Valuable plant products

Dried herbs (blends)

Essential oils
Extracts (aqueous, organic solvents)
Isolated bioactive constituents
Parameters affecting the quality

Seasonal variation
Geographic variation
Post harvesting drying and storage of plant tissues
Method of processing
Pre-extraction preparation of plant samples

•Fresh
•Dry
•Grinded or
•Powdered
 EXTRACTION OF NATURAL PERFUME INGREDIENTS

Both old and new methods fall into five basic classes:

1. Enfleurage
2. Expression
3. Distillation
4. Solvent extraction
5. Modern Methods
 1. ENFLEURAGE
Essential Oil Extraction with Cold Fat (Enfleurage)
The principles of enfleurage are simple. Certain flowers (e.g. tuberose and
jasmine) continue the physiological activities of developing and giving off
perfume even after picking.
Every jasmine and tuberose flower resembles, a tiny factory continually
emitting minute quantities of perfume. Fat possesses a high power of
absorption and, when brought in contact with fragrant flowers, readily
absorbs the perfume emitted.

This principle, methodically applied on a large scale, constitutes enfleurage.

During the entire period of harvest, which lasts for eight to ten weeks,
batches of freshly picked flowers are strewn over the surface of a specially
prepared fat base (corps), let there (for 24 h in the case of jasmine and longer
in the case of tuberose), and then replaced by fresh flowers. At the end of the
harvest, the fat, which is not renewed during the process, is saturated with
flower oil. Thereafter, the oil is extracted from the fat with alcohol and then
isolated.
Enfleurage and Defleurage
Every enfleurage building is equipped with thousands of so called chassis,
which serve as vehicles for holding the fat corps during the process. A
chassis consists of a rectangular wooden frame. The frame holds a glass
plate upon both sides of which the fat corps is applied with a spatula at
the beginning of the enfleurage process. When piled one above the other,
the chassis form airtight compartments, with a layer of fat on the upper
and lower side of each glass plate.
Every morning during the harvest the freshly picked flowers arrive, and
after being cleaned of impurities, such as leaves and stalks, are strewn by
hand on top of the fat layer of each glass plate. Blossoms wet from dew or
rain must never be employed, as any trace of moisture will turn the corps
rancid. The chassis are then piled up and left in the cellars for 24 h or
longer, depending upon the type of flowers. The latter rest in direct
contact with one fat layer (the lower one), which acts as a direct solvent
whereas the other fat layer (beneath the glass plate of the
chassis above) absorbs only the volatile perfume given off by the flowers.
Quality & quantity depends on

•Type of fat
soft or hard
(Tallow, Lard)
•Preparation of plant material
 2. EXPRESSION
Cold Pressing

odorants are forced out of the natural source by physical pressure

fragrant oils obtained using this method is the peels of fruits in the citrus family.
This is due to the large quantity of oil present in the peels of these fruits

oil glands in the peel are crushed or broken to release the oil.
 EXPRESSION contd.
elatrice Process

Citrus fruits are fed from a hopper into the abrasive shell
The fruits are rotated against the abrasive shell by a slow-moving
screw whose surface rasps the fruit surfaces causing some of the
essential oil cavities on the peel to burst and release their
oil-water emulsion.
This screw further transports the fruit into a hopper in which
rollers covered with abrasive spikes burst the remaining oil cavities.
The oil and water emulsion is washed away from the fruit by a
fine spray of water.
The emulsion next passes through a separator where any solids are
removed, after which it passes through two centrifugal separators
working in series to yield the pure oil.
Sfumatrice Process

1. The sfumatrice equipment consists of a metallic chain that

is drawn by two horizontal ribbed rollers.
2. The peels are conveyed through these rollers during which
time they are pressed and bent to release their oil.
3. As in pelatrice, the oil is washed away from the sfumatrice
rollers by fine sprays of water. Again, the oil is initially
passed through a separator prior to being sent to two
centrifuges in series, so that purified oil can be produced.
 •Distillation

3. DISTILLATION
•common technique for obtaining aromatic compounds from plants
•The raw material (flowers, leaves, wood, bark, roots, seeds, or peel) is
heated and the fragrant compounds are re-collected through condensation of
the distilled vapor.
•Distilled products are known either as essential oils or ottos.

Types of Distillation used for Fragrance extraction:

Types of Distillation used for Fragrance extraction:
 
·Dry distillation
Dry distillation
·Hydro distillation
Hydro distillation
Water distillation
Water distillation
Water and steam distillation
Water and steam distillation
Direct steam distillation
Direct steam distillation
Dry distillation (rectification)

 Direct heating by flame

 Anhydrous pyrolysis which results in the formation of different

fragrant compounds, and thus different fragrant notes.

 This technique is reserved for oils of highest boiling point, Used for
Fossil Amber & Woods, Cade as burned and toasted odor is desired.
 •Hydro distillation

• Hydro distillation

Mechanism of Distillation
Hydrodistillation of plant material involves the following main physicochemical processes:

i) Hydro diffusion
ii) Hydrolysis
iii) Decomposition by heat
Hydro diffusion

Diffusion of essential oils and hot water through plant membranes is known
as Hydro diffusion.

When the plant material is soaked with water, exchange of vapors within the
tissue is based on their permeability while in swollen condition.

Membranes of plant cells are almost impermeable to volatile oils.

Therefore, in 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.
Unlike traditional steam distillation, hydro diffusion works off the
diffusion principle of allowing steam to enter the top of the plant
charge and diffuse its through the charge by gravity.

The process uses principle of osmotic pressure to diffuse oil from

the oil glands.

The system is connected and low pressure steam is passed into the
plant material from a boiler from the top.

The condenser, generally of tubular construction which is directly

under the basket within the still, is used for cooling. The oil and water are
collected below the condenser in a typical oil separator.

It would appear that hydro diffusion is an efficient process to use

as it gives good yield of the oil. But due to co extraction of other non volatiles
and polar components with the essential oils complicated the process
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

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.
Disadvantages of Water Distillation
1. Oil components like esters are sensitive to hydrolysis (since the pH
of water is often reduced during distillation, hydrolytic reactions are
facilitated)

RCO-OR' + H20 → RCO-OH + R'-OH

while others like acyclic monoterpene hydrocarbons and aldehydes

are susceptible to polymerization.
Disadvantages of Water Distillation (contd.)

2. Oxygenated components such as phenols have a tendency to dissolve in

the still water, so their complete removal by distillation is not possible.

3. 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.

4. Water distillation is a slower process than either “water and steam

distillation” or “direct steam distillation”.
Water and Steam Distillation

In water and steam distillation, the steam can be generated within the still, although
separated from the plant material.

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.

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, In fact, it is common that persons performing water distillation
eventually progress to water and steam distillation.
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 constantly re-vaporized, condensed and re-vaporized

again, any dissolved oxygenated 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 considerably hotter than 100° C, then the chances of degradation are
enhanced.
As a result, the practice of cohobation is not recommended unless the temperature
to which oxygenated constituents in the distillate are exposed is no higher than
100° C.
Direct Steam Distillation

Steam distillation 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.

Direct steam distillation is the process of distilling plant material with steam
generated outside the still in a satellite steam generator generally referred to as a
boiler. 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.
 Solvent Extraction
Maceration
In this process, the whole or coarsely powdered plant 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.

Soxhlet extraction
The process of transferring the partially soluble components of a solid to the liquid
phase using a Soxhlet extractor. The solid is placed in a filter paper thimble which
is then placed into the main chamber of the Soxhlet extractor. The solvent (heated
to reflux) travels into the main chamber and the partially soluble components are
slowly transferred to the solvent.

Percolation
Percolation is an extraction process that involves the slow descent of a solvent
through a powdered substance until it absorbs certain constituents and drips out
through the filtered bottom of the container. 
Conventional extractions

Problems

1. High temperatures
2. Solvent contamination, reduces product quality
3. Inflammability or explosion risks
4. Time, solvent & energy consuming
5. Composition varies with solvent & extraction technique
Modern (Non-traditional) Methods of Extraction of Essential Oils
Traditional methods of extraction are the methods most widely used
on commercial scale.
However, with technological advancement, new techniques have been
developed which may not necessarily be widely used for commercial
production of essential oils but are considered valuable in certain
situations, such as the production of costly essential oils in a natural
state without any alteration of their thermosensitive components or
the extraction of essential oils for micro-analysis.

These techniques are as follows:

• Supercritical Fluid Extraction (SFE)
• Microwave distillation
•Accelerated Solvent Extraction (ASE)
•Headspace trapping techniques
Supercritical fluid
A supercritical fluid is any substance at a temperature and pressure above its critical
point. The supercritical fluid state occurs when a fluid is above its critical temperature
(Tc) and critical pressure (Pc), when it is between the typical gas and liquid state.
Manipulating the temperature and pressure of the fluid can solubilize the material of
interest and selectively extract it.

It can diffuse through solids like a gas, and

dissolve materials like a liquid.
Additionally, close to the critical point, small changes in pressure or temperature
result in large changes in density, allowing many properties of a supercritical fluid to
be "fine-tuned".
At a certain temperature and pressure condition, liquid and vapour phases of a substance
become indistinguishable. Known as CRITICAL CONDITION
Substances above critical point- “SUPERCRITICAL FLUIDS” (SCF)
PROPERTIES OF SCF

• Physical and thermal properties of SCFs are in between pure liquid and gas, hence
can also be known as ‘Compressible liquids’ or ‘dense gases’

• Changes in properties are for a SCF are as follows:

– Liquid like densities (100-1000 times greater than gases)

– Diffusivities higher than liquids (10-3 and 10-4cm2/s)
– Good solvating power
– Reduction in surface tension
– Low viscosity (10-100 times less than liquid)
– Gas like compressibility properties

Therefore they posses high penetrating power

Carbon dioxide and water are the most commonly used supercritical fluids

1. Because it has a near ambient critical temperature (310C), thus biological materials
can be processed at temperatures around 350C.
2. The density of the supercritical CO2 at around 200 bar pressure is close to that of
hexane, and the solvation characteristics are also similar to hexane; thus, it acts as a
non-polar solvent.
3. Around the supercritical region, CO2 can dissolve at concentrations up to 1% mass.

4. The major advantage is that a small reduction in temperature, or a slightly larger

reduction in pressure, will result in almost the entire solute precipitating out as the
supercritical conditions are changed or made sub critical.

5. Supercritical fluids can produce a product with no solvent residues.

1. The sample is placed in an extraction vessel and pressurized with CO 2 to dissolve the
sample.
2. Transferred to a fraction collector, the contents are depressurized and the CO 2 loses its
solvating power causing the desired material to precipitate.
3. The condensed CO2 can be recycled.
SUPER CRITICAL FLUID EXTRACTION
Supercritical Fluid Extraction
Solvents of supercritical fluid extraction

The choice of the SFE solvent is similar to the regular extraction. Principle
considerations are the followings:

* Good solving property

* Inert to the product
* Easy separation from the product
* Cheap
* Low production cost because of economic reasons
Advantages

1. Dissolving power of the SCF is controlled by pressure and/or temperature

2. SCF is easily recoverable from the extract due to its volatility
3. Non-toxic solvents leave no harmful residue
4. High boiling components are extracted at relatively low temperatures
5. Separations not possible by more traditional processes can sometimes be effected
6. Thermally labile compounds can be extracted with minimal damage as low
temperatures can be employed by the extraction

Disadvantages

* Elevated pressure required

* Compression of solvent requires elaborate recycling measures to reduce energy costs
* High capital investment for equipment
Carbon dioxide is the most commonly used SCF, due primarily to its low critical
parameters (31.1°C, 73.8 bar), low cost and non-toxicity. However, several other
SCFs have been used in both commercial and development processes.

Fluid Critical Critical Pressure

Temperature (K) (bar)
Carbon dioxide >304.1 > 73.8
Ethane >305.4 >48.8
Ethylene >282.4 >50.4
Propane >369.8 >42.5
Propylene >364.9 >46.0
Trifluoromethane (Fluoroform) >299.3 >48.6

Chlorotrifluoromethane >302.0 >38.7

Trichlorofluoromethane >471.2 >44.1

Ammonia >405.5 >113.5
Water >647.3 >221.2
Cyclohexane >553.5 >40.7
n-Pentane >469.7 >33.7
Toluene >591.8 >41.0
 PRINCIPLE OF ASE
EXTRACTION AT VERY HIGH TEMPERATURE AND PRESSURE

•Organic solvents used in extractions boil at relatively low temperatures.

•The highest temperatures at which extractions take place in these techniques will be the
boiling point of the solvent.

•If sufficient pressure is exerted on the solvent during the extractions, solvent temperatures
above the boiling point can be used. This means that all of the advantages of working at
elevated temperature can be realized even with solvents of relatively low boiling points.

•Operating at elevated pressures also helps the extraction process to happen more quickly.

• Pumping solvent through a packed bed is easier at elevated pressures; pressurized solvent
is forced into the pores of the sample matrix.

•Hence, the combination of elevated temperatures and pressures allows extractions to

•occur rapidly and completely.
When extractions are achieved at elevated temperatures, several factors
contribute to improved speed, efficiency and reduced solvent use:
1) Solvent strength is higher
2) Diffusion rates are faster due to break of solute–matrix interactions
3) Solvent viscosity is decreased
4) Solute-matrix interactions (dipole attractions, van der Waals forces,
hydrogen bonding, etc.) are more easily disrupted allowing the analytes to
be removed from the matrix.
The net result means performing extractions at elevated temperatures uses
less time and with less solvent.
Accelerated Solvent Extraction (ASE) System.......
Automated extraction technique that uses liquid solvents and solvent
mixtures
Extracts solid or semisolid samples
Uses elevated temperature (40-200 °C) and pressure (1500 psi)
Elevated temperature and pressure accelerate the extraction process
Requires small quantities of solvent in short periods of time
■ ASE: 15 mL and 15 min for 10-g samples
■ Soxhlet: 8-48 h and 300-500 mL
■ Sonication: 1-2 hours and 200-500 mL
Supports a wide range of sample sizes (mg-100 g)
 Microwave-assisted Extraction (MAE)

Dried plants contain a minute microscopic trace of moisture which serves as

target for microwave heating.
• High temperature and pressure is generated inside the oven.
• High temperature causes dehydration of cellulose which accounts for its
reduction of mechanical strength.

In MAE, heating occurs in a targeted and selective manner with practically no

heat being lost to the environment as the heating occurs in a closed system.
This unique heating mechanism significantly reduces the extraction time
(usually less than 30min) as compared to Soxhlet.
 EXTRACTION PRINCIPLE
The MAE process is as follows:
– Microwave radiation
– Moisture get heated up
– Moisture evaporates
– Generation of tremendous pressure on cell wall
– Swelling of plant cell
– Rupture of the cell
– Leaching out of phyto-constituents

This phenomenon can be intensified if the plant matrix is impregnated

with solvents with higher heating efficiency under microwave.
 FACTORS AFFECTING MAE
Solvent:
Extraction time:
By increasing extraction time, quantity of analytes is increased but there is the
risk of degradation.
Microwave power:
The power must be correctly chosen to minimise the time needed for
extraction. However, increased power may cause solvent loss by evaporation.
Maximum power used ranges between 600W and 1000W for closed systems and
around 250Wfor open systems.
Matrix characteristics:
The plant particle size and the status in which it is presented for MAE can
affect the recoveries of compounds. The particle sizes of the extracted materials are
generally in the range of 100 micro m – 2mm.
Fine powders enhance extraction as they provide a larger surface area.
Temperature:
Temperature should be sufficient to ensure good solubility of compounds and a
good penetration of solvent in the plant matrix to enhance extraction yield.
However, it should not be too high enough to degrade the target compounds.