EXTRACTION METHODS OF NATURAL ESSENTIAL OILS
Essential oils are used in a wide variety of consumer goods such as detergents, soaps, toilet products, cosmetics, pharmaceuticals, perfumes, confectionery food products, soft drinks, distilled alcoholic beverages (hard drinks) and insecticides.
The world production and consumption of essential oils and perfumes are increasing very fast. Production technology is an essential element to improve the overall yield and quality of essential oil. The traditional technologies pertaining to essential oil processing are of great significance and are still being used in many parts of the globe. Water distillation, water and steam distillation, steam distillation, cohobation, maceration and enfleurage are the most traditional and commonly used methods. Maceration is adaptable when oil yield from distillation is poor. Distillation methods are good for powdered almonds, rose petals and rose blossoms, whereas solvent extraction is suitable for expensive, delicate and thermally unstable materials like jasmine, tuberose, and hyacinth. Water distillation is the most favored method of production of citronella oil from plant material. Sources of natural essential oil Essential oils are generally derived from one or more plant parts, such as flowers (e.g. rose, jasmine, carnation, clove, mimosa, rosemary, lavander), leaves (e.g. mint, Ocimum spp., lemongrass, jamrosa), leaves and stems (e.g. geranium, patchouli, petitgrain, verbena, cinnamon), bark (e.g. cinnamon, cassia, canella), wood (e.g. cedar, sandal, pine), roots (e.g. angelica, sassafras, vetiver, saussurea, valerian), seeds (e.g fennel, coriander, caraway, dill, nutmeg), fruits (bergamot, orange, lemon, juniper), rhizomes (e.g. ginger, calamus, curcuma, orris) and gums or oleoresin exudations (e.g. balsam of Peru, Myroxylonbalsamum, storax, myrrh, benzoin). Methods of Producing Essential Oils Regarding hydrodistillation, the essential oils industry has developed terminology to distinguish three types: water distillation; water and steam distillation; and direct steam distillation.
Originally introduced by Von Rechenberg, these terms have become established in the essential oil industry. All three methods are subject to the same theoretical considerations which deal with distillation of two-phase systems. The differences lie mainly in the methods of handling the material. Some volatile oils cannot be distilled without decomposition and thus are usually obtained by expression (lemon oil, orange oil) or by other mechanical means. In certain countries, the general method for obtaining citrus oil involves puncturing the oil glands by rolling the fruit over a trough lined with sharp projections that are long enough to penetrate the epidermis and pierce the oil glands located within outer portion of the peel (ecuelle method). A pressing action on the fruit removes the oil from the glands, and a fine spray of water washes the oil from the mashed peel while the juice is extracted through a central tube that cores the fruit. The resulting oil-water emulsion is separated by centrifugation. A variation of this process is to remove the peel from the fruit before the oil is extracted.
Often, the volatile oil content of fresh plant parts (flower petals) is so small that oil removal is not commercially feasible by the aforementioned methods. In such instances, an odorless, bland, fixed oil or fat is spread in a thin layer on glass plates. The flower petals are placed on the fat for a few hours; then repeatedly, the oil petals are removed, and a new layer of petals is introduced. After the fat has absorbed as much fragrance as possible, the oil may be removed by extraction with alcohol. This process, known as enfleurage, was formerly used extensively in the production of perfumes and pomades. In the perfume industry, most modern essential oil production is accomplished by extraction, using volatile solvents such as petroleum ether and hexane. The chief advantages of extraction over distillation is that uniform 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 absence of air. When wood or resin of members of the Pinaceae or Cupressaceae 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.
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. In steam and water distillation, the plant material cannot be in direct contact with the fi re 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 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.
Advantages of Water and Steam Distillation over Water Distillation
• Higher oil yield.
• Components of the volatile oil are less susceptible to hydrolysis 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 distillation, for example lemongrass is produced in Bhutan with a rural steam and water distillation system.
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 distillation 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.
Direct Steam Distillation –
As the name suggests, 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. 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 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 cedarwood, 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.
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.
Disadvantage of Direct Steam Distillation
• Much higher capital expenditure needed to establish this activity than for the other two processes.
Certain plant materials require maceration in warm water before they release their essential oils, as their volatile components are glycosidically bound. For example, leaves of wintergreen (Gaultheria procumbens) 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 similar examples include brown mustard (sinigrin), bitter almonds (amygdalin) and garlic (alliin).
Every enfleurage building is equipped with thousands of socalled 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.
After 24 hours, the flowers have emitted most of their oil and start to wither, developing an objectionable odor. They must then be removed from the corps, which process, despite all efforts to introduce labor-saving devices, is still done by hand. Careful removal of the flower (defleurage) is almost more important than charging the corps on the chassis with fresh flowers (enfleurage) and, therefore, the persons doing this work must be experienced and skilled. Most of the exhausted flowers will fall from the fat layer on the chassis glass plate when the chassis is struck lightly against the working table, but since it is necessary to remove every single flower and every particle of the flower, tweezers are used for this delicate operation. Immediately following defleurage, that is, every 24 h, the chassis are recharged with fresh flowers. For this purpose the chassis are turned over and the fat layer, which in the previous operation formed the top (ceiling) of the small chamber, is now directly charged with flowers. In the case of jasmine, the entire enfleurage process lasts about 70 days: daily the exhausted flowers are removed and the chassis are recharged with fresh ones. At the beginning of, and several times during, the harvest, the fat on the chassis is scratched over with metal combs and tiny furrows are drawn in order change and increase the surface of absorption. At the end of the harvest, the fat is relatively saturated with flower oil and possesses the typical fragrance. The perfumed fat must then be removed from the glass plates between the chassis. For this purpose, it is scraped off with a spatula and then carefully melted and bulked in closed containers. The final product is called pomade (pomade de jasmine, pomade de tuberous, pomade de violet, etc.). The most highly saturated pomade is pomade no. 36, because the corps on the chassis have been treated with fresh flowers 36 times during the whole process of enfleurage. At the beginning of the harvest, every chassis is charged with about 360 g fat corps on each side of the glass plate, in other words, with 720 g per chassis. Every kilogram of fat corps should be in contact with about 2.5 kg (preferably with 3.0 kg) of jasmine flowers for the entire period of enfleurage, which lasts from 8 to 10 weeks. The quantities differ somewhat for different flowers. At the end of enfleurage, the fat corps has lost about 10% of its weight because of the various manipulations.
Despite the introduction of the modern process of extraction with volatile solvents, the old fashioned method of enfleurage, as passed on from father to son and perfected in the course of generations, still plays an important role. Enfleurage on a large scale is today carried out only in the Grasse region of France, with the possible exception of isolated instances in India where the process has remained primitive. 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, so to speak, 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. The success of enfleurage depends to a great extent upon the quality of the fat base employed. Utmost care must be exercised when preparing the corps. It must be practically odorless and of proper consistency. If the corps is too hard, the blossoms will not have sufficient contact with the fat, curtailing its power of absorption and resulting in a subnormal yield of flower oil. On the other, if it is too soft, it will tend to engulf the flowers and the exhausted ones will adhere; when removed, the flowers will retain adhering fat, resulting in considerable shrinkage and loss of corps. The consistency of the corps must, therefore, be such that it offers a semihard surface from which the exhausted flowers can easily be removed. The process of enfleurage is carried out in cool cellars, and every manufacturer must prepare the corps according to the prevailing temperature in the cellars during the months of the flower harvest. Many years of experience have proved that a mixture of one part of highly purified tallow and two parts of lard is eminently suitable for enfleurage. This mixture assures a suitable consistency of the corps in conjunction with high power of absorption. The fat corps thus prepared is white, smooth, absolutely of uniform consistency, free of water and practically odorless. Some manufacturers also add small quantities of orange flower or rose water when preparing the corps. This seems to be done for the sake of convention. Such additions somewhat shade the odor of the finished product by imparting a slight orange blossom or rose note.
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, particularly 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 emulsion absorbed by the sponge was removed by squeezing it into the concolina or some other container. It is reported that oil produced this way contains more of the fruit odor character than oil produced by any other method. A second method known as equaling (or the scodella method), uses a shallow bowl of copper (or sometimes brass) with a hollow central tube; the equaling tool is similar in shape to a shallow funnel. The bowl is equipped with brass points with blunt ends across which the whole citrus fruit is rolled by hand with some pressure until all of the oil glands have burst. The oil and aqueous cell contents are allowed to dribble down the hollow tube into a container from which the oil is separated by decantation. Obviously, hand pressing is impractical because it is an extremely slow process, e.g. on average only 2-4 lbs oil per day can be produced by a single person using one of these hand methods. As a result, over the years a number of machines have been designed to either crush the peel of a citrus fruit or crush the whole fruit and then separate the oil from the juice.
In this process, the long enfleurage time is reduced by the immersion of petals in molten fat heated at 45°-60° C for 1 to 2 h, depending upon the plant species. After each immersion, the fat is filtered and separated from the petals. After 10 to 20 immersions, the fat is separated from waste flowers and water. Absolute of maceration is then produced from fat containing oil through the process of extraction and concentration under reduced pressure. It is mainly used for highly delicate flowers whose physiological activities are lost rapidly after their harvest, such as lily of valley.
Another aspect of hydrodiffusion is that the speed of oil vaporization 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-soluble 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.
In order to isolate essential oils by hydrodistillation, the aromatic 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. Mechanism of Distillation Hydrodistillation of plant material involves the following main physicochemical processes: i) Hydrodiffusion ii) Hydrolysis iii) Decomposition by heat
Hydrolysis in the present context is defined as a chemical reaction 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 relationship between the molal concentrations of various constituents at equilibrium 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. Furthermore, 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.
These techniques are as follows:
- Headspace trapping techniques
– Static headspace technique
– Vacuum headspace technique
– Dynamic headspace technique
- Solid phase micro-extraction (SPME)
- Supercritical fluid extraction (SFE)
- Phytosol (phytol) extraction
- Protoplast technique
- Simultaneous distillation extraction (SDE)
- Microwave distillation
- Controlled instantaneous decomposition (CID)
- Molecular spinning band distillation
- Membrane extraction
In the pelatrice process, citrus fruits are fed from a hopper into the abrasive shell of the machine. The fruits are rotated against the abrasive shell by a slow-moving Archimedian 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. Most bergamot oil and some lemon oil are produced this way in Italy.
The sfumatrice equipment consists of a metallic chain that is drawn by two horizontal ribbed rollers. The peels are conveyed through these rollers during which time they are pressed and bent to release their oil. As in pelatrice, the oil is washed away from the sfumatrice rollers by fi ne 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. At one time, sfumatrice was the most popular process for citrus oil isolation in Italy; however, today the pelatrice method appears more popular.
In water and steam distillation, the steam can be generated either in a satellite boiler or within the still, although separated from the 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 persons 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 sufficient 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 condensate water will allow it to become saturated with dissolved constituents, after which more oil will dissolve in it.
Some of the major constraints in sustainable industrial exploitation of medicinal and aromatic plants (MAPs) are due to the fact that the countries of South East Asia have poor agricultural practices for MAPs, unscientific and indiscriminate gathering practices from the wild, poor postharvest and post-gathering practices leading to poor quality raw material, lack of research for the development of high-yielding varieties of MAPs, poor propagation methods, inefficient processing techniques, poor quality control procedures, lack of research on process and product development, difficulty in marketing, non-availability of trained personnel, lack of facilities and tools to fabricate equipment locally, and finally lack of access to the latest technologies and market information. This calls for co-operation and coordination among various institutes and organizations of the region, in order to develop MAPs for sustainable commercial exploitation. The process of extracting MAPs determines how efficiently we add value to MAP bioresources. In the case of essential oils, the extraction process affects the physical as well as internal composition. External appearance, at times, can result in rejection of the batch even if the analytical results are within acceptable limits. Furthermore, essential oils are evaluated internationally for their olfactory properties by experienced perfumers and these olfactory qualities supersede analytical results. Variations in the chemical constituents of the extracts of medicinal plants may result by using non-standardized procedures of extraction. Efforts should be made to produce batches with quality as consistent as possible (within the narrowest possible range). – Link to original paper