.
Tall towers have been replaced by extractors of smaller height for which the
H/D ratio is not more than 1.5.

These extractors have perforated baskets in which the material to

be extracted is charged. These perforated baskets, when loaded outside, can
be inserted into the extractor with a chain pulley block and, after the extraction,
they can be lifted out from the extractor for discharging the marc. Some extrac-
tors have an electrical hoist for the charging the material and discharging the
marc, which makes the operation less labor-intensive, quick and efficient.

The other type of instrument for extraction of medicinal ingre-

dients from plant material is the Soxhlet apparatus, which consists of an
extractor, a distillation still, a tubular condenser for the distillation still, a tu-
bular condenser for the recovery of solvent from the marc, a receiver for col-
lecting the condensate from the condenser, and a solvent storage tank. The
plant material is fed into the extractor, and solvent is added until it reaches
the siphon point of the extractor. Then, the extract is siphoned out into the
distillation still, which is heated with steam. The solvent vapors go to the
distillation condenser, get condensed and return to the extractor. The level
of the solvent in the extractor again rises to the siphon point and the extract
is siphoned out into the distillation still. In this way, fresh solvent comes in
contact with the plant material a number of times, until the plant material is
completely extracted. The final extract in the distillation still, which is rich in
active principle, is concentrated and the solvent is recovered.

[Link].3 Concentration

The enriched extract from percolators or extractors, known as

miscella, is fed into a wiped film evaporator where it is concentrated under
vacuum to produce a thick concentrated extract. The concentrated extract is
further fed into a vacuum chamber dryer to produce a solid mass free from
solvent. The solvent recovered from the wiped film evaporator and vacuum
chamber dryer is recycled back to the percolator or extractor for the next
batch of plant material. The solid mass thus obtained is pulverized and used
directly for the desired pharmaceutical formulations or further processed for
isolation of its phytoconstituents.

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temperature (usually 50° C) can be maintained during the process, As a result,

extracted oils have a more natural odor that is unmatched by distilled oils, which
may have undergone chemical alteration by the high temperature. This feature
is of considerable importance to the perfume industry; however, the established
distillation method is of lower cost than the extraction process.

Destructive distillation means distilling volatile oil in the ab-

sence of air. When wood or resin of members of the Pinaceae or Cupressace-
ae is heated without air, decomposition takes place and a number of volatile
compounds are driven off. The residual mass is charcoal. The condensed
volatile matter usually separates into 2 layers: an aqueous layer containing
wood naptha (methyl alcohol) and pyroligneous acid (crude acetic), and a
tarry liquid in the form of pine tar, juniper tar, or other tars, depending on the
wood used. This dry distillation is usually conducted in retorts and, if the
wood is chipped or coarsely ground and the heat is applied rapidly, the yield
often represents about 10% of the wood weight used.

[Link].1 Hydrodistillation

In order to isolate essential oils by hydrodistillation, the aro-

matic plant material is packed in a still and a sufficient quantity of water
is added and brought to a boil; alternatively, live steam is injected into the
plant charge. Due to the influence of hot water and steam, the essential oil
is freed from the oil glands in the plant tissue. The vapor mixture of water
and oil is condensed by indirect cooling with water. From the condenser,
distillate flows into a separator, where oil separates automatically from the
distillate water.

[Link].1.1 Mechanism of Distillation

Hydrodistillation of plant material involves the following main

physicochemical processes:
i) Hydrodiffusion
ii) Hydrolysis
iii) Decomposition by heat

[Link].1.1.1 Hydrodiffusion

Diffusion of essential oils and hot water through plant mem-

branes is known as hydrodiffusion. In steam distillation, the steam does not
actually penetrate the dry cell membranes. Therefore, dry plant material can
be exhausted with dry steam only when all the volatile oil has been freed
from the oil-bearing cells by first thorough comminution of the plant material.
But, when the plant material is soaked with water, exchange of vapors within
the tissue is based on their permeability while in swollen condition. Mem-
branes of plant cells are almost impermeable to volatile oils. Therefore, in

40
 EXTRACTION TECHNOLOGIES FOR MEDICINAL AND AROMATIC PLANTS

the actual process, at the temperature of boiling water, a part of volatile oil
dissolves in the water present within the glands, and this oil-water solution
permeates, by osmosis, the swollen membranes and finally reaches the
outer surface, where the oil is vaporized by passing steam.

Another aspect of hydrodiffusion is that the speed of oil vapori-

zation is not influenced by the volatility of the oil components, but by their
degree of solubility in water. Therefore, the high-boiling but more water-sol-
uble constituents of oil in plant tissue distill before the low-boiling but less
water-soluble constituents. Since hydrodiffusion rates are slow, distillation
of uncomminuted material takes longer time than comminuted material.

[Link].1.1.2 Hydrolysis

Hydrolysis in the present context is defined as a chemical re-

action between water and certain constituents of essential oils. Esters are
constituents of essential oils and, in the presence of water, especially at
high temperatures, they tend to react with water to form acids and alcohols.
However, the reactions are not complete in either direction and the relation-
ship between the molal concentrations of various constituents at equilib-
rium is written as:

(alcohol) x (acid)
K=
(ester) x (water)

where K is the equilibrium constant.

Therefore, if the amount of water is large, the amounts of alcohol and acid
will also be large, resulting in a decreased yield of essential oil. Further-
more, since this is a time-dependent reaction, the extent to which hydrolysis
proceeds depends on the time of contact between oil and water. This is one
of the disadvantages of water distillation.

[Link].1.1.3 Effect of Heat

Almost all constituents of essential oils are unstable at high

temperature. To obtain the best quality oil, distillation must be done at low
temperatures. The temperature in steam distillation is determined entirely
by the operating pressure, whereas in water distillation and in water and
steam distillation the operating pressure is usually atmospheric.

All the previously described three effects, i.e. hydrodiffusion,

hydrolysis and thermal decomposition, occur simultaneously and affect one
another. The rate of diffusion usually increases with temperatures as does
the solubility of essential oils in water. The same is true for the rate and
extent of hydrolysis. However, it is possible to obtain better yield and quality
of oils by: (1) maintaining the temperature as low as possible, (2) using as

41
1 AN OVERVIEW OF EXTRACTION TECHNIQUES FOR MEDICINAL AND AROMATIC PLANTS

little water as possible, in the case of steam distillation, and (3) thoroughly
comminuting the plant material and packing it uniformly before distillation.

[Link].2 Three Types of Hydrodistillation

Three are three types of hydrodistillation for isolating essential

oils from plant materials:
1. Water distillation
2. Water and steam distillation
3. Direct steam distillation

[Link].2.1 Water Distillation

In this method, the material is completely immersed in water,

which is boiled by applying heat by direct fire, steam jacket, closed steam
jacket, closed steam coil or open steam coil. The main characteristic of
this process is that there is direct contact between boiling water and plant
material.

When the still is heated by direct fire, adequate precautions

are necessary to prevent the charge from overheating. When a steam jacket
or closed steam coil is used, there is less danger of overheating; with open
steam coils this danger is avoided. But with open steam, care must be taken
to prevent accumulation of condensed water within the still. Therefore, the
still should be well insulated. The plant material in the still must be agitated
as the water boils, otherwise agglomerations of dense material will settle
on the bottom and become thermally degraded. Certain plant materials like
cinnamon bark, which are rich in mucilage, must be powdered so that the
charge can readily disperse in the water; as the temperature of the water
increases, the mucilage will be leached from the ground cinnamon. This
greatly increases the viscosity of the water-charge mixture, thereby allowing
it to char. Consequently, before any field distillation is done, a small-scale
water distillation in glassware should be performed to observe whether any
changes take place during the distillation process. From this laboratory trial,
the yield of oil from a known weight of the plant material can be determined.
The laboratory apparatus recommended for trial distillations is the Clev-
enger system (Figure 7).

During water distillation, all parts of the plant charge must be

kept in motion by boiling water; this is possible when the distillation material
is charged loosely and remains loose in the boiling water. For this reason
only, water distillation possesses one distinct advantage, i.e. that it permits
processing of finely powdered material or plant parts that, by contact with
live steam, would otherwise form lumps through which the steam cannot
penetrate. Other practical advantages of water distillation are that the stills

42
 EXTRACTION TECHNOLOGIES FOR MEDICINAL AND AROMATIC PLANTS

are inexpensive, easy to construct and suitable for field operation. These
are still widely used with portable equipment in many countries.

The main disadvantage of water distillation is that complete

extraction is not possible. Besides, certain esters are partly hydrolyzed and
sensitive substances like aldehydes tend to polymerize. Water distillation
requires a greater number of stills, more space and more fuel. It demands
considerable experience and familiarity with the method. The high-boiling
and somewhat water-soluble oil constituents cannot be completely vapor-
ized or they require large quantities of steam. Thus, the process becomes
uneconomical. For these reasons, water distillation is used only in cases in
which the plant material by its very nature cannot be processed by water and
steam distillation or by direct steam distillation.

Figure 7: Clevenger-type laboratory-scale hydrodistillation apparatus

[Link].2.1.1 Traditional Method of Producing Attar Using Hydrodistillation

Floral attars are defined as the distillates obtained by hydrodis-

tillation of flowers (such as saffron, marigold, rose, jasmine, pandanus) in
sandal wood oil or other base materials like paraffin.

Attar manufacturing takes place in remote places because

the flowers must be processed quickly after collection. The apparatus and
equipment used to manufacture attar are light, flexible, easy to repair, and
have a fair degree of efficiency. Keeping in view these facts, the traditional
“deg and bhapka” process has been used for centuries and is used even
now with the following traditional equipment (Figure 8).
• Deg (still)
• Bhapka (receiver)
• Chonga (bamboo condenser)

43
1 AN OVERVIEW OF EXTRACTION TECHNIQUES FOR MEDICINAL AND AROMATIC PLANTS

• Traditional bhatti (furnace)

• Gachchi (cooling water tank)
• Kuppi (leather bottle)

Figure 8: Traditional process of water distillation for making attar

[Link].2.1.2 Disadvantages of Water Distillation

• Oil components like esters are sensitive to hydrolysis while

others like acyclic monoterpene hydrocarbons and aldehydes
are susceptible to polymerization (since the pH of water is
often reduced during distillation, hydrolytic reactions are fa-
cilitated).
• Oxygenated components such as phenols have a tendency
to dissolve in the still water, so their complete removal by
distillation is not possible.
• As water distillation tends to be a small operation (operated
by one or two persons), it takes a long time to accumulate
much oil, so good quality oil is often mixed with bad quality
oil.
• The distillation process is treated as an art by local distill-
ers, who rarely try to optimize both oil yield or quality.
• Water distillation is a slower process than either water and
steam distillation or direct steam distillation.

[Link].2.2 Water and Steam Distillation

In water and steam distillation, the steam can be generated

either in a satellite boiler or within the still, although separated from the

44
 EXTRACTION TECHNOLOGIES FOR MEDICINAL AND AROMATIC PLANTS

plant material. Like water distillation, water and steam distillation is widely
used in rural areas. Moreover, it does not require a great deal more capital
expenditure than water distillation. Also, the equipment used is generally
similar to that used in water distillation, but the plant material is supported
above the boiling water on a perforated grid. In fact, it is common that per-
sons performing water distillation eventually progress to water and steam
distillation.

It follows that once rural distillers have produced a few batches

of oil by water distillation, they realize that the quality of oil is not very good
because of its still notes (subdued aroma). As a result, some modifications
are made. Using the same still, a perforated grid or plate is fashioned so
that the plant material is raised above the water. This reduces the capacity
of the still but affords a better quality of oil. If the amount of water is not suf-
ficient to allow the completion of distillation, a cohobation tube is attached
and condensate water is added back to the still manually, thereby ensuring
that the water, which is being used as the steam source, will never run out.
It is also believed that this will, to some extent, control the loss of dissolved
oxygenated constituents in the condensate water because the re-used con-
densate water will allow it to become saturated with dissolved constituents,
after which more oil will dissolve in it.

[Link].2.2.1 Cohobation

Cohobation is a procedure that can only be used during water

distillation or water and steam distillation. It uses the practice of returning
the distillate water to the still after the oil has been separated from it so
that it can be re-boiled. The principal behind it is to minimize the losses of
oxygenated components, particularly phenols which dissolve to some extent
in the distillate water. For most oils, this level of oil loss through solution
in water is less than 0.2%, whereas for phenol-rich oils the amount of oil
dissolved in the distillate water is 0.2%-0.7%. As this material is being con-
stantly re-vaporized, condensed and re-vaporized again, any dissolved oxy-
genated constituents will promote hydrolysis and degradation of themselves
or other oil constituents. Similarly, if an oxygenated component is constantly
brought in contact with a direct heat source or side of a still, which is consid-
erably hotter than 100° C, then the chances of degradation are enhanced.
As a result, the practice of cohobation is not recommended unless the tem-
perature to which oxygenated constituents in the distillate are exposed is
no higher than 100° C.

In steam and water distillation, the plant material cannot be

in direct contact with the fire source beneath the still; however, the walls of
the still are good conductors of heat so that still notes can also be obtained
from the thermal degradation reactions of plant material that is touching the
sides of the still. As the steam in the steam and water distillation process is
wet, a major drawback of this type of distillation is that it will make the plant

45
1 AN OVERVIEW OF EXTRACTION TECHNIQUES FOR MEDICINAL AND AROMATIC PLANTS

material quite wet. This slows down distillation as the steam has to vaporize
the water to allow it to condense further up the still. One way to prevent the
lower plant material resting on the grid from becoming waterlogged is to use
a baffle to prevent the water from boiling too vigorously and coming in direct
contact with the plant material.

[Link].2.2.2 Advantages of Water and Steam Distillation over Water Distillation

• Higher oil yield.

• Components of the volatile oil are less susceptible to hy-
drolysis and polymerization (the control of wetness on the
bottom of the still affects hydrolysis, whereas the thermal
conductivity of the still walls affects polymerization).
• If refluxing is controlled, then the loss of polar compounds
is minimized.
• Oil quality produced by steam and water distillation is more
reproducible.
• Steam and water distillation is faster than water distillation,
so it is more energy efficient.

Many oils are currently produced by steam and water distilla-

tion, for example lemongrass is produced in Bhutan with a rural steam and
water distillation system.

[Link].2.2.3 Disadvantages of Water and Steam Distillation

• Due to the low pressure of rising steam, oils of high-boiling

range require a greater quantity of steam for vaporization -
hence longer hours of distillation.
• The plant material becomes wet, which slows down distil-
lation as the steam has to vaporize the water to allow it to
condense further up the still.
• To avoid that the lower plant material resting on the grid
becomes waterlogged, a baffle is used to prevent the water
from boiling too vigorously and coming in direct contact with
the plant material.

[Link].2.3 Direct Steam Distillation

As the name suggests, direct steam distillation is the proc-

ess of distilling plant material with steam generated outside the still in a
satellite steam generator generally referred to as a boiler. As in water and
steam distillation, the plant material is supported on a perforated grid above
the steam inlet. A real advantage of satellite steam generation is that the
amount of steam can be readily controlled. Because steam is generated in
a satellite boiler, the plant material is heated no higher than 100° C and,
consequently, it should not undergo thermal degradation. Steam distillation

46
 EXTRACTION TECHNOLOGIES FOR MEDICINAL AND AROMATIC PLANTS

is the most widely accepted process for the production of essential oils on
large scale. Throughout the flavor and fragrance supply business, it is a
standard practice.

An obvious drawback to steam distillation is the much higher

capital expenditure needed to build such a facility. In some situations, such
as the large-scale production of low-cost oils (e.g. rosemary, Chinese ce-
darwood, lemongrass, litsea cubeba, spike lavender, eucalyptus, citronella,
cornmint), the world market prices of the oils are barely high enough to
justify their production by steam distillation without amortizing the capital
expenditure required to build the facility over a period of 10 years or more.

[Link].2.3.1 Advantages of Direct Steam Distillation

• Amount of steam can be readily controlled.

• No thermal decomposition of oil constituents.
• Most widely accepted process for large-scale oil production,
superior to the other two processes.

[Link].2.3.2 Disadvantage of Direct Steam Distillation

• Much higher capital expenditure needed to establish this

activity than for the other two processes.

[Link].3 Essential Oil Extraction by Hydrolytic Maceration

Distillation

Certain plant materials require maceration in warm water be-

fore they release their essential oils, as their volatile components are gly-
cosidically bound. For example, leaves of wintergreen (Gaultheria procum-
bens) contain the precursor gaultherin and the enzyme primeverosidase;
when the leaves are macerated in warm water, the enzyme acts on the
gaultherin and liberates free methyl salicylate and primeverose. Other sim-
ilar examples include brown mustard (sinigrin), bitter almonds (amygdalin)
and garlic (alliin).

[Link].4 Essential Oil Extraction by Expression

Expression or cold pressing, as it is also known, is only used

in the production of citrus oils. The term expression refers to any physical
process in which the essential oil glands in the peel are crushed or broken
to release the oil. One method that was practiced many years ago, par-
ticularly in Sicily (spugna method), commenced with halving the citrus fruit
followed by pulp removal with the aid of sharpened spoon-knife (known as
a rastrello). The oil was removed from the peel either by pressing the peel
against a hard object of baked clay (concolina) which was placed under
a large natural sponge or by bending the peel into the sponge. The oil

47
 EXTRACTION TECHNOLOGIES FOR MEDICINAL AND AROMATIC PLANTS

3 Maceration, Percolation and Infusion

Techniques for the Extraction of
Medicinal and Aromatic Plants
J. Singh

Abstract
Techniques of maceration, percolation and infusion have been traditionally used for
making galenicals and tinctures from medicinal and aromatic plants (MAPs). This ar-
ticle describes the underlying principals and mechanisms of these extraction tech-
niques, and discusses the various modifications made for the small- and large-scale
extraction of MAPs, the factors affecting the extraction process, and the quality of the
extracts produced.

3.1 Introduction

Before the nineteenth century, there was no real progress in

methods of extraction of plant materials for industrial use. Nonetheless, the
various classes of preparations involving simple expression and extraction
techniques were in vogue for a long time for the preparation of medicines
used in traditional medicine and in complimentary and alternative medicine,
practiced throughout the world. The techniques available were limited to ex-
pression, aqueous extraction and evaporation; later on, the use of extraction
processes was extended by using alcohol as a solvent. Such techniques
were highly successful in the phytochemical field and, consequently, single
pure molecules were isolated for industrial and medicinal uses. After the
nineteenth century, rapid progress was made in extraction processes which
led to the isolation and characterization of many groups of plant metabo-
lites of therapeutic importance, including both single chemical constituents
as well as standardized extracts of crude drugs. In manufacturing various
classes of medicinal plant preparations, such as decoctions, infusions, fluid
extracts, tinctures, semisolid extracts (pilular) and powdered extracts, popu-
larly known as galenicals, both simple traditional methods and advanced
technologies are used, conforming to the official procedures and specifica-
tions as laid down in various pharmacopoeias and codices of the world.

Maceration, percolation and infusion are the general tech-

niques used for the extraction of medicinal plants and are mostly applied
for galenical preparations. The sole purpose of such basic extraction pro-
cedures is to obtain the therapeutically desirable portion and eliminate the
inert material by treatment with a selective solvent known as menstruum.
These techniques also play a decisive role in the qualitative and quantita-
tive evaluation of the extracts. The standardized extracts thus obtained are
further processed for inclusion in other solid and semisolid herbal dosage

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3 MACERATION, PERCOLATION AND INFUSION TECHNIQUES FOR THE EXTRACTION OF MEDICINAL AND AROMATIC PLANTS

forms. These extracts are also used as sources of therapeutically active

chemical constituents for various dosage forms of modern medicines.

Historically, galenical preparations were much more extensively

used than they are at the present time. Nonetheless, due to resurgence in
interest of herbal drugs throughout the world, these extraction procedures
are still relevant and are mentioned in official and unofficial monographs
about drug preparations. The preparations involving these procedures are
primarily intended for extemporaneous dispensing and must be freshly pre-
pared, due to the fact that they rapidly produce a deposit because of coagu-
lation of inert colloidal material and readily support microbial growth due to
absence of preservatives.

This article describes the principal methods of extraction by

maceration, percolation and infusion as well as the modifications in these
procedures for small-scale, official and large-scale extraction. In addition,
the paper discusses the choice of extraction method, quality assurance, and
factors affecting the extraction procedures.

3.2 General Principles and Mechanisms Involved

in Crude Drug Extraction by Maceration,
Percolation and Infusion

The general principles and mechanisms involved in macera-

tion, percolation and infusion for the extraction of the crude drugs are same
as to those for the extraction of soluble constituents from solid materials
using solvent, which is generally referred to as leaching. The processes of
leaching may involve simple physical solution or dissolution. The extraction
procedures are affected by various factors, namely the rate of transport of
solvent into the mass, the rate of solubilization of the soluble constituents
by the solvent, the rate of transport of solution out of the insoluble material.
The extraction of crude drugs is mostly favored by increasing the surface
area of the material to be extracted and decreasing the radial distances
traversed between the solids (crude drug particle). Mass transfer theory
states that the maximum surface area is obtained by size reductions which
entail reduction of material into individual cells. However, this is not possible
or desirable in many cases of vegetable material. It has been demonstrated
that even 200 mesh particles contain hundred of unbroken cells with intact
cell wall. Therefore, it is pertinent to carry out extraction with unbroken cells
to obtain an extract with a high degree of purity and to allow enough time for
the diffusion of solvent through the cell wall for dissolution of the desired
solute (groups of constituents) and for diffusion of the solution (extract) to
the surface of the cell wall.

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 EXTRACTION TECHNOLOGIES FOR MEDICINAL AND AROMATIC PLANTS

3.3 Factors Affecting the Choice of Extraction

Process

The choice of the process to be used for the extraction of a

drug depends on a number of factors.

3.3.1 Nature of the Crude Drug

The choice to use maceration or percolation primarily depends

upon the nature and characteristics of the crude drugs to be extracted.
Therefore, knowledge of the type of organs and tissues of the plant matter
is essential for achieving the best result.

3.3.2 Stability of the Crude Drug

Continuous hot extraction procedures should be avoided when

constituents of the drug are thermolabile.

3.3.3 Cost of the Crude Drug

When the crude drug is expensive (e.g. ginger), it is desirable

to obtain complete extraction. Therefore, from the economic point of view,
percolation should be used. For inexpensive drugs, maceration, despite its
lower efficiency, is acceptable in view of its lower cost.

3.3.4 Solvent

Selection of the solvent depends on the solubility of the de-

sired components of the material. If the constituents demand a solvent
other than a pure boiling solvent or an azeotrope, continuous extraction
should be used.

3.3.5 Concentration of the Product

Dilute products such as tinctures can be made by maceration

or percolation. For semi-concentrated preparations, the more efficient per-
colation process is used. Concentrated preparations, such as liquid or dry
extracts, are made by percolation.

3.3.6 Recovery of Solvent

Solvent is preferably recovered under reduced pressure to save

thermolabile constituents.

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3 MACERATION, PERCOLATION AND INFUSION TECHNIQUES FOR THE EXTRACTION OF MEDICINAL AND AROMATIC PLANTS

3.4 Quality Assurance: the Extraction Process

and Solvent

The type of extraction procedure also plays a decisive role in

determining the qualitative and quantitative composition of the extract. Some
important points regarding the quality of the extracts need to be considered:
i) The more exhaustive the extraction, the better is the yield of
the constituents from the herbal drugs.
ii) If maceration is facilitated by stirring and by use of commi-
nuted material, the additional stirring and shearing forces
may lead to better extraction.
iii) Other factors determining the quality of the extracts are ex-
traction time, temperature and solvent volume.
iv) Some drugs (e.g. Hypericum spp.) are extracted very slowly
so that exhaustive extraction can only be achieved by per-
colation or multistage motion extraction. In many cases,
the transfer of quality-relevant constituents from the herbal
drugs to the extract (i.e. extraction rate) can be considerably
improved by raising the temperature. Hypericin, pseudohy-
pericin and biapigenin are extracted better at higher tem-
perature and with longer extraction times.
v) The quality of the extracts and the spectrum of constituents
obtained by maceration or digestion (i.e. maceration at higher
temperature) are also influenced by the ratio of herbal drug
to solvent. The quantity of extracted matter increases with
the volume of extraction solvent. For example, maceration of
Salvia officinalis flowers achieves almost exhaustive extrac-
tion and thus the full spectrum of constituents obtained with
percolation can be achieved with a drug:solvent ratio of 1:20.
vi) The composition of an herbal extract depends on the type,
concentration and elution strength of the solvent. The spec-
trum of constituents may vary considerably depending on
the hydrophilic or lipophilic nature of the solvent.

3.5 Maceration Processes (Steady-state

Extraction)

3.5.1 General Procedure

The general process of maceration on a small scale consists

of placing the suitably crushed plant material, or a moderately coarse pow-
der made from it, in a closed vessel and adding the selected solvent called
menstruum. The system is allowed to stand for seven days, with occasional
shaking. The liquid is then strained off and the solid residue, called marc,

70
 EXTRACTION TECHNOLOGIES FOR MEDICINAL AND AROMATIC PLANTS

is pressed to recover as much occluded solution as possible. The strained

and expressed liquid thus obtained is mixed and clarified by filtration. Plant
material in fine powder form is never used, as it makes subsequent clarifica-
tion of the extract difficult. In the case of vegetable drugs, sufficient time
is allowed for the menstruum to diffuse through the cell wall to solubilize
the constituents within the cells and for the resulting solution to diffuse
out. As the system is static, except for occasional shaking, the process of
extraction works by molecular diffusion, which is very slow. Occasional shak-
ing assists diffusion and also ensures dispersal of the concentrated solu-
tion accumulating around the surface of the particles, thereby bringing fresh
menstruum to the particle surface for further extraction. A closed vessel is
used to prevent evaporation of the menstruum during the extraction period
and thus avoids batch to batch variation.

At the end of the maceration process, when equilibrium has

been reached, the solution is filtered through a cloth; the marc may be
strained through a special press. The concentrations of active constitu-
ents in the strained and expressed liquids, sometimes called miscella, are
the same and hence they can be combined. The expressed liquid may be
cloudy with colloidal and small particles, and sufficient time (perhaps sev-
eral weeks) is necessary for coagulation and settling. The settled matter is
filtered through a filter press or any other suitable equipment.

3.5.2 Maceration Process for Organized and Unorganized

Crude Drugs

Organized drugs have a defined cellular structure whereas un-

organized drugs are non-cellular. Bark and roots are examples of organized
crude drugs, while gum and resin are unorganized crude drugs. The proc-
esses of maceration for organized and unorganized drugs are slightly differ-
ent, as shown in Table 1.

Table 1: Four differentiating steps of the maceration process, for organized and
unorganized crude drugs

Organized drugs Unorganized drugs

(i) Drug + entire volume of menstruum (i) Drug + four-fifths of

menstruum (in most cases)
(ii) Shake occasionally for 7 days (ii) Shake occasionally on days 2
to 7, as specified
(iii) Strain liquid, press the marc (iii) Decant the liquid. Marc is
not pressed
(iv) Mix the liquids, clarify by subsidence for (iv) Filter the liquid and add
filtration. Filtrate is not adjusted for volume remaining menstruum through
the filter

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3 MACERATION, PERCOLATION AND INFUSION TECHNIQUES FOR THE EXTRACTION OF MEDICINAL AND AROMATIC PLANTS

During maceration of organized drugs, the marc is pressed be-

cause a considerable proportion of liquid adheres to it and cannot other-
wise be separated. Moreover, the volume is not adjusted because a variable
amount of liquid containing soluble matter is left in the marc. If the volume
is adjusted, a weak product will result. Omitting adjustment, the volume of
liquid expressed influences the product yield and the percentage of soluble
matter, regardless of the efficiency with which the marc is pressed in a hand
press, screw press or hydraulic press; the strength of the product is not
affected. Preparations made by this processes include vinegar of squill (Brit-
ish Pharmaceutical Codex, BPC), oxymel of squill (BPC), tincture of orange
(Indian Pharmacopoeia, IP), tincture of capsicum (BPC), compound tincture
of gentian, tincture of lemon, and tincture of squill (BPC).

In maceration of unorganized drugs, the marc is not pressed

because the desirable material is mostly dissolved and the remaining marc
is gummy and slimy. Thus, it is neither practicable nor necessary to press
it. Moreover, the volume is adjusted because the clear upper layer is easily
separated by filtration from the lower layer. The solution contains practically
all the soluble matter of the drug; the small amount adherent to the gummy
matter is recovered when the marc is washed by menstruum in the filter.
Therefore, adjustment of volume leads to uniformity. Preparations made by
this process include compound tincture of benzoin, tincture of myrrh (BPC),
and tincture of tolu (BPC).

3.5.3 Modifications to the General Processes of

Maceration

Repeated maceration may be more efficient than a single mac-

eration process, as described earlier, because an appreciable amount of
active principle may be left behind in the first pressing of the marc. Double
maceration is used when the active constituents are particularly valuable
and also when the concentrated infusions contain volatile oil. Where the
marc cannot be pressed, a process of triple maceration is sometimes em-
ployed. The total volume of solvent used is, however, large and the second
and third macerates are usually mixed and evaporated before being added
to the first macerate.

3.5.4 Large-scale Extraction Procedures

For large-scale, industrial extraction, certain modifications are

warranted. When the extraction vessel contains a small amount of solvent
(500-1000 ml), occasional shaking is no problem. But, for industrial work
where a large amount of solvent and huge vessels are involved, shaking the
vessels is difficult. Obviously, there are alternative methods of agitation that
are just as effective and much simpler to put into practice. In addition, eco-
nomics become increasingly important and one of the most important objec-
tives is to improve the efficiency of extraction so that less solvent is needed

72
 EXTRACTION TECHNOLOGIES FOR MEDICINAL AND AROMATIC PLANTS

and evaporation requirements for concentrated products are reduced. Reduc-

ing the cost of evaporation has the further advantage of minimizing the heat
damage to thermolabile constituents. Some of the modified maceration pro-
cedures used for large-scale extraction are described in the next paragraphs.

[Link] Circulatory Extraction

The efficiency of extraction in a maceration process can be

improved by arranging the solvent to be continuously circulated through the
drug, as indicated in the Figure 1. Solvent is pumped from the bottom of the
vessel (through an outlet) and is distributed by spray nozzles over the sur-
face of the drug. The movement of the solvent reduces boundary layers and
the uniform distribution minimizes local concentration in a shorter time.

Figure 1: Circulatory extraction

[Link] Multistage Extraction

In the normal maceration process, extraction is incomplete,

since mass transfer ceases when equilibrium is reached. This problem can
be overcome using a multistage process. The equipment needed for this
method is a vessel for the crude drug, a circulating pump, spray distributors
and a number of tanks to receive the extracted solution. The extractor and
tanks are connected with piping and valves as shown in Figure 2, so that any
of the tanks may be connected to the extractor for transfer of the solution.
Each batch of drug is treated several times with solvent and, once a cycle
is in process, the receivers contain solution with the strongest in receiver 1
and the weakest in receiver 3.

73
3 MACERATION, PERCOLATION AND INFUSION TECHNIQUES FOR THE EXTRACTION OF MEDICINAL AND AROMATIC PLANTS

[Link].1 Advantages

The crude drug is extracted as many times as there are receiv-

ers (in Figure 2 there are three receivers). If more extraction stages are
required, it is only necessary to have more receivers. The last treatment of
the drug – before it is discharged – is with fresh solvent, giving maximum
extraction. The solution is in contact with fresh drug before removal for
evaporation, giving the highest possible concentration.

[Link].2 Procedure

Fill the extractor with crude drug, add solvent and circulate.
Run off to receiver 1. Refill the extractor with solvent and circulate. Run off
to receiver 2. Refill the extractor with solvent and circulate. Run off to re-
ceiver 3. Remove drug from the extractor and recharge. Return solution from
receiver 1 to the extractor. Remove for evaporation. Return solution from
receiver 2 to the extractor and circulate. Run off to receiver 1. Return solu-
tion from receiver 3 to the extractor and circulate. Run off to receiver 2. Add
fresh solvent to the extractor and circulate. Run off to receiver 3. Remove
drug from the extractor and recharge. Repeat cycle.

Figure 2: Multistage extraction

[Link].3 Extraction Battery

In the normal percolation process, the percolate is a very dilute

solution, while the ideal situation is to obtain the maximum concentration
possible. Continuous extraction devices of battery type are used when large
amounts of a single material are handled. Such devices can be achieved by
treating percolation as a multistage process. In an extraction battery proc-
ess, a series of vessels is used and extraction is semicontinuous.

[Link].4 Equipment

An extraction battery consists of a number of vessels with in-

terconnecting piping. Vessels are so arranged that solvent can be added
to and the product taken from any vessel. These vessels can, therefore, be

74
 EXTRACTION TECHNOLOGIES FOR MEDICINAL AND AROMATIC PLANTS

made into a series with any of vessels as the first of the series. The use
of an extraction battery is illustrated in Figure 3, which shows the simplest
arrangement of three vessels.

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3.6 Percolation (Exhaustive Extraction)

3.6.1 General Process of Percolation

In this process, an organized vegetable drug, in a suitably pow-

dered form, is packed in a percolator and the solvent is allowed to percolate
through it. Although some materials (e.g. ginger) may be packed directly into
the percolator in a dry state, this may cause difficulties with other drugs. With
the addition of solvent, the dry material swells and this swelling increases
with increasing aqueous nature of the solvent. This swelling reduces or blocks
the flow of the solvent, thus seriously affecting the extraction process. Fur-

75
3 MACERATION, PERCOLATION AND INFUSION TECHNIQUES FOR THE EXTRACTION OF MEDICINAL AND AROMATIC PLANTS

thermore, if the dry powder is packed, fine particles may be washed down the
column and settle at the lower levels, reducing the porosity drastically, blocking
the column and making the column nonuniform. The finer particles may even
be washed out of the column. These difficulties can be prevented by a prelimi-
nary uniform moistening of the raw material with the menstruum for a period
of 4 h in a separate closed vessel; this process is called imbibition. During
this period, the crude drug is allowed to swell to the maximum extent. Hence,
when aqueous solvents are used for extraction, more menstruum is needed
during imbibition. Also, the occluded air in the drug powder is replaced by the
vapor of the solvent, thereby enabling the material to be more evenly packed
and allowing the menstruum to flow more uniformly. Uneven packing permits
more solvent to pass through channels offering less resistance to the flow of
the solvent, thus resulting in inefficient extraction. After imbibition, the drug is
packed evenly into the percolator. The imbibed drug is packed over a loose plug
of tow or other suitable material previously moistened with the solvent. Even
packing can be achieved by introducing the material layer by layer and pressing
it with a suitable implement to give even compression; the pressure exerted on
the material depends on the nature of the material and its permeability. After
packing is over, a piece of filter paper is placed on the surface followed by a
layer of clean sand such that the top layer of the drug is not disturbed when
solvent is added for extraction. Sufficient menstruum is now poured over the
drug slowly and evenly to saturate it, keeping the tap at the bottom open to
allow the occluded gases between particles to pass out. Menstruum should
never be poured with the tap closed since the occluded air will escape from
the top, disturbing the bed. When the menstruum begins to drip through the
tap, the tap is closed; sufficient menstruum is added to maintain a small layer
above the drug and allowed to stand for 24 h. The layer of menstruum above
the surface of the bed prevents drying of the top layer, which may result in the
development of cracks on the top surface of the bed. The 24-h maceration pe-
riod allows the solvent to diffuse through the drug, solubilize the constituents
and leach out the soluble material. In this way, the extraction is more efficient
than carrying out percolation without the maceration period.

After the maceration, the outlet is opened and the solvent is

percolated at a controlled rate with continuous addition of fresh solvent. The
volume of percolate collected depends on the nature of the final product. In
general, about 75% of the volume of the finished product is collected, the
marc is pressed and the expressed liquid is added to the percolate, giving
about 80%-90% of the final volume. After assay, the volume is adjusted with
calculated quantities of fresh menstruum. If no assay is available, the volume
is adjusted after adding the other constituents, if any. In percolation, the ex-
pressed liquid is devoid of active constituents as they are already extracted
during the percolation period; pressing the marc is only to recover the valuable
solvent. This is in contrast with maceration in which the marc is pressed.

76
 EXTRACTION TECHNOLOGIES FOR MEDICINAL AND AROMATIC PLANTS

3.6.2 Modifications to the General Process of Percolation

In the general process of percolation, particularly in the manu-
facture of concentrated preparations like liquid extracts, the following prob-
lems may arise:
• If the active substances are thermolabile, evaporation of
large volumes of dilute percolate may result in partial loss
of the active constituents.
• In the case of alcohol-water mixtures, evaporation results
in preferential vaporization of alcohol, leaving behind an al-
most aqueous concentrate. This may not be able to retain
the extracted matter in solution and hence the substances
may precipitate.

In such cases, the general process of percolation is modified,

as described in the next paragraphs.

[Link] Reserved Percolation

In this case, extraction is done through the general percolation

procedure. At the end, the evaporation is done under reduced pressure in
equipment like a climbing evaporator to the consistency of a soft extract
(semisolid) such that all the water is removed. This is then dissolved in the
reserved portion, which is strongly alcoholic and easily dissolves the evapo-
rated portion with any risk of precipitation.

[Link] Cover and Run Down Method

This is a process that combines the maceration and percola-

tion techniques. This process cannot be used for materials that contain
volatile principles or for those which undergo change during the evaporation
stage. This procedure is advantageous because industrial methylated spirit
may be used for extraction instead of the costly rectified spirit.

The detailed procedure is as follows. After the imbibition stage,

the material is packed in a percolator and macerated for a few hours with a
suitable diluted industrial methylated spirit. Then, the liquid is run off and the
bed is covered with more menstruum. Maceration is done as before and the
second volume of the extract is collected. This process is repeated several
times with the later weaker extracts used for extraction of a fresh batch of the
drug. More concentrated fractions are evaporated under reduced pressure to
eliminate the toxic methanol. After the concentrate is assayed for the active
principle or for total solids content, it is diluted with water and ethanol to ob-
tain the correct concentration of alcohol and active principle.

77
3 MACERATION, PERCOLATION AND INFUSION TECHNIQUES FOR THE EXTRACTION OF MEDICINAL AND AROMATIC PLANTS

3.6.3 Percolators

Different types of percolators are used for small- and large-

scale extraction.

[Link] Small-scale or Laboratory-scale Extraction

The processes for the manufacture of concentrated preparations,

maceration and percolations, are involved in extraction followed by the evapora-
tion of solvents. The two operations are combined in a continuous extraction
process.
The general procedures and apparatus used for small- or labo-
ratory-scale extraction are described in the following paragraphs.

[Link].1 Soxhlet Apparatus

On the laboratory scale, the Soxhlet apparatus is used. It con-
sists of a flask, a Soxhlet extractor and a reflux condenser. The raw material
is usually placed in a thimble made of filter paper and inserted into the wide
central tube of the extractor. Alternatively, the drug, after imbibition with men-
struum, may be packed in the extractor taking care that the bottom outlet
for the extract is not blocked. Solvent is placed in the flask and brought to
its boiling point. Its vapors pass through the larger right hand tube into the
upper part of the extractor and then to the condenser where they condense
and drop back onto the drug. During this period, the soluble constituents
are extracted. When the level of the extract reaches the top of the syphon
tube, the entire volume of extract syphons over into the flask. The process
is continued until the drug is completely extracted. The extract in the flask is
then processed. This procedure is thus a series of short macerations.

Figure 4: Soxhlet apparatus for hot extraction

78
 EXTRACTION TECHNOLOGIES FOR MEDICINAL AND AROMATIC PLANTS

[Link].2 Official Extractor

An official extractor, as described in the official monographs

(e.g. IP, British Pharmacopoeia), is illustrated in Figure 5. In this case, the
extraction is a continuous percolation procedure. In this apparatus, vapors
rise through the extraction chamber passing the drug container; the vapor
condenses in the reflux condenser and returns through the drug, taking the
soluble constituents to the flask.

Figure 5: Apparatus for the continuous extraction of drugs

[Link] Limitations of the Official Extractor

It is not useful when the raw material contains thermolabile

active constituents, because the extraction is carried out at an elevated
temperature and the extract in the flask is also maintained in the hot condi-
tion until the process is complete. It can be used only with pure solvents
or with solvent mixtures forming azeotropes. If an ordinary binary mixture is
used as the menstruum, the composition of the vapor will be different from
the liquid composition.

Similar methods can be used in large-scale production.

A typical industrial set-up for continuous extraction is shown in

Figure 6. The principle of operation resembles that of the laboratory equip-
ment.

79
3 MACERATION, PERCOLATION AND INFUSION TECHNIQUES FOR THE EXTRACTION OF MEDICINAL AND AROMATIC PLANTS

Figure 6: Continuous extraction: large-scale plant

[Link] Large-scale Extractor

The drug is supported on a perforated metal plate covered with

a layer of sacking or straw. The percolator has a removable lid which contains
portholes for running the solvent in and for observing the flow of solvent.
The outlet from the percolator is fitted with a tap and pipeline. This outlet
permits removal of the percolate for subsequent processing or for use as a
menstruum in a second percolator in series, resulting in more efficient use
of the menstruum by carrying out the extraction in a counter-current man-
ner. On the small scale, copper percolators were originally used but these
are now largely replaced with percolators made of glass or stainless steel.
A slightly conical percolator is better than a cylindrical one since the sloping
sides permit the eventual expansion of the bed and also allow the solvent
to permeate the material present near the sides at the bottom, which is a
problem with a cylindrical percolator.

Figure 7: Commercial scale percolator

80
 EXTRACTION TECHNOLOGIES FOR MEDICINAL AND AROMATIC PLANTS

3.7 Infusion

3.7.1 General Considerations

Infusions are dilute solutions containing the readily soluble

constituents of crude drugs. Formerly, fresh infusions, prepared by macerat-
ing the drug for a short period in cold or boiling water, were used and diluted
to eight volumes but, now, infusions are usually prepared by diluting one
volume of a concentrated infusion to ten volumes with water. Concentrated
infusions are prepared by a modified percolation or maceration process.
After dilution with water, concentrated infusions resemble in potency and
aroma the corresponding fresh infusion. Infusions are liable to fungal and
bacterial growth, and it is necessary to dispense them within 12 h of their
preparation.

3.7.2 General Method for Preparing Fresh Infusions

The coarsely powdered crude drug (50 g) is moistened, in a

suitable vessel with a cover, with 50 ml cold water and is allowed to stand
for 15 min. Then, 900 ml boiling water is added, and the vessel is covered
tightly and allowed to stand for 30 min. The mixture is strained and enough
water is passed to make the infusion measure 1000 ml. Some drugs are
supplied (accurately weighed) in muslin bags for preparing specific amounts
of infusion and as such are used for infusion preparation. If the activity of
the infusion is affected by the heat of the boiling water, cold water should be
used. As fresh infusions do not keep well, they should be made extempora-
neously and in small quantities at the time of use.

3.7.3 Preparation of Concentrated Infusions

The official monographs also recognize certain “concentrated

infusions” in which 25% alcohol is added during or after the infusion process
and then diluted as per pharmacopoeial (official) requirement. Concentrated
infusions are especially prepared in cases in which the active and desirable
principles of drug are equally soluble in water and in the menstruum used
for both concentrates and infusions.

3.8 Evaporation

One quality-relevant parameter is the evaporation of the eluate

from the soft extract. The state of art is cautious vacuum evaporation, in
which evaporation temperatures do not exceed 55° C. The temperature in
relation to the evaporation time is of special importance for quality of this
step, especially if the extract contains volatile or thermolabile constituents.

81
3 MACERATION, PERCOLATION AND INFUSION TECHNIQUES FOR THE EXTRACTION OF MEDICINAL AND AROMATIC PLANTS

3.9 Conclusions

The spectrum of constituents obtained by steady-state extrac-

tion (simple maceration) differs from that obtained by exhaustive extraction
(percolation). With maceration, one can achieve a spectrum of constituents
similar to that of percolation. Different extraction procedures may be con-
sidered to be equivalent if they respect critical quality parameters and if the
analysis of numerous production batches confirms their compliance with
standards.

Bibliography
Anonymous, 1955, Indian Pharmacopoeia, the Manager of Publication, Delhi, p.
273

Anonymous, 1973, British Pharmaceutical Codex, the Pharmaceutical Press, London,

p. 703-704

Anonymous, 1980, British Pharmacopoeia, VOL. II, University Press, Cambridge, Lon-
don, p. 576

Anonymous, 2002, Bentley’s Text book of Pharmaceutics EA Rawlins (Ed.). Reprint,

Bailliere Tindall, London/All India Traveller Book Selter, New Delhi

Cooper, J. W. and Gunn, C., 1975, Tutorial Pharmacy, S. J., Carter Reprint, CBS Pub-
lication, Delhi, p. 251- 261

Cooper, J. W. and Gunn, C., 1985, General Pharmacy, CBS Publishers and Distribu-
tors Delhi, p. 308-333

Evans, W. C., 1998, Trease and Evan’s Pharmacognosy (14th Edition), W. B. Saun-
ders Company Limited, London, p. 119

Sambamurthy, K., 2002, Pharmaceutical Engineering Reprint, New Age International

(P.) Ltd., New Delhi, p. 173-194

Singh, J., Bagchi, G. D., and Khanuja, S. P .S., 2003, Manufacturing and quality
control of Ayurvedic and herbal preparations, In: Verpoorte, R. and Mukherjee,
P. K.(Eds), GMP for Botanicals, Regulatory and Quality Issues on Phytomedicine
(1st Edition), Business Horizons, New Delhi, p. 201-230

Waldesch, F. G., Konigswinter, B. S., and Blasius, H., 2003, Herbal Medicinal Prod-
ucts, Medpharm, Stuttgart, Germany and CRS Press, London, p. 48-54

82
 EXTRACTION TECHNOLOGIES FOR MEDICINAL AND AROMATIC PLANTS

4 Hydrolytic Maceration, Expression

and Cold Fat Extraction

A. K. Singh

Abstract
The incorporation of bioactive ingredients without loss of activity into foods, flavors,
pharmaceuticals, pesticides and cosmaceutical products is very important. Extraction
of active constituents from raw materials is an important and critical step in main-
taining bioactivity. A number of methods are available for extraction, and these are
selected in such a way that the activity of the phytoconstituents is retained. This paper
discusses the processes of hydrolytic maceration, expression and cold fat extraction.

4.1 Introduction

The extraction of active constituents from plants is one of the

most critical steps in the development of natural products for commercial
use. The simplest example of extraction may be brewing a cup of coffee,
wherein caffeine and tannins are extracted from coffee beans in hot water.
All living organisms contain complex mixtures of chemicals, usually held
within cellular structural material (protein, lipid, polysaccharides etc.) of
which some are desired while others are not. Thus, taking out the desired
part from the whole crude drug is referred to as extraction and it is done in
solvents where ingredients move from one phase to another.

A number of methods are available for extraction and the choice

among them is dictated by the physicochemical properties and stability of
the phytoconstituents to be obtained. For the extraction of essential oils,
the simplest methods are hydrodistillation and steam distillation while other
methods also employed are cold fat extraction, expression, maceration and
solvent extraction. Nowadays, more advanced technologies are used, such
as supercritical fluid extraction, solid phase micro-extraction and phytonic
extraction. The present article deals with extraction by hydrolytic macera-
tion, expression and cold fat extraction.

4.2 Hydrolytic Maceration

The word maceration is derived from the Latin word macera-

tus, which means to soften. In reference to medicinal and aromatic plants,
maceration refers to the preparation of a solution by soaking plant material
in vegetable oil or water. Maceration methods are based on the immersion
of crude drug in bulk solvent, while percolation methods depend on the flow

83
4 HYDROLYTIC MACERATION, EXPRESSION AND COLD FAT EXTRACTION

of solvent through the powdered drug. The rate of extraction depends upon
the following:
• The rate of transport of solvent into the mass to be leached.
• The rate of solubilization of soluble constituents into solvent.
• The rate of transport of solute out of the insoluble material
and from the surface of the insoluble material into the solu-
tion.

In the process of maceration, the powered solid material is

placed in a closed vessel (to prevent evaporation) and the chosen solvent
(menstruum) is added. It is allowed to stand for a long time (varying from
hours to days) with occasional shaking. Sufficient time is allowed for the
menstruum to diffuse through the cell wall to solubilize the constituent
present in the cells and for the resulting solution to diffuse out. The proc-
ess takes place only by molecular diffusion. After the desired time, the
liquid is strained off; the solid residue (marc) is pressed to recover as
much solvent as possible. When the menstruum is water and the period
of maceration is long, a small quantity of alcohol may be added to prevent
microbial growth.

Cold maceration of crushed grapes is done at room tempera-

ture before the onset of fermentation. In this process, the skin and seeds
are permitted to soak for one to two days prior to the initiation of fermenta-
tion to get more aqueous extraction without the effect of ethanol on grape
cells. In certain cases, hydrolysis is done with a suitable agent (enzyme)
prior to maceration, e.g. maceration of wine. The quality of wine is judged
by its appearance, color, aroma, taste (mouth feel) and flavor. Grape-derived
aroma and flavor precursors exist partially as non-volatile, sugar-bound gly-
cosides. Hydrolysis modifies sensory attributes and potentially enhances
wine quality. Flavored aglycones potentially affect the wine quality after hy-
drolysis. Cell wall-degrading enzymes help in the release of grape aroma,
when cold maceration prior to fermentation has been carried out.

4.3 Expression Extraction of Essential Oils

Most essential oils are isolated from the respective plant parts
by the process of hydrodistillation or steam distillation. A few essential oils
such as those present in the citrus fruit peel can be, and in large part are,
obtained by pressing, which yields a product of superior quality. The long
action of heat with boiling water affects some thermolabile constituents
which may decompose due to hydrolysis, polymerization and resinification.
Therefore, the essential oil obtained by distillation does not represent the
natural oil as it originally occurred in the plant material. In such plant ma-
terials, essential oil is extracted by the process of expression or solvent
extraction.

84
 EXTRACTION TECHNOLOGIES FOR MEDICINAL AND AROMATIC PLANTS

Before dealing with the process of expression in citrus oil, it is

important to review the structure of a citrus peel. The citrus peel contains
numerous oval, balloon-shaped oil sacs and glands or vesicles (0.4-0.6 mm
diameter). These are ductless glands which are irregularly distributed in the
outer colored (flavedo) portion of the peel of maturing and matured fruit,
in the outer mesocarp beneath the epicarp and hypoderm and above the
inner mesocarp (albedo), respectively. Albedo is made of cellulose, hemicel-
lulose, lignin, pectin, sugars, glycosides, etc. On maturation, cells of albedo
become elongated and branched, with large intracellular spaces which give
the ripe peel its spongy texture. The spongy layer plays an important role
in the expression of oil, but it easily absorbs the oil ejected from the sacs
and causes some mechanical difficulties in oil extraction. The freshness
and stage of maturity affect the oil ejection from the peel. The total weight
of the peel is about half that of the fruit and the oil content is 0.5%-0.7%.
The cells surrounding the oil sac contain salt (colloids) in aqueous solution.
In contact with water, the higher osmotic pressure of the cell results in diffu-
sion of water into them, increasing turgor pressure and causing the oil sac
to stress from every side. If the spongy tissue is not filled with water, it will
absorb the oil as the sacs are broken and hold it with great tenacity. So the
pressure exerted yields first aqueous fluid and later oil.

In Sicily, peels are immersed in water for several hours before

being subjected to a “sponge” process. A dilute aqueous solution of salt
acts as a carrier to prevent loss by spurting. The product of expression is
not a simple mixture of oil and water but a thin emulsion which is left to
stand; gradually a supernatant layer forms. Filtration through a sponge ab-
sorbs the colloidal material and leaves the mixture of oil and water.

4.3.1 Process of Expression

[Link] Hand Process

In this process, the freshly harvested fruits are cut transversely

into two halves. The pulp is removed with a sharp-edged spoon called rastrel-
lo. The peel is then immersed in water for several hours and finally pressed
by hand. The worker holds, with the left hand, either one large or two smaller
flat sponges on top of a wooden crossbar and, with the right hand, presses
the peel against the upper sponge. Thinner peels can be pressed from in-
side. The emulsion ejected from the oil sacs is soaked by the sponge, which
retains solid matter and absorbs colloidal substances. Squeezing the con-
tent of the sponge from time to time, oil is finally decanted and drawn off.
This process requires much labor and the yield of this method is 50%-70% of
the total oil present in the peel. The quality of oil obtained from hand press-
ing is near to the quality present in fruit peel. A large number of small units
in Sicily and Calabria were formerly responsible for the entire Italian produc-
tion of lemon and orange oil, but the process is not in use now.

85
4 HYDROLYTIC MACERATION, EXPRESSION AND COLD FAT EXTRACTION

[Link] Ecuelle Process

This process was common in the south of France. Ecuelle con-

sists of a shallow bowl of copper with a hollow central tube with which it
forms a sort of funnel. The bowl is equipped with large brass nails with blunt
ends, on which the fruit is rolled by hand with some pressure until the entire
surface of fruit yields its oil. The oil and aqueous cell contents drain into the
central tube where they are separated by decantation. The yield is only 20%
of the total oil present in the peel.

These methods were quite laborious and, with the advance of

technology, machines have been invented to do them. Nowadays, rinds are
extracted for oil using centrifugal force.

[Link] Hand Machine

For expression, the peel is placed in a hollow sponge attached

with other sponges to a plate actuated by the lever and fixed below with
additional sponges to the base. The sponge is fitted with a funnel through
which oil and aqueous material pass to the receiving vessel. The part that
comes in contact with oil is made of brass or bronze.

[Link] Sfumatrici and Pelatrici

The machines that treat only the peel after removal of juice
and pulp are called sfumatrici, while those that process the whole fruit are
known as pelatrici.

[Link].1 Special Sfumatrice

This is a specially designed roller type machine in which each

peel is bent to expel the maximum quantity of oil. Not much pressure is ex-
erted to expel other contents of the cells. The emulsion is collected and fil-
tered through wool or sponges to yield oil and water. A number of sfumatrici
have been developed and were in use in many countries.

In expression using sfumatrici, two approaches are used. In

the first approach (used by Ramino Sfumatrice), only the peel is treated, so
halving the fruit, removing the pulp and expressing the peel are the steps
involved. In the second approach, the oil is extracted by either puncturing
the peel glands or cutting a superficial layer of peel to expose the oil glands;
this is followed by washing away the oil with a spray of water.

In whole fruit extraction with a rasping machine, the whole fruit

is crushed and oil is subsequently separated from the aqueous phase (juice
and cell liquid). As citrus peel oil is a byproduct of the citrus juice industry,
both the oil and juice are extracted subsequently, e.g. in a rotatory juice

86
 EXTRACTION TECHNOLOGIES FOR MEDICINAL AND AROMATIC PLANTS

extractor or Pipkin peel oil press. Here, the fruit is washed automatically,
sorted according to size and then cut in two halves. The halved fruit is
passed between two cylinders which remove only the juice by gentle press-
ing without affecting the oil glands on the surface. The residual halved peels
are extracted for essential oil. In the Pipkin peel oil press, for example, oil is
expressed by two close stainless steel cylinders with capillary grooves run-
ning around the circumference. The expressed oil automatically comes out
of the grooves and there is no need to spray water..

[Link] Modern Machines

Nowadays, complete mechanization has been achieved and

whole fruit processing machines have been developed. These machines ei-
ther crush whole fruit and then separate the oil from the aqueous phases
by distillation or centrifugation, or they express the oil in such a way that it
does not come in contact with the juice during the process. The oil extractor
developed by Brown International, California, liberates the essential oil from
whole citrus fruit. Oil removal is achieved by lightly puncturing the entire
surface of the fruit with over three million sharp stainless steel points con-
figured in the form of rotating rolls. An adjustable speed differential between
adjacent rolls controls the amount of pressure applied to the fruit. Whole
fruits roll across the brown oil extractor (BOE, Figure 1), which is made of
toothed rollers partially set in a flowing bed of water which propels the fruit
across the machine and simultaneously punctures the peel to release the
oil from the glands. The fruit proceeds to the extractor and the oil-water mix-
ture goes to centrifugation and to the oil recovery chamber.

Figure 1: Brown oil extractor

[Link] FMC Whole Fruit Extractor

Food Machinery Corporation (FMC) of San José, California, has

developed many designs and improved extractors in which both the juice
and the volatile oil are extracted without getting mixed with each other. Fur-
ther details are available at: [Link]
ties/History/Landmarks/[Link].

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4 HYDROLYTIC MACERATION, EXPRESSION AND COLD FAT EXTRACTION

Figure 2: FMC whole fruit extractor

The FMC juice extractor has two inter-meshing jaws which encom-
pass the fruit, crushing it between them. The juice exits through a mesh screen
which penetrates the center of the fruit and the juice is separated from the
peel, pith and seeds. This crushing action is sufficient to force the oil out of the
glands on the surface of the flavado. The FMC machine sprays water onto the
surface of the fruit, and the oil-water emulsion is subjected to centrifugation.
Traces of water and waxy material are separated by keeping low temperature.
About 75% of citrus oil production utilizes this technology. The odor of cold
pressed oil is true in nature and similar to that of the oil present in fruit.

4.4 Cold Fat Extraction (Enfleurage)

Certain high-quality odor-producing flowers such as jasmine,

tuberose and gardenia yield small quantities of oil and cannot be distilled
by hydrodistillation. Furthermore, the oil components are thermolabile and
such flowers, even after plucking, continue to emit small quantities of per-
fume. The oil from these types of flowers is extracted by cold fat extraction,
i.e. enfleurage.

Figure 3: Chassis for holding the fat crops

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 EXTRACTION TECHNOLOGIES FOR MEDICINAL AND AROMATIC PLANTS

Fat possesses a high power of absorption of volatile oil and, if

brought in contact with fragrant flowers, it absorbs the perfume. This princi-
ple methodically applied on large scale constitutes enfleurage. The quality
of the fat base is important for the quality of the flower oil. It must be odor-
less and of proper consistency. If the crops (fat) is too hard, the blossoms
will not have sufficient contact with it, the absorption will be insufficient,
and the quality and yield will be poor. If the crops is loose, it may engulf the
flowers so that exhausted ones are difficult to remove and retain adhering
fat when removed. The crops must have a consistency suitable to produce
a semihard surface from which exhausted flowers can be removed easily.
Saturated fragrant fat extract is known as pomade. Enfleurage process of
cold extraction is carried out in Bulgaria, Egypt, Algeria, Sicily (Italy), and
Grasse (France). France remains the main centre of production of highly
prized so-called natural flower oil. Natural flower oil does not include the
distilled essential oil but applies only to flower oils obtained by enfleurage,
maceration or solvent extraction. The whole process is carried out in cold
atmosphere cellars (cold rooms). The mixture of one part highly purified tal-
low and two parts lard is best suited for enfleurage.

Different bases have been used in the preparation of crops.

For example, vegetable fat, mineral oil, esters of polyhydric aliphatic alcohol
(ester of glycol, glycerol, mannitol, hexitol), and fatty acids of high molecular
weight have been tried, but the best results were from the old-fashioned
mixture of lard and tallow. To purify tallow, it is melted after cleaning, wash-
ing and removing blood and muscles; the skin is beaten and cleaned, and
benzoin (0.6%) and alum (0.15%-0.30%) are added. Benzoin is a preserva-
tive while alum causes impurities to coagulate during heating. Warm melted
fat is filtered through cloth and left to cool.

The vehicle for holding the fat crops during the process is a
specially designed “chassis”. These are rectangular wooden frames (2 in.
high, 20 in. long and 16 in. wide) that hold a glass plate (Figure 3). The fat
crops is applied to both sides of the glass with a spatula at the beginning of
enfleurage: 360 g crops on each side is required. When piled one above the
other, the chassis form an air-tight compartment with a layer of fat on the
upper and lower sides of each glass (Figure 4). Every morning, freshly picked
flowers are cleaned by removing the leaves and stalks and eliminating the
moisture from dew or rain. The flowers are strewn (Figure 3) by hand on top
of the fat layer of each glass plate. Traces of moisture will cause the crops
to go rancid, so precaution must be taken.

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4 HYDROLYTIC MACERATION, EXPRESSION AND COLD FAT EXTRACTION

Figure 4: Pile of chassis

When chassis are piled one above the other, flowers remain in
contact with the lower fat crops which acts as direct solvent, whereas the
upper fat layer (beneath the glass plate of the chassis) absorbs only the
volatile perfume given off by the flowers. After 24 h, the flowers are removed
from the chassis. The time of removal, however, depends on type of the flow-
ers. Removal of the flowers from the crops is known as defleurage. Immedi-
ately following defleurage, the chassis are recharged with fresh flowers. For
this purpose, the chassis are turned over, thus the fat layer which in the pre-
vious operation formed on top (ceiling) of the small chamber is now directly
charged with fresh flowers. When the fat crops becomes saturated with
fragrance (pomade), the crops is removed from the chassis with a spatula.
The pomades are extracted with absolute alcohol in a process called extrait.
At the beginning and several times during the harvest, the fat on the chas-
sis is scratched over with a metal comb and tiny furrows are drawn in order
to change and increase the surface area available for maximum absorption.
The most highly saturated pomade is pomade no. 36, meaning the crops
on the chassis has been treated with fresh flowers 36 times during the
whole process of enfleurage. In the case of jasmine, every kilogram of fat is
charged with 3 kg flowers during the entire period. The alcohol washing of
pomade no. 36 are called extrait no. 36, which reproduces the natural flower
oil to a remarkable degree. Sometimes a fatty note is present in the extrait,
which can be removed by freezing and filtering the alcoholic washes.

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 EXTRACTION TECHNOLOGIES FOR MEDICINAL AND AROMATIC PLANTS

Figure 5: Batteuses

Pomades are processed during winter in cool cellars called

batteuses (Figure 5) made of copper and equipped with stirrers. Several
batteuses are arranged serially. The alcohol driven from one batteuse is
poured in second, third and first washings of successive batteuses. For the
last washing, fresh alcohol is used. Extrait no. 36 is cooled in a refrigerator
to separate the fat. The exhausted fat is odorless and used for the manu-
facture of soap. Complete concentration of extrait is done under vacuum at
low temperature to remove alcohol, producing absolute of enfleurage which
is semisolid in nature. The flowers removed from the chassis are extracted
with solvents (petroleum ether) and the concentrated residue is dissolved in
absolute alcohol. The fat is removed by freezing. This preparation is known
as absolute of chassis. Absolute of enfleurage and absolute of chassis
logically supplement one another because each represents only part of the
total oil present in the flowers but, due to cost difference, they are kept
separately.

4.5 Conclusions

In spite of recent technological development in the field of

extraction, hydrolytic maceration, expression and cold fat extraction tech-
niques are inevitable for certain types of raw material. For these materials,
no substitutes are available at present, although hydrodistillation or solvent
extraction can be used for essential oils of citrus and flower oils or other
perfumery materials. Nonetheless, the real replication of essential oil or
the true natural fragrances present in these materials can only be produced
by expression and cold fat extraction. Only technological improvements for
easy extraction can be made without affecting the basic principles of these
processes.

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5 Decoction and Hot Continuous

Extraction Techniques
S. Tandon and S. Rane

Abstract
The chapter describes the techniques, parameters and equipment used for the extrac-
tion of plants by decoction and hot continuous extraction. Principles, mechanisms,
merits and demerits of conventional solvent extraction and accelerated solvent extrac-
tion are also discussed.

5.1 Introduction

Of the traditional methods of extraction of medicinal plant ma-

terial for making an aqueous extract, decoction is one of the most described.
Decoction is a water-based preparation to extract active compounds from
medicinal plant materials. In this process, the liquid preparation is made
by boiling the plant material with water. Decoction differs from infusion in
that the latter is not actively boiled. Decoction is the method of choice
when working with tough and fibrous plants, barks and roots and with plants
that have water-soluble chemicals. The plant material is generally broken
into small pieces or powdered. Different methods have been described for
the preparation of decoctions. In the Ayurvedic method, traditionally known
as kwatha, the crude drug in form of yavakuta (small pieces) is placed in
earthen pots or tinned copper vessels with clay on the outside. Water is
added and the pot is heated on a fire. If the material is soft, four times water
is used per 1 part drug; if the drug is moderately hard, eight times water is
used and if the drug is very hard, sixteen times water is recommended. The
mixture is then boiled on low flame until it is reduced to one-fourth starting
volume, in case of soft drugs, and one-eighth in case of moderately or very
hard drugs. The extract is then cooled and strained, and the filtrate is col-
lected in clean vessels.

5.2 Solid-liquid Extraction Process

Solid-liquid extraction is one of the most widely used unit

operations in the medicinal and aromatic plant industry. One example of
solid-liquid extraction is the solvent extraction of herbs. This process, also
referred to as leaching, is a separation technique that is often employed
to remove a solute from a solid mixture with the help of a solvent. The in-
soluble solid may be colossal and permeable; more often it is particulate
and the particles may be openly porous, cellular with selectively permeable
cell walls, or surface-activated. The stream of solids being leached and the
accompanying liquid are known as the underflow. The solid content of the

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5 DECOCTION AND HOT CONTINUOUS EXTRACTION TECHNIQUES

stream is called marc. The stream of liquid containing the leached solute is
known as the overflow.

5.3 Process Parameters Affecting Solid-liquid

Extraction

The following parameters generally affect the rate of solid-liq-

uid extraction (leaching):
• Post-harvest processing
• Matrix characteristics
• Choice of solvent
• Method of contact
• Temperature of extraction
• Number of washes
• Condition for extraction (e.g. agitation)

5.3.1 Post-harvest Processing

After harvesting, most herbs have a moisture content of
60%-80% and cannot be stored without drying. Otherwise, important com-
pounds can breakdown or micro-organisms may contaminate the material.
Drying of the herbs in shade in a thin layer is generally preferred. Some
medicinal plants, like pyrethrum, lose their active constituents if exposed to
direct sun light for a long period. For drying large quantities of plant mate-
rial, a hot air drying oven is used where material can be placed on a large
number of trays stacked over each other. Oven temperature must be kept
at a safe level so as not to damage the active constituents of the medicinal
plant.

5.3.2 Matrix Characteristics

Knowledge of the matrix characteristics of the carrier solid is
important to determine whether it needs prior treatment to make the solute
more associable to the solvent. Grinding of plant material means mechani-
cally breaking down leaves, roots, seeds, or other parts of a plant into small
units, ranging from large course fragments to fine powder.

Solute may exist in the inert solids in a variety of ways:

1. On the surface of the solid,
2. Surrounded by a matrix of inert material, Chemically com-
bined, or inside the cells.

Solute adhering to the solid surface is readily removable by

solvent. When the solute exists in pores surrounded by a matrix of inert
material, the solvent has to diffuse to the interior of the solid to capture the

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 EXTRACTION TECHNOLOGIES FOR MEDICINAL AND AROMATIC PLANTS

solute. In the medicinal plant industry, generally ball mills and fluid mills are
employed for powdering, and the optimum particle size is established prior
to the large-scale extraction.

5.3.3 Choice of Solvent

The following factors should be considered when selecting a
solvent for commercial use:
• Solvent power (selectivity). Only the active, desired constit-
uents should be extracted from the plant material, which
means that a high selectivity is required.
• Boiling temperature. The boiling point of the solvent is as
low as possible in order to facilitate removal of the solvent
from the product.
• Reactivity. The solvent should not react chemically with the
extract, nor should it readily decompose.
• Viscosity. A low viscosity of the solvent leads to low pressure
drop and good heat and mass transfer.
• Safety. The solvent should be non-flammable and non-cor-
rosive, and should not present a toxic hazard; its disposal
should not imperil the environment.
• Cost. The solvent should be readily available at low cost.
• Vapor pressure. To prevent loss of solvent by evaporation, a
low vapor pressure at operating temperature is required.
• Recovery. The solvent has to be separated easily from the
extract to produce a solvent-free extract.

5.3.4 Conditions for Extraction

Too fine particle size may result in problems with packing of

solids for extraction, preventing free flow of solvent through the solid bed. In
such a case, extraction is more difficult, especially when finely divided sol-
ids are treated in an un-agitated state. Dispersion of the particles in liquid
solvent by agitation facilitates contact of the solid with the solvent. Agita-
tion, while giving good extraction, may cause suspension of fine particles in
overflowing solution.

5.4 Method of Solid-liquid Extraction

The three principle types of flow used in leaching systems

are:
1. Single-stage system
2. Multistage counter-current system
3. Multistage co-current system

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5 DECOCTION AND HOT CONTINUOUS EXTRACTION TECHNIQUES

FRESH SOLVENT OVERFLOW SOLUTION

EXTRACTION
STAGE
SOLID UNDERFLOW SOLID FEED

Figure 1: Single-stage solid-liquid extraction

The single-stage system represents the complete operation

of contacting the solid feed and fresh solvent. This is rarely encountered
in industrial practice because of the low recovery of solute obtained and
relatively dilute solution produced. Efficiency of extraction is somewhat im-
proved by dividing the solvent into a number of smaller portions and then
carrying out multiple successive extractions instead of only one contact of
the entire amount of solvent with the solid.

FRESH SOLVENT
OVERFLOW SOLUTION
EXTRACTION EXTRACTION EXTRACTION
STAGE 1 STAGE 2 STAGE n
SOLID FEED
SOLID UNDERFLOW

Figure 2: Multistage counter-current solid-liquid extraction

In the continuous counter-current multistage system shown in

Figure 2, the underflow and overflow streams flow counter-current to each
other. This system allows high recovery of solute with a highly concentrated
product because the concentrated solution leaves the system after contact
with fresh solid.

FRESH SOLVENT FRESH SOLVENT

FRESH SOLVENT

EXTRACTION EXTRACTION
EXTRACTION STAGE n
STAGE 1 STAGE 2
SOLID FEED SOLID UNDERFLOW
OVERFLOW SOLUTION
OVERFLOW SOLUTION
OVERFLOW SOLUTION

Figure 3: Multistage co-current solid-liquid extraction

In the multistage co-current (parallel) system shown in Figure

3, fresh solvent and solid feeds are contacted in the first stage. Underflow

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 EXTRACTION TECHNOLOGIES FOR MEDICINAL AND AROMATIC PLANTS

from the first stage is sent to the second stage, where it comes in contact
with more fresh solvent. This scheme is repeated in all succeeding stages.

5.5 Solid-liquid Extraction Equipment

Equipment for solid-liquid extraction is of two types:

a) Batch solid-liquid extractor
b) Continuous solid liquid extractor

The most common batch extractors employed for solid-liquid

extraction of medicinal plants are:
• Pot extractor. The extractor has a volume of 2-10 m3 and a
mixer is necessary to guarantee good mixing for treatment
of fine materials. For structured materials, the mixer is only
used for evaporation of the solvent and for emptying the
extractor.
• Rotating extractor. The extractor is filled with extraction ma-
terial and solvent and starts then to rotate. The installation
of heating coils and the use of a double jacket make it pos-
sible to evaporate the solvent at the end of the extraction
cycle. A special form of heating coil can act as mixer during
the extraction period.

The advantage of batch extractors is that they are simple to

operate and are robustly constructed. Disadvantages of batch extractors are
the limited capacity and the discontinuous output of the product.

Figure 4: Pot extractor and rotating extractor

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5 DECOCTION AND HOT CONTINUOUS EXTRACTION TECHNIQUES

5.5.1 Continuous Extraction

For continuously operating extraction, percolation and immer-

sion are used.

[Link] Percolation

The solvent passes through the non-moving solid material and

extracts the soluble active constituents. One advantage of this method is
that the solid material requires little mechanical treatment because it does
not need to move in the percolator while the product passes in the solution.
Moreover, since self-filtration takes place, there is minimum content of fine
solid particles in the extract.

[Link] Immersion

In this process, the solid material dips completely into the sol-
vent and is mixed with it. Therefore, no special percolation properties of the
solid material are necessary. The disadvantage is that no self-filtration of the
extract solution takes place. Therefore, a filtration step has to be added.

5.5.2 Continuous Extraction Equipment

[Link] Continuous Horizontal Extractor

The solid material is placed in baskets and comes in contact

with the solvent by percolation. The flow of solvent through the extractor is
counter-current to the flow of solid material.

Figure 5: Continuous horizontal extractor

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 EXTRACTION TECHNOLOGIES FOR MEDICINAL AND AROMATIC PLANTS

[Link] Hildebrandt Extractor

The solid material is extracted according to the immersion

method. Screw conveyors are installed in the extractor for transporting the
solid material. Again, the solvent flows counter-current to the solid materials
through the extractor.

Figure 6: Hildebrandt extractor

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5 DECOCTION AND HOT CONTINUOUS EXTRACTION TECHNIQUES

[Link] Bonotto Extractor

The Bonotto extractor is used for counter-current extraction ac-

cording to the immersion method. The solid material is transported by the
mixer on a tray until it reaches the open sector where it falls onto the next
tray. The screw conveyor at the outlet withdraws the extracted solid material
(underflow) and prevents the solution from flowing out of the extractor.

Figure 7: Bonotto extractor

[Link] Bollmann Extractor

The fresh solvent is added during the upward movement of the

baskets so that this part operates in counter current. The already preload-
ed solution is withdrawn from the bottom of the extractor and enters the
downward-moving baskets so that this part of the extractor operates in a
co-current way. The full miscella is withdrawn at the bottom of the extractor.

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 EXTRACTION TECHNOLOGIES FOR MEDICINAL AND AROMATIC PLANTS

In the baskets, self-filtration takes place, so that no further treatment of the

miscella before distillation is necessary.

Figure 8: Bollmann extractor

[Link] Kennedy Extractor

The solid material is transported by paddles from one chamber

to the next, in counter-current way to the solvent. The chamber where the
miscella is withdrawn is used as a filtration unit where fine particles are
separated from the extract solution.

Figure 9: Kennedy extractor

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5 DECOCTION AND HOT CONTINUOUS EXTRACTION TECHNIQUES

5.6 Conventional Solvent Extraction

5.6.1 Principles and Mechanisms

Classic techniques for the solvent extraction of active constitu-

ents from medicinal plant matrices are based on the choice of solvent cou-
pled with the use of heat or agitation. Existing classic techniques used to
obtain active constituents from plants include: Soxhlet, hydrodistillation and
maceration with an alcohol-water mixture or other organic solvents. Soxhlet
extraction is a general and well-established technique, which surpasses in
performance other conventional extraction techniques except for, in limited
fields of application, the extraction of thermolabile compounds.

Figure 10: Soxhlet extractor

In a conventional Soxhlet system, as shown in Figure 10, plant

material is placed in a thimble-holder, which is filled with condensed fresh
solvent from a distillation flask. When the liquid reaches the overflow level, a
siphon aspirates the solution of the thimble-holder and unloads it back into
the distillation flask, carrying extracted solutes into the bulk liquid. Solute is
left in the flask and fresh solvent passes back into the plant solid bed. The
operation is repeated until complete extraction is achieved.

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5.6.2 Advantages and Disadvantages of Soxhlet Extraction

Advantages:

1. The displacement of transfer equilibrium by repeatedly bringing

fresh solvent into contact with the solid matrix.
2. Maintaining a relatively high extraction temperature with heat
from the distillation flask.
3. No filtration of the extract is required.

Disadvantages:

1. Agitation is not possible in the Soxhlet device.

2. The possibility of thermal decomposition of the target com-
pounds cannot be ignored as the extraction usually occurs
at the boiling point of the solvent for a long time.

Worldwide, most of the solvent extraction units are based on the

Soxhlet principle with recycling of solvents. Basic equipment for a solvent extrac-
tion unit consists of a drug holder-extractor, a solvent storage vessel, a reboiler
kettle, a condenser, a breather system (to minimize solvent loss) and support-
ing structures like a boiler, a refrigerated chilling unit and a vacuum unit.

Table 1: Some common solvents used for the extraction of medicinal and aromatic plants

Threshold limit
Solvent Boiling point, °C Miscibility with H2O
values, ppm
Acetone 56 ∞ 1000
Acetic acid 116-117 ∞ 10
Ethyl acetate 77 80% 400
Benzene 80 <0.01% 25
2-Butanol 79.5 19% 2200
Cyclohexane 80.7 <0.01% 300
Dichloromethane 39.7 1.3% 2200
Chloroform 61 8% 50
Carbon tetrachloride 76.77 0.8% 10
Hexane 69 <0.01% -
Ethanol 78 ∞ 1000
Ethyl ether 34.6 1.2% 400
Petrol ether 30-50 - 500
Propanetriole 290* ∞ -
Methanol 64.7 ∞ 200
1-Propanol 91 M 400
2-Propanol 82.4 M? 400
Toluene 110.6 0.06 100
t = < 0.01%; * with decomposition; M miscible; ∞ completely miscible

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5 DECOCTION AND HOT CONTINUOUS EXTRACTION TECHNIQUES

5.7 Accelerated Solvent Extraction

5.7.1 Principles and Mechanisms

Accelerated solvent extraction (ASE) is a solid-liquid extraction
process performed at elevated temperatures, usually between 50° and 200°
C, and at pressures between 10 and 15 MPa. Therefore, accelerated solvent
extraction is a form of pressurized solvent extraction. Increased tempera-
ture accelerates the extraction kinetics and elevated pressure keeps the
solvent in the liquid state, thus achieving safe and rapid extraction. Also,
high pressure allows the extraction cell to be filled faster and helps to force
liquid into the solid matrix. A typical accelerated solvent extraction system is
illustrated in Figure 11. Although the solvent used in ASE is usually organic,
pressurized hot water can also be used. In these cases, one refers to pres-
surized hot water extraction or sub-critical water extraction.

Figure 11: Accelerated solvent extraction

5.7.2 Advantages and Disadvantages of Accelerated

Solvent Extraction

Compared with traditional Soxhlet extraction, ASE presents a

dramatic reduction in the amount of solvent and extraction time. Particular
attention should be paid to ASE performed at high temperature, which may
lead to degradation of thermolabile compounds.

5.8 Important Factors for Designing a Solvent

Extraction Plant for Medicinal Plants
• High efficiency of extraction
• Minimal solvent loss
• Facilities for cold and hot extractions
• Extraction with agitation

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 EXTRACTION TECHNOLOGIES FOR MEDICINAL AND AROMATIC PLANTS

• Multiple solvent extraction systems

• Multiple fraction collection systems
• On-line filtration unit
• Solvent recycling and condensing unit
• Vent lines with breather for minimizing solvent loss and max-
imizing safety
• Brine circulation unit
• Fractionating column for separation of solvent mixtures
• Efficient evaporating systems like falling film, wiped film or
rotary evaporators to work under low pressures
• Vacuum manifold system with cold traps
• GMP compatible
• Automation

Figure 12: Solvent extraction plant at CIMAP, India

5.9 Conclusions

Decoction, a water-based preparation, is one of the most used

traditional methodologies for the extraction of active constituents of a me-
dicinal plant. It is generally carried out by boiling the plant part for a fixed
period. Hot continuous extraction or solvent extraction technique is one of
the most widely used extraction techniques for the processing of medicinal
plants. The solvent extraction method is simple, well established and eco-
nomical. Important factors that can affect the efficiency of extraction, such
as post-harvest processing, solid characteristics, choice of solvent, method
of contact, and temperature, should be optimized for best yield. The choice
of solvent especially for commercial plants and high efficiency usually de-

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5 DECOCTION AND HOT CONTINUOUS EXTRACTION TECHNIQUES

pends on many factors such as selectivity, polarity, boiling point, chemical

and thermal stability, safety, flammability, and costs. Despite the economic
advantages of solvent extraction, the use of volatile organic solvents such
as hexane, acetone and methanol for processing medicinal plants has been
limited due to environmental considerations. Hot continuous extraction
technology shall always remain the method of choice for high efficiency,
economical extraction and with less capital investment.

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ing, Analysis and Application of Essential Oils, 1st Edition, Har Krishan Bhalla &
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Gamse, T., 2002, Lecture on Liquid-liquid Extraction and Solid-liquid Extraction. Avail-
able at: [Link]/separacion/archivos/[Link]

Hazra, P. et al., 1989, Solvent extraction of Artemisia annua L. on pilot scale, Re-
search and Industry, 36: 14-16

Kahol, A. P., Tandon, S. and Singh, K. L., 1998, Developments in separation technolo-
gies for the processing of medicinal and aromatic plants, PAFAI Journal, 20(3):
17-28

Pangarkar, V. G., 1990, Liquid-liquid contact operation: review of equipment, PAFAI

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7 Distillation Technology for Essential Oils

S. Tandon

Abstract
In many developing countries, the technology employed for extraction of essential oils
from aromatic plants is primitive and obsolete. This results in low yield and poor quality
of essential oils. Thus, there is great need for attaining adequate technological capabil-
ity in the area of processing essential oil plants. This article deals with the different
techniques of distillation, the principles of distillation, and important processing and
design aspects which affect the yield and quality of the essential oils.

7.1 Introduction

Distillation is the most popular, widely used and cost-effective

method for producing essential oils throughout the world.

Distillation of aromatic plants simply implies vaporizing or lib-

erating the oils from the plant cellular membranes in the presence of mois-
ture, by applying high temperature and then cooling the vapor mixture to
separate the oil from the water on the basis of the immiscibility and density
of the essential oil with respect to water.

7.2 Principles of Distillation

The choice of a particular process for the extraction of essen-

tial oil is generally dictated by the following considerations:
a) Sensitivity of the essential oil to the action of heat and water
b) Volatility of the essential oil
c) Water solubility of the essential oil

Essential oils with high solubility in water and those that are sus-
ceptible to damage by heat cannot be steam distilled. Also, the oil must be
steam volatile for steam distillation to be feasible. Most of the essential oils
in commerce are steam volatile, reasonably stable to heat and practically in-
soluble in water; hence they are suitable for processing by steam distillation.

Essential oils are a mixture of various aroma chemicals, basi-

cally monoterpenes, sesquiterpenes and their oxygenated derivatives, hav-
ing a boiling point ranging from 150° to 300° C. When the plant material is
subjected to heat in the presence of moisture from the steam, these oils are
liberated from the plant. For the oil to change from the liquid to the vapor
phase, it must receive latent heat that, within the tank, can only come from
condensing steam. Consequently, the temperature of the steam within the

115
7 DISTILLATION TECHNOLOGY FOR ESSENTIAL OILS

still must be higher than the temperature at which the oil boils in the pres-
ence of water on the surface of the plant material, otherwise there would
not be a temperature gradient to take the latent heat from the condensing
steam to vaporize the oil droplet. Thus, the energy from the steam in form
of heat as latent heat of vaporization converts the oil into a vapor. But, as
the boiling point of the oil is higher than that of water, the vaporization takes
place with steam on the basis of their relative vapor pressures.

It is imperative to note that a liquid always boils at the tem-

perature at which its vapor pressure equals the atmospheric or surround-
ing pressure. For any two immiscible liquids, the total vapor pressure of
the mixture is always equal to the sum of their partial pressures. The
composition of the mixture in the vapor phase (in this case, oil and water)
is determined by the concentration of the individual components multi-
plied by their respective partial pressures. For example, if a sample of
an essential oil comprised of component A (boiling point, 190° C) and
water (boiling point, 100° C) is boiled, after some time, once their vapors
reach saturation, the temperature will immediately drop to 99.5° C, which
is the temperature at which the sum of the two vapor pressures equals
760 mmHg. In other words, the oil forms an azeotropic mixture with water.
Thus, any essential oil having high boiling point can be evaporated with
steam in a ratio such that their combined vapor pressures equal the at-
mospheric pressure; the essential oil can be recovered from the plant by
the wet distillation process.

7.3 Methods for Distillation

The following four techniques for the distillation of essential

oils from aromatic plants are employed:
1. Water distillation (or hydrodistillation)
2. Water and steam distillation
3. Direct steam distillation
4. Distillation with cohobation

7.3.1 Hydrodistillation

Hydrodistillation is the simplest and oldest process available

for obtaining essential oils from plants. Hydrodistillation differs from steam
distillation mainly in that the plant material is almost entirely covered with
water in the still which is placed on a furnace. An important factor to consid-
er in water distillation is that the water present in the tank must always be
enough to last throughout the distillation process, otherwise the plant mate-
rial may overheat and char. In this method, water is made to boil and the
essential oil is carried over to condenser with the steam which is formed.
Water-distilled oil is slightly darker in color and has much stronger still notes
than oils produced by other methods. The stills based on this principle are

116
 EXTRACTION TECHNOLOGIES FOR MEDICINAL AND AROMATIC PLANTS

simple in design and are extensively used by small-scale producers of es-

sential oils. Care should be taken during distillation of powdered herbs, as
they tend to settle on the bottom of the still and get thermally degraded.
Also, for plant material that tends to form mucilage and increase the viscos-
ity of the water, the chances of charring are greater. For plant material that
has a tendency to agglomerate or to agglutinate into an impenetrable mass
when steam is passed through (like rose petals), water distillation is the
preferred method of oil isolation.

The primitive, traditional Indian system of essential oil distilla-

tion, bhapka method, is also based on water distillation (Figure 1). In this
process, the plant material is entirely covered with water in a distillation still,
which is made of copper and is known as deg. This deg is placed in a brick
furnace. Another copper vessel with a long neck is placed in a water tank or
natural pond to serve as a condenser. A bamboo pipe is used as the vapor
connection and mud is used to seal the various joints. The water is boiled,
the oil vapors along with steam are condensed in the copper vessel, and oil
is separated. The capacity of one deg is around 40 kg/batch. These types of
units are still being used in Kannauj in Uttar Pradesh and in the Ganjam dis-
trict of Orissa, India for the preparation of rooh and attars of gulab, kewda,
khus, rajnigandha, and bela. These units can easily be transported from one
place to another, but are not suitable for large-scale distillation of aromatic
crops like grasses and mints.

Figure 1: Traditional Indian deg bhapka method

Although hydrodistillation (water distillation) is still being used,

the process suffers from the following serious drawbacks:

117
7 DISTILLATION TECHNOLOGY FOR ESSENTIAL OILS

a) As the plant material near the bottom of the still comes in

direct contact with the fire from the furnace, it may char and
thus impart an objectionable odor to the essential oil.
b) The prolonged action of hot water can cause hydrolysis of
some constituents of the essential oil, such as esters.
c) Heat control is difficult, which may lead to variable rates of
distillation.
d) The process is slow and distillation times are much longer
than those of steam distillation.

7.3.2 Water and Steam Distillation

To eliminate some of the drawbacks of water distillation, some

modifications were made to the distillation units. A perforated grid was intro-
duced in the still, to support the plant material and to avoid its direct contact
with the hot furnace bottom. When the water level is kept below the grid, the
essential oil is distilled by the rising steam from the boiling water. This mode
of distillation is generally termed water and steam distillation.

The field distillation unit (FDU), also known as a directly fired-

type distillation unit, is designed according to the principle of water and
steam distillation. The FDU consists of a still or tank made of mild stainless
steel with a perforated grid and is fitted directly to a brick furnace. A chimney
is connected to the furnace to minimize the pollution at the workplace and
also to induce proper firing and draft. The plant material is loaded on the
perforated grid of the tank and water is filled below it. The tank is connected
to the condenser through a vapor line. The water is boiled and the steam
vapors pass through the herb, vaporize the oil and get condensed, mostly in
a coil condenser by cooling water. The condensate (oil-vapor mixture) is then
separated in the oil separator.

These units are simple to fabricate and can be installed in the

farmer’s field. Due to their simple construction, low cost and easy opera-
tion, FDUs are extremely popular with essential oil producers in developing
countries. The furnace is always fueled by locally available firewood or straw.
This makes the unit suited for use in remote areas where the raw material
is available. This also helps in reducing transportation costs in the produc-
tion of essential oils. FDUs are currently finding application in distillation of
patchouli oil in Indonesia, aromatic grass and mint oil in India, citronella oil
in Taiwan and many more all over the world. A local FDU currently being used
by rural farmers in India for the distillation of mint oils is shown in Figure 2.
Such field units generally can hold 100-2000 kg plant material. Total time
for distillation with these units is about 6-8 h.

118
 EXTRACTION TECHNOLOGIES FOR MEDICINAL AND AROMATIC PLANTS

Figure 2: Local type field distillation unit in India

[Link] Improved Field Distillation Units

Due to the limited heating surface available, the rate of steam

production in the FDU is always insufficient. This results in prolonged distil-
lation periods and sometimes lower oil yields. Refluxing of oil back into the
still due to inadequate steam rate may lead to decomposition reactions and
poorer oil quality. Experimental measurements made at the Central Institute
of Medicinal and Aromatic Plants (CIMAP), India, have shown that firewood
consumption in a conventional field still may be up to 2.5-times greater than
that of a modern steam distillation unit operated by an external boiler. This
factor may not be critical where fuel supplies are cheap and abundant but, in
many developing countries, fuel supplies are getting scarce and costly and
low thermal efficiency can directly affect the cost of production.

Figure 3: CIMAP’s improved field distillation unit

119
7 DISTILLATION TECHNOLOGY FOR ESSENTIAL OILS

Considering the previously mentioned demerits of FDUs, de-

signs of economical and improved units with capacities 500-2000 kg per
batch are now being preferred (Figure 3). The units are fabricated with high
quality mild stainless steel, keeping in view the plant materials to be dis-
tilled. The improved distillation unit consists of a cylindrical distillation tank
fitted on a square inbuilt boiler (calandria) having smoke pipes which reduc-
es the heating time of the water, resulting in a high rate of steam generation
and lower fuel consumption (20%-30%). Hot flue gasses of the furnace are
led through the smoke tubes where they impart heat to the water, thus rais-
ing additional steam. The tank is fitted on a specially designed furnace hav-
ing fire grate, flue ducts and fire door for proper controlling of the firing and
draft. The furnace is connected to a chimney of optimum height to maximize
the air draft and control the pollution by smoke in the workplace. A similarly
designed stainless steel shell and tube-type condenser having higher con-
densation capacity are used for cooling the vapors. It prevents loss of oil
due to improper condensation. The condensed oil-water mixture is then al-
lowed to pass through a specially designed stainless steel oil separator. The
separator has an inbuilt baffle to maximize the retention time of the mixture,
thereby resulting in no loss of oil with the outgoing water from the separator.
The unit also has a chain pulley hoist system with a support structure that
makes work easier and saves time during discharge of the distillation waste
material from the tank. CIMAP has designed, fabricated and supplied these
improved units to entrepreneurs and farmers in different parts of India.

7.3.3 Direct Steam Distillation

In direct steam distillation, plant material is distilled with steam

generated outside the tank in a steam generator or boiler. As in water and
steam distillation, the plant material is supported on a perforated grid above
the steam inlet. As already noted, the steam in an FDU is at atmospheric
pressure and hence its maximum temperature is 100° C. But, steam in a
modern pressure boiler operating at, for example, 50 psi pressure will have
a temperature correspondingly higher. Moreover, there is no limitation to the
steam generation when an external boiler is used as a source of steam. The
use of high-pressure steam in modern steam distillation units permits much
more rapid and complete distillation of essential oils.

Steam distillation is preferred when a lot of area is under cultiva-

tion and more than one unit is to be installed. Also, for distillation of high boiling
oils and hardy materials such as roots and woods like sandalwood, cedar wood
and nagarmotha, steam distillation is more efficient. Steam distillation also
reduces the time required for the extraction of oils. A charge of Java citronella,
which takes up to 5 h in an FDU, is processed within two to 3 h in a steam
distillation still. In this method of distillation, steam is generated separately in
a steam boiler and is passed through the distillation tank through a steam coil
(Figure 4). The plant material is tightly packed above the perforated grid. Steam,
containing the oil vapor, is condensed in a tube condenser and is separated in

120
 EXTRACTION TECHNOLOGIES FOR MEDICINAL AND AROMATIC PLANTS

the oil receiver. Fuel costs are generally lower in modern steam distillation units
due to higher thermal efficiency at which most of the boilers operate. Capital
cost is higher, thus only bigger producers can afford to own such units. Still
capacities range from 1 to 3 tonne plant material per batch.

Figure 4: Boiler-operated steam distillation unit

[Link] Comparison of Boiler-operated Unit with Directly

Fired Type

a) It is possible to run a large number of distillation units by a

single steam boiler. Hence a boiler system is ideal for large-
scale production of essential oils. An FDU is more suited for
small and medium-sized farmers.
b) The efficiency of extraction of essential oil in a well-designed
FDU can equal that obtained by a boiler unit. But in a poorly
designed FDU, oil recovery may be low and fuel wastage may
be heavy accompanied by smoke pollution.
c) Steam injection rate in a boiler-operated unit can be adjust-
ed with ease but steam generation rate in an FDU is limited
by the heat transfer area provided in the unit. Insufficient
steam generation in an FDU can result in low oil yield.
d) Boiler-operated units require a skilled boiler man for oper-
ation but an FDU can be operated by relatively low-skilled
workers.

7.3.4 Distillation with Cohobation

Cohobation is a technique that can be used for water distillation

or for water and steam distillation. It uses the process of returning the distil-
late water to the still after the oil has been separated from it so that it can be
re-boiled. This is basically an improvised methodology of the directly fired type

121
7 DISTILLATION TECHNOLOGY FOR ESSENTIAL OILS

steam and water distillation units for oils which have partial solubility in water.
Although most of the essential oils have finite solubility in water, some oils
like those of rose, lavender and geranium have comparatively higher solubility.
In such extractions, the loss of oil with the outgoing water of distillation can
become alarmingly high. This problem can be solved by returning the conden-
sate water from the separator back to the still; this is known as cohobation. It
is evident that this cannot be done with steam distillation as the water level in
the still will keep building up due to continuous steam injection.

In a further improved version, a packed column is placed on top

of the column for providing mass transfer to the oil-water vapors, so as to
increase the concentration of the outgoing condensate and to coalesce the
oil droplets in the oil separator (Figure 5). The condenser is placed above the
column so that the condensate water from the separator can be recycled back
to the still by means of gravity. Additional heat, if required, can be provided by
a closed steam coil immersed in the tank bottom. The condenser is moved
above the distillation still so that condensed water from the separator can flow
by means of gravity to the still. By limiting the total quantity of water in this
closed cycle operation, it is possible to obtain increased yields of essential
oils that are more water soluble. It is relevant to point out here that prolonged
recirculation of the distillation water allows the various impurities and plant
decomposition products to build up in the system. This may sometimes affect
the quality of the oil. One must always keep this in mind when considering a
cohobation distillation system for any application.

Figure 5: Distillation unit with cohobation

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 EXTRACTION TECHNOLOGIES FOR MEDICINAL AND AROMATIC PLANTS

7.4 Hydrodiffusion

This system was first described in 1983. Unlike traditional

steam distillation, hydrodiffusion works on the diffusion principle of allowing
steam to enter the top of the plant charge and diffuse through the charge
by gravity. The process uses the principle of osmotic pressure to diffuse oil
from the oil glands. The system is connected to a steam source, and low
pressure steam is passed into the plant material from a boiler. The condens-
er, which is directly under the basket within the still, is of the tube type. The
oil and water are collected below the condenser in a typical oil separator.
Hydrodiffusion is an efficient process that is easy to use, especially regard-
ing the processes of loading and unloading the plant material. The yield of
oil is higher and the process is advantageous because of the reduced steam
consumption, shorter distillation time and absence of hydrolysis, as the raw
material does not come in contact with boiling water. However, because of
the downward flow of steam and condensate, co-extraction of other non-
volatile compounds (such as lipids, chlorophyll and fatty acids) and polar
components makes the process complicated. Although it may seem that
hydrodiffusion is a better alternative to conventional distillation processes,
the fact remains that commercial ventures based on hydrodiffusion have not
been able to take off successfully.

7.5 Parameters Affecting Yield and Quality

of Essential Oils

The yield and quality of essential oil from steam distillation is

affected by the various process parameters. It is advisable to keep them in
mind while designing such systems. Some of the important parameters are
being listed below.

7.5.1 Mode of Distillation

The technique for distillation should be chosen considering the

boiling point of the essential oil and the nature of the herb, as the heat
content and temperature of steam can alter the distillation characteristics.
For high boiling oils such as woody oils (e.g. sandalwood, cedar wood) and
roots (e.g. Cyperus), the oil should be extracted using boiler-operated steam
distillation. Since the heat content and temperature of steam depend upon
its pressure, a change in steam pressure can alter the distillation charac-
teristics. High-boiling constituents of essential oils normally require high-
pressure steam to distill over. For oil of rose and other florals, the material
is generally immersed in water, i.e. hydrodistillation, as flowers tend to ag-
gregate and form lumps which cannot be distilled using water and steam
distillation or direct steam distillation.

123
 EXTRACTION TECHNOLOGIES FOR MEDICINAL AND AROMATIC PLANTS

10 Supercritical Fluid Extraction of

Medicinal and Aromatic Plants:
Fundamentals and Applications
A. Bertucco and G. Franceschin

Abstract
The main issues related to supercritical fluid extraction of medicinal and aromatic
plants are discussed in view of the development of this separation technique at indus-
trial scale. After an introduction to supercritical fluid extraction, the roles of thermo-
dynamics and mass transfer properties are emphasized, and the effects of the main
operating variables on product recovery are briefly examined. Fundamental concepts
about the equipment needed and basic technology are presented, including economi-
cal evaluation. Finally, a short literature survey of successful supercritical extraction
processes of medicinal and aromatic plants is reported and a future outlook is given.

10.1 Introduction

In the second half of last century, an increasing interest has

been paid to supercritical fluids as alternate solvents for the extraction of
natural bioactive molecules from plants. The main reason for the interest
in supercritical fluid extraction (SFE) was the possibility of carrying out ex-
tractions at temperature near to ambient, thus preventing the substance of
interest from incurring in thermal denaturation.

A thorough review of the results achieved up to the early 1980s

is presented in a book by Stahl et al., published in 1986. Clearly, by that
time, the fundamentals of this new extraction process were already under-
stood, even though the technical-economical assessment and the design
criteria for large-scale application of SFE were still missing. After twenty
years of research and development, it is now possible to say that such
achievements are at hand, so SFE is currently a well-established unit opera-
tion for extraction and separation. Moreover, its design and operating crite-
ria are fully understood, so that it can profitably be applied in the extraction
of medicinal and aromatic plants (MAPs).

10.2 Supercritical Fluids

A fluid at supercritical condition, also referred to as a dense

gas, is a fluid above its critical temperature (TC) and critical pressure (PC) to
a certain extent: to be supercritical, the reduced temperature Tr (i.e. T/TC)
must not exceed 1.2 or 1.3, whereas the reduced pressure Pr (i.e. P/PC) may
be as high as allowed by technological limits.

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10 SUPERCRITICAL FLUID EXTRACTION OF MEDICINAL AND AROMATIC PLANTS: FUNDAMENTALS AND APPLICATIONS

At suitable conditions, any fluid can reach its supercritical

state. However, only those having a critical temperature not far from ambi-
ent temperature can be used as alternative solvents for the extraction of
MAPs. Carbon dioxide (CO2), with TC=31.06° C and PC=73.81 bar, is the
most attractive solvent, because of its proprieties regarding toxicity, flam-
mability and cost.

The possibility of using supercritical fluids (SFs) as extraction

solvents is directly linked to their density. In fact, according to an empirical
correlation proposed by Chrastil in 1982,

s = ρa exp ( bT + c) (1)

where s is the solute solubility, ρ is the solvent density and T is the absolute
temperature; a, b and c are correlation parameters to be adjusted to experi-
mental solubility data in supercritical CO2.

When a fluid approaches the critical conditions, its density gets

closer and closer to that of the liquid state. This can be seen, for CO2, in
Figure 1, where density isotherms are plotted against the reduced pressure.
For example, at T = 35° C and P = 200 bar, ρ = 866 kg/m3.

It is also clear from Figure 1 that, close to the critical point,

both the compressibility and expansion coefficient of the fluid are high, so
slight changes in the operating conditions can significantly modify the den-
sity, i.e. the supercritical fluid solvent power. The importance of the Chrastil
equation (Eq. 1) lies in the fact that solvent density is identified as the key
factor in a successful SFE process.

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Figure 1: Density vs. pressure diagram for carbon dioxide

When plotted against solvent density, solubility data for super-

critical CO2 always display a regular trend such as that in Figure 2a, whereas
a more complex behavior is seen when pressure is improperly used as the
independent process variable (Figure 2b).

170
 EXTRACTION TECHNOLOGIES FOR MEDICINAL AND AROMATIC PLANTS


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Figure 2: Solubility of 1,4-bis-(n-propylamino)-9,10-anthraquinone in supercritical CO2: as a

function of solvent density (2a) and of pressure (2b)

Coming back to Eq. 1, is important to point out that it is not theo-

retically correct and must be applied within restricted temperature ranges only.

More importantly, the exponential form of Eq. 1 does not guar-

antee that the solubility of a solute in SF is high. The solubility depends on
parameters a, b and c; in fact, in the case of CO2, the solubility of a solute
of interest for MAP applications is at best in the range of 1 to 1000 by
weight or often 1 to 10,000 (Figure 2a illustrates this). This is because CO2
is a poor solvent, even at supercritical conditions. In addition, this holds
for non-polar substances only, as supercritical CO2 does not dissolve polar
molecules at all. Actually, CO2 is a good solvent only for low molecular weight
solutes.

The limit on solubility is dictated by thermodynamics. Accord-

ing to the iso-fugacity criterion applied to the substance to be extracted,
between the two phases at equilibrium (the condensed one – either solid or
liquid – and the supercritical one), we have:
Psat
yi = Ei (2)
P

ϕio, v P – Psat
Ei =
ϕiv
exp v S/L
RT ( ) (3)

where yi is the mole fraction of i in the supercritical phase, ϕio,v and ϕiv are
the fugacity coefficients of i in the standard state and in the mixture, respec-
tively, at the process conditions, Psat is the solute saturation (or sublimation)
partial pressure (i.e. the component volatility), and vS/L is the molar volume
of the condensed phase (either solid or liquid). T is the absolute tempera-
ture and R is the universal gas constant. Ei is the so-called enhancement
factor, which accounts for the increasing solubility due to system nonideali-
ties with respect of the ideal behavior (given by Eq. 2).

171
10 SUPERCRITICAL FLUID EXTRACTION OF MEDICINAL AND AROMATIC PLANTS: FUNDAMENTALS AND APPLICATIONS

According to Eq. 2, the solubility of i in the SF can be calculated

at the process condition, provided that the fugacity coefficients ϕi can be
evaluated accurately by means of an equation of state. However, the sub-
stance vapor pressure directly influences the solubility when Psat is as usual
for MAPs, very low. Only an equally low value of the fugacity coefficient, i.e.
a high system nonideality, can partially counteract the lack of volatility of the
pure component.

Regardless of the way its value has been obtained, i.e. from
Eq. 1 or Eqs. 2-3, the solubility is only one of two fundamental pieces of
information that must be known in order to assess the feasibility of an SFE
process for MAPs. The second one is selectivity, which is defined as the ra-
tio of the solubility of the substance i of interest with respect to a reference
substance j:
si
αij = (4)
sj
If on one hand high solubility is desirable, to reduce the solvent
consumption per unit product extracted, on the other hand selectivity must
be as far as possible from 1, to ensure that the substance of interest is ex-
tracted as pure rather than in mixture with other components. In summary,
to develop a successful SFE process for MAPs, both solubility and selectivity
issues must be fulfilled properly.

Coming back to CO2, it must be kept in mind that this solvent

is rather non-selective: when it is able to dissolve a group of similar sub-
stances (for example, in terms of carbon atoms), all of them are extracted
to a similar extent, provided they have similar polarities.

Therefore, it can be stated that CO2 alone is not as selective as

a good and pure solvent. It is also noteworthy that CO2 capacity and selectiv-
ity may be improved by using an organic solvent as the entrainer, also called
the co-solvent, with the function of modifying chemical interactions between
CO2 and the substance to be dissolved in it.

But by doing this, the SFE process becomes more complicated,

as an extra chemical component needs to be introduced into the process.
However, the co-solvent can be easily separated from the product down-
stream, due to the high selectivity displayed by supercritical CO2 in this
respect.

10.3 SFE Processes

An SFE process for extracting MAPs is basically composed of two

main sections (Figure 3a). The feed, containing the substance of interest, in-
dicated by A, comes in contact with supercritical CO2, at suitable temperature

172
 EXTRACTION TECHNOLOGIES FOR MEDICINAL AND AROMATIC PLANTS

and pressure, in an extraction device. In this simple scheme, component A is

selectively extracted and must be recovered from the supercritical solution,
which is usually a dilute one for the reason explained in the previous section.
Product recovery occurs in the separation section, whose temperature and
pressure can be adjusted in order to optimize the amount of A produced.

Note that, due to the low solubility in supercritical CO2, after

recovery of the product of interest the solvent must be recycled and pumped
back to the extractor, in order to minimize operating costs. It is also note-
worthy that the separator can be operated either at the same temperature
or at the same pressure of the extractor, the best condition resulting from
an economical analysis of the overall production costs.

If the temperature is kept constant, product separation is

achieved by depressurization (Figure 3a), and mechanical energy has to be
provided to the system to raise the CO2 pressure from the separator to the
extractor conditions. On the other hand, extracted products can be sepa-
rated from CO2 by increasing the temperature, and thermal energy must be
supplied in this case (Figure 3b), where the circulation of the solvent can
be done at nearly isobaric conditions. Of course, the way the separation
of products from CO2 is achieved can be more complex: for instance, both
temperature and pressure can be varied when passing from the extractor
to the separator sectors, or a solid can be used to promote separation by
adsorption.

Figure 3: Block flow diagrams of simple SFE processes: with separation obtained by
pressure change (a) and by temperature change (b)

If, as it often occurs, many substances are extracted by CO2 at

the extraction conditions because of lower CO2 selectivity, their fractionation
can also be achieved in the separation section, by simply using more than one
separator, operated at different conditions. As shown in Figure 4, multiple frac-
tions with different properties can be recovered from the same extraction.

173
10 SUPERCRITICAL FLUID EXTRACTION OF MEDICINAL AND AROMATIC PLANTS: FUNDAMENTALS AND APPLICATIONS

extractor separator

fraction 1 fraction 2 fraction 3

Figure 4: Single extractor, multiple separator scheme

Finally, a multiple extractor scheme can also be envisaged, as

represented in Figure 5 with only one separation step, for sake of clarity. This
configuration is particularly useful when, as in the case of SFE of MAPs, the sub-
stances to be extracted are embedded in a solid matrix, which is initially loaded
in the extraction vessel as a fixed bed. In this case, the extractors can be con-
nected either in parallel or in series, depending on specific requirements.

More details on the development of SFE processes are pro-

vided in a book by Brunner listed in the bibliography. SFE of solids is a
semibatch operation, which can also be operated in a simulated moving bed
configuration to obtain a continuous production.

1 2 3 4

extract

Figure 5: Multiple extractor, single separator scheme

Typical extraction profiles from solid materials (single vessel)

are shown in Figure 6 where the extractor yield, i.e. the amount of substance
of interest extracted with respect to the total amount initially contained in
the solid, is plotted against extraction time. The profiles, which are steeper
if the temperature is higher, have two parts: a straight line corresponding
to the extraction of the substance “readily available” to supercritical CO2,
and an asymptotic curve representing the extraction of the part attached to
the solid matrix. In the first case, the extraction is limited by solubility; in
the second, mass transport (diffusion) properties are important and can be
limiting and crucial for the success of SFE.

174
 EXTRACTION TECHNOLOGIES FOR MEDICINAL AND AROMATIC PLANTS

The effects of operating temperature are also clear in Figure 6.

Other important operating variables are pressure, CO2 flow rate and humidity
of the material to be extracted.


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Figure 6: Extraction yield versus time at different temperatures

10.4 The SFE Process and Equipment

Development

In order to design and develop an SFE process for MAPs with

CO2 (possibly assisted by ethanol or water as entrainers), we need to know
and optimize:

1. The solubility of the substance of interest

2. The selectivity of this substance with respect to others that
are extracted simultaneously
3. The extraction profiles (such as those in Figure 6)
4. The way to separate the substance of interest from the total
extract

All this information can be obtained by simple measurements

performed in a laboratory-scale apparatus of minimum volume such as that
illustrated in Figure 7.

Figure 7: Laboratory-scale apparatus for SFE process design

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10 SUPERCRITICAL FLUID EXTRACTION OF MEDICINAL AND AROMATIC PLANTS: FUNDAMENTALS AND APPLICATIONS

To measure extraction profiles, a small pilot-scale apparatus can

be used. Extractor and separator volumes do not need to exceed 1 liter each.
The analytical system must be suitable to measure the concentration and purity
of the products of interest. Basic requirements in terms of equipment are:
1. A liquid CO2 storage tank
2. A pump for liquid CO2
3. A cooler to prevent CO2 from evaporating in the pump
4. A heat exchanger to control the temperature of CO2 entering
the extractor
5. An extraction vessel
6. A heat exchanger to control the CO2 plus solute mixture en-
tering the separator
7. A separation vessel

Note that condensing and recycling of CO2 after separation is

not needed at the laboratory-scale developmental level, whereas these are
essential requirements at the industrial production level.

All parts of the SFE laboratory-scale plant must be designed

in order to resist the maximum operating pressure. If this does not exceed
300-350 bar, the entire equipment (e.g. vessels, valves, fittings) is pretty
much of standard type and relatively inexpensive. If, as usual, stainless
steel is used, the thickness of any part of the plant can be easily calculated
by applying the Von-Mises equation:
k2
Pi 2 √
⎯3 < σam (5)
k –1
with:
σs
σam = (6)
Sf
where Pi is the internal pressure, k is the external to internal diameter ratio,
σs is the yield stress, and Sf is a suitable safety factor (usually Sf=1.5).

From Eq. 5, it can be seen that the thickness of a cylindrical

vessel depends on its diameter. Examples are given in Table 1 for a vessel
of 0.2 m internal diameter, with both stainless steel and carbon steel con-
struction materials.

Table 1: Thickness (s) of a thick-wall cylindrical vessel of 200 mm internal diameter

as a function of pressure (SS=stainless steel, CS=carbon steel)

P [atm] 50 100 150 200 250 300

SS 3.8 8.1 12.9 18.5 25.0 32.7
s [mm]
CS 2.2 4.6 7.2 10.0 13.0 16.2

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 EXTRACTION TECHNOLOGIES FOR MEDICINAL AND AROMATIC PLANTS

Special care must be paid to closures and seals. SFE of MAPs

is mostly an extraction operation from solid materials, which is carried out in
batch or semibatch mode. Therefore, extraction vessels need to be pressu-
rized, depressurized, opened, filled, and closed again several times per day.
In order to ensure fast and safe operation procedures and reliable seals,
gaskets like O-rings are useful and closure devices have been specifically
designed. Again, the technology needed is already fully developed. We refer
to chapter 4 of the book by Bertucco and Vetter for details. The book also
describes the machinery for moving fluids under pressure, i.e. pumps and
compressors. We conclude that setting up a laboratory-scale apparatus with
which to perform feasibility studies concerning the possibility of applying
SFE to MAPs is not really an issue, and can be done with a relatively small
capital cost.

However, this does not mean that SFE of MAPs is in itself an

economically convenient operation. An accurate evaluation of production
costs, including both capital and utility costs, must be performed before
scaling up a process whose technical feasibility has been demonstrated at
the laboratory level. Costs are also discussed in the book by Bertucco and
Vetter (chapter 8), but are only indicative. The reader should remember that
capital costs have been steadily decreasing in the last years must be taken
into account.

10.5 SFE Applied to Medicinal and Aromatic

Plants

A large number of MAPs has been considered for possible

extraction by supercritical CO2. The most recent developments suitable to
have industrial relevance are listed in Table 2. These examples illustrate the
great potential of SFE in this field.

Table 2: Medicinal and aromatic plants extracted by SFE

Plant name
Product(s) extracted Reference
(part used)
Calendula Oleoresin Campos et al., 2005, Experimental
officinalis data and modeling the supercritical
(flowers) fluid extraction of marigold (Calendula
officinalis) oleoresin, J Supercritical
Fluids, 34: 163-170
Danielski et al., 2007, Marigold
(Calendula officinalis L.) oleoresin:
solubility in SC-CO2 and composition
profile, Chem Eng Proc, 46: 99–106

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10 SUPERCRITICAL FLUID EXTRACTION OF MEDICINAL AND AROMATIC PLANTS: FUNDAMENTALS AND APPLICATIONS

Plant name
Product(s) extracted Reference
(part used)
Echinacea Alkamides, polyphenolics Catchpole et al., 2002, Supercritical
purpurea including chichoric acid, extraction of herbs I: saw palmetto,
(whole herb) carbohydrates St John's wort, kava root, and
Echinacea, J Supercritical Fluids, 22:
129-138
Eucalyptus spp. Essential oil Della Porta, et al., 1999, Isolation
(leaves) of eucalyptus oil by supercritical
fluid extraction, Flavour Fragr J, 14:
214–218
Ginkgo biloba Flavonol glycosides Chun Yang et al., 2002, Extraction
(leaves) (flavonoids) and of pharmaceutical components
terpenoids from Ginkgo biloba leaves using
supercritical carbon dioxide, J Agric
Food Chem, 50: 846-849
Hypericum Naphthodianthones, Catchpole et al., 2002
perforatum hypericin and
(herb) pseudohypericin
Levisticum Essential oil Daukšas et al., 1999, Supercritical CO2
officinale extraction of the main constituents
(dry rhyzomes, of lovage (Levisticum officinale Koch.)
roots) essential oil in model systems and
overground botanical parts of the
plant, J Supercritical Fluids, 15: 51–62
Matricaria Oleoresin Kotnik et al., 2007, Supercritical
chamomilla fluid extraction of chamomile flower
(flowers) heads: comparison with conventional
extraction, kinetics and scale-up,
J Supercritical Fluids, Available online
13 February 2007 (in print)
Mentha spp. Essential oil Marongiu et al., 2001, Extraction
(leaves) and isolation of Salvia desoleana
and Mentha spicata subsp. insularis
essential oils by supercritical CO2,
Flavour Fragr J, 16: 384–388
Origanum spp. Essential oil Leeke et al., 2002, Eng Chem Res,
(herb) 41: 2033–2039
Piper Kava lactones Catchpole et al., 2002
methysticum
(roots,
rhizomes)
Piper nigrum Oleoresin Ferreira et al., 1999, Supercritical
(fruit) fluid extraction of black pepper (Piper
nigrum L.) essential oil, J Supercritical
Fluids, 14: 235–245.

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 EXTRACTION TECHNOLOGIES FOR MEDICINAL AND AROMATIC PLANTS

Plant name
Product(s) extracted Reference
(part used)
Saccharum spp. Long chain n-alcohols De Lucas et al., 2005, Supercritical
(crude wax) extraction of long chain n-alcohols
from sugar cane crude wax,
J Supercritical Fluids, 34: 163-170
Salvia desoleana Essential oil Marongiu et al., 2001
(leaves)
Serenoa repens Free fatty acids, Catchpole et al., 2002
(fruit) phytosterols (low
concentrations), fatty
alcohols and triglycerides
Solanum Carotenoids, tocopherols Vagi et al., 2007, Supercritical carbon
lycopersicum and sitosterols dioxide extraction of carotenoids,
(fruit) tocopherols and sitosterols from
industrial tomato by-products,
J Supercritical Fluids, 40: 218–226
Taxus brevifolia Taxol Jennings et al., 1992, Supercritical
(bark) extraction of taxol from the bark of
Taxus, J Supercritical Fluids, 5: 1-6
Taxus cuspidate Paclitaxel and baccatin III Moon-Kyoon Chun et al., 1996,
(needles) Supercritical fluid extraction of
paclitaxel and baccatin III from
needles of Taxus cuspidate,
J Supercritical Fluids, 9: 192-198
Vitis vinifera Procyanidins Cao et al., 2003, Supercritical fluid
(seeds) extraction of grape seed oil and
subsequent separation of free fatty
acids by high-speed counter-current
chromatography, J Chromatogr A
1021: 117–124
Zingiber Oleoresin Badalyan et al., 1998, Extraction of
officinale Australian ginger root with carbon
(rhizome) dioxide and ethanol entrainer,
J Supercritical Fluids, 13: 319-324

10.6 Conclusions

SFE with CO2 is a technically and possibly economically valid

technique to extract bioactive components from MAPs. Organic solvent-free
products can be obtained and the low operating temperature makes it pos-
sible to preserve all their natural properties. The feasibility study on specific
products can be performed rather easily at laboratory scale. However, ac-
curate evaluation of production costs, including both capital and operating
ones, must be done in order to exploit SFE at the industrial level.

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