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R.

Guba,
Essential Therapeutics Pty Ltd., 100
The modern
Dight Street, Collingwood, Vic.
3066, Australia.
alchemy of
E-mail: esstherapeutics@ozemail.
com.au
carbon dioxide
extraction
Ron Guba

W
e must thank the practi- Lastly, the remaining plant resi- tillation, and less commonly,
tioners of the ancient due or fixed sulphur would be com- through solvent extraction (the
hermetic art of alchemy pletely burnt or calcined, the ash flower absolutes, generally extracted
for what we know as essential oils would be washed with water and the using the petrochemical, hexane).
today. The famous physician and al- water evaporated, to liberate the wa- I would like to consider another
chemist Ibn Sina or Avicenna (AD ter soluble mineral salts or the sal form of the preparation of volatile
980–1037) is credited with perfecting (which represents the ‘body’ or ve- sulphur, using the modern alchemy
the process of steam distillation to hicle of the first two principles). of dense carbon dioxide extraction.
produce pure essential oils. This ex- The three ‘principles’ were then Cagniard de la Tour first dis-
traction method was only part of the joined together to create a finished covered the phenomenon of a su-
process for creating an alchemical preparation. In the view of alchem- percritical fluid back in 1822. In 1879
‘spagyric’ preparation (from the ists, ordinary plant tinctures only and 1880, the first research was
Greek spagyria – spao- to draw out or utilise part of the curative powers of published detailing that various gases
divide and ageiro – to gather bind or the plant. Spagyric preparation under high pressure were found to
join: hence to ‘dissolve and bind’). ‘opens’ the plant, and liberates exhibit excellent solvent qualities for
As in the treatises of the ‘father’ stronger curative powers. As in Ho- lipophilic compounds (i.e., com-
of western alchemy, Paraecelsus (AD meopathy and other forms of vibra- pounds that dissolve in non-polar
1493–1541), the creation of aspagyric tional medicine, spagyric solvents such as vegetable oil, etha-
plant remedy was based on the lib- preparations are based on their syn- nol, benzene, etc.).
eration and joining together of the ergistic and ‘energetic’ effects, in- Due to the lack of technology in
‘three philosophical principles’ of stead of simply looking at developing the key high pressure
the plant. pharmacologically active compo- equipment required, supercritical
First, the volatile sulphur would be nents (Junius, 1985). fluid extraction was not commercia-
liberated via steam distillation. This is In Aromatherapy then, we have lised for over 50 years. Eventually, in
the essential oil that represents the an entire therapeutic approach the 1980s, a number of supercritical
very ‘soul’ or consciousness of the based on the volatile sulphur of the carbon dioxide extraction plants
plant. Sulphur is fiery, radiant and a alchemists. We can see where the came into operation (Supercritical
masculine or active yang principle. term ‘essential oil’ derived from – Technology Consultants, 2002).
Then, the plant residues would ‘essence’ meaning the ‘soul’ or deeper A number of gases have been
be fermented with yeast to produce ‘personality’ of the individual plant trailed for supercritical extraction,
ethanol – or grain alcohol. This was (and with mercury, we can still go to including trifluromethane, ethane,
distilled to create the pure mercury, the liquor store and purchase a bot- dinitrogen monoxide, sulphur hexa-
which represents the principle of life; tle of ‘spirits’). fluoride and propane. However, car-
the vital power or ‘life force’, prana Traditionally, Aromatherapy has bon dioxide has been accepted as the
Qi, etc. It represents the feminine or employed the use of essential oils extraction medium of choice, for the
passive Yin principle. created primarily through steam dis- extraction of volatile compounds for

0962-4562/02/$ - See Front Matter


 2002 Published by
Elsevier Science Ltd
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flavour, fragrance and therapeutic Yet, this ‘fluid’ also shares the prop- importantly compounds found
use, for decaffeinating coffee beans, erties of a liquid, with its high density in essential oils: ethers, esters, ter-
for extraction of cocoa butter and and excellent solvating power. As the pene hydrocarbons, alcohols, ke-
other vegetable oils and on (Stahl et pressure is increased, the dissolving tones, etc.
al., 1988; Phasex Corporation, 2002). power of the supercritical carbon di- 2. At higher pressure and tempera-
oxide increases. In Fig. 2, we see the ture, triglycerides (vegetable oils
solubility of a variety of aromatic and animal fats), wax esters (as
Carbon dioxide
compounds found in essential oils, in in Jojoba oil) and other higher
We generally know of carbon dioxide carbon dioxide. At pressure levels weight non-polar compounds
(CO2 Þ in two forms: solid, dry ice, below the supercritical state, these can be extracted.
and as a gas. A liquid form does not compounds will only dissolve to a 3. As in the above two statements,
exist at normal atmospheric pressure small degree, but as the supercritical compounds that are predomi-
(see Fig. 1). state is reached the solubility in- nantly non-polar are best ex-
However, as pressure increases creases to quite high levels as the tracted in carbon dioxide, which
we can create a liquid form of CO2 pressure is increased further. functions as a non-polar solvent.
(liquid CO2 plants often operate at The solubility of typical essential Hence, the presence of po-
50–60 bar pressure at around 10 C oil components in dense carbon di- lar functional groups will
(1 bar ¼ 1 atm (normal atmospheric oxide at 40 C is shown in Fig. 3. lower the extraction to varying
pressure) ¼ 10 kPa ¼ 76 mm Hg ¼ ap- degrees.
proximately 14–15 lb/in:2 pressure). 4. Not extractable are polar com-
As we take the pressure and pounds such as sugars, glycosides,
What can be extracted with
temperature beyond the ‘critical amino acids, and lecithins;
carbon dioxide?
point’ (T c and P c ), carbon dioxide alkaloids are extracted at varying
becomes supercritical, this being the levels. Hence, carbon dioxide is
boundary where the difference be- 1. The compounds that are most not suitable for the extraction
tween being a gas and a liquid dis- easily extractable (up to 300 bar of all medicinal plants – it is
solve. Hence, we have an extremely pressure) are lipophilic (‘oil-lov- dependent on the solubility of
dense ‘fluid’ with the properties of a ing’), compounds that have a the most active compounds
gas – it diffuses easily throughout the high vapour pressure (volatility) desired.
plant material being extracted and it and a low molecular weight (up 5. More polar modifying com-
has low viscosity and surface tension. to 400 Da). This includes most pounds, such as water, can be

Fig. 1 Solid–liquid–gas – supercritical fluid diagram. Pc , critical pressure; Tc , critical termperature. The critical pressure and temperature for
carbon dioxide is 73.79 bar and 31.04 C, respectively. The triple point is where the solid, liquid, and gas phase co-exist in equilibrium.

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Fig. 2 The solubility of naphthalene in carbon dioxide increases greatly as the supercritical state is reached, and with further increase of
pressure.

Fig. 3 The solubility of typical essential oil components in dense carbon dioxide at 40 C (Franchomme, 1984).

added to the extraction process used to create extracts from aromatic


Varieties of carbon dioxide
to increase the extraction of plants and for the extraction of veg-
extraction
more polar compounds. This in- etable oils, antioxidant compounds,
cludes the extraction of the alka- Supercritical CO2 plants generally and other therapeutically active
loids caffeine from coffee beans operate from 80 to 500 bar pressure compounds that cannot be extracted
and nicotine from tobacco as from 40 to 60 C. This supercritical via steam distillation.
prime examples (Stahl et al., extraction is of most interest in Aro- Liquid CO2 extraction is the
1988; Amajuoyi, 2001). matherapy and herbal medicine, as other major variant. As a prime

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example, the prime flavouring of steam, and condense upon cool- carbon atoms). The ‘heavier’ the
compounds from pelletised Hops ing. compound, the higher its boiling
for use in beer, are extracted Generally, steam distillation is point and vapour pressure, and
by liquid carbon dioxide as in carried out at a temperature of hence heavier compounds remain
my hometown, Melbourne, Aus- 100 C, the boiling point of water. At behind in the still.
tralia at the Carlton United this temperature, in the presence of Depending on the plant and
Breweries. oxygen, water, and elevated temper- whether active ingredients can pass
Supercritical extraction is the ature, various changes can occur in over with steam, a more complete
basis of the remainder of the manu- the structure of aromatic com- extract can be of higher therapeutic
script (see Fig. 4). pounds. Certain compounds are heat value.
Solubility isotherms of typical sensitive, or thermo labile.
essential oil components in dense In other cases, various proteins Solvent extraction
carbon dioxide. present will decompose, creating what A variety of organic non-polar sol-
Supercritical carbon dioxide ex- are known as artefacts. These can be vents can be used for extracting
traction demonstrates a number of various types of decomposition prod- lipophilic (oil loving) compounds,
advantages over the traditional ucts such as hydrogen sulphide, am- such as ethanol (in herbal tinctures,
methods of obtaining essential oils monia, acetaldehyde, and others. etc.), benzene, and trichloroethyl-
and absolutes. Linalyl acetate will decompose back to ene.
linalool and acetic acid in lavender In Aromatherapy, we see are the
oil; the sesquiterpene lactone, matri- floral absolutes, obtained using the
Carbon dioxide vs. steam
cin (above 80 C) will decompose to petrochemical solvents hexane and
distillation
the intensely blue sesquiterpene hy- pentane.
Steam distillation is the oldest and drocarbon, chamazulene in German The traditional fat-extraction
most common method of obtaining Chamomile. This is why the very ex- method, or enfleurage is hardly used
essential oils. In fact, we can define pensive Bulgarian Damask Rose oil these days, due to the very high la-
an essential oil as the volatile com- does not quite smell like a Rose – it has bour costs involved. Almost all ‘ab-
pounds that will be removed via been changed to some degree during solutes’ are produced via hexane/
steam distillation. steam distillation. pentane extraction, as well as a few
Volatile aromatic compounds, As well, steam distillation favours other novel hydrocarbon solvents
with a boiling point of 150–200 C, only the most volatile compounds, (butane, for example).
are selectively separated out from starting with monoterpenes (10 car- Solvent extraction is generally
other plant constituents via the heat bon atoms) and lastly diterpenes (20 employed for the finest floral fra-

Fig. 4 Diagram of a supercritical carbon doxide extraction plant.

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grances, as the process creates less Carbon dioxide extraction, on bush still, CO2 extraction plants
‘re-arrangement’ of compounds than the other hand, bypasses the above are very expensive, in the range
steam distillation (hence truer to the problems. of millions of US dollars. This is
fragrance of the original flower) and • CO2 extraction uses relatively low a major reason why there are but
temperature; in the absence of ox- a handful of CO2 plants in opera-
will also extract heavier lipophilic
ygen and water. Hence, no decom- tion. This, however, does not
components. translate to extraordinary prices
position products or artefacts are
Although this is valuable for the for the extracts. Some extracts
formed. The final extract contains
perfume and flavour industry (and are comparable in cost to a corre-
what originally was in the plant.
hexane extraction is also the domi- • As in hexane solvent extraction, all sponding, high quality essential
nant method for the extraction of the heavier, less volatile compo- oil. Other extracts, depending on
commercial vegetable oils), we find nents will be extracted, without yield and other factors, are signifi-
problems with the use of solvent the problem, however, of any sol- cantly more expensive.
vent residues. At the end of extrac- • Pesticide residues. As compared to
extracted absolutes in Aroma-
tion, the pressure is reduced to the amount of pesticide residues
therapy. in spices that can be extracted by
normal and the CO2 simply evapo-
Firstly, hexane, being simply conventional liquid solvent extrac-
rates.
high-vapour-pressure petrol, is very tion, carbon dioxide extraction
• CO2 extracts do not require fur-
volatile, flammable and explosive. ther processing, as hexane ex- has been demonstrated to concen-
Numerous hexane extraction plants tracted concretes do. More highly trate from seven to 53 times more
have exploded and burned over the volatile ‘top notes’ are retained. pesticide residues in the final ex-
past 50 years, often with the loss of • CO2 extraction is non-toxic, non- tract. This can be addressed, of
flammable and is environmentally course, by only extracting plant
multiple lives (PNP Inc., 2002). It
safe without harmful emissions or material from certified organic
has also been suggested that pro-
toxic by-products. In the case of growing practices, or shown to be
longed exposure to hexane amongst pesticide-free by analysis. Varying
one large manufacturer, Flavex Na-
workers in extraction plants leads to different parameters of the extrac-
turextrakte, natural carbon dioxide
a variety of illnesses (Franchomme, is collected from areas of volcanic tion process will also reduce the
1984). activity. Hence, no additional CO2 extraction of pesticides (Amajuoyi,
A severe environmental prob- is added to the atmosphere. 2001).
lem exists with the inevitable loss of Supercritical CO2 extraction also has
hexane to the atmosphere during the unique capacity to selectively ex-
tract different components. At 80– Carbon dioxide extracts for
manufacturing and processing. Even
100 bar pressure at 40–60 C, super- therapeutic use
a state-of-the-art, medium sized soy-
critical CO2 will extract primarily
bean oil producing plant is esti- The major market for CO2 extracts is
the volatile aromatic compounds,
mated to leak approximately termed a ‘select’ extract. This is their application in flavours and fra-
88,000 kg of hexane into the somewhat comparable to a hexane grances. Additionally, there are a
atmosphere each week (PNP Inc., extracted absolute. number of extracts available that
2002). By increasing the pressure from have definite applications in herbal
Lastly, no matter how efficient 200 to 500 bar with a longer extrac- and aromatic medicine. A selected
the final extraction of hexane is tion cycle, heavier lipophilic compo- list of such extracts includes: Calen-
from the finished absolute, some nents are removed, including waxes, dula, German Chamomile, Frankin-
hexane residues do remain in the triglycerides (vegetable oils), wax es- cense, Ginger, Kava Kava, Marjoram,
final product. The current Euro- ters (as in Jojoba), carotenoids, etc. Melissa, and Rosemary; primarily
pean Union standards are for less These are termed total extracts and vegetable oil extracts of Borage,
than 10 parts per million solvent are somewhat comparable with a Evening Primrose, Neem, Rose Hip,
residues in a finished absolute. This hexane extracted concrete. and Sea Buckthorn.
permitted level is small (0.001% or Let us consider three extracts
less), nevertheless, from a thera- Disadvantages of carbon dioxide with outstanding therapeutic prop-
peutic perspective, a solvent-free extraction erties.
extract for topical application, cer- Calendula CO2 total extract
tainly for ingestion, would be pre- • The first limitation is that of cost. As (Calendula officinalis) contains the
ferred. compared to the set-up costs of a active triterpene monools, diols, and

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Anti-inflammatory activity of Calendula officinalis extracts in
Table 1 reducing croton oil-induced oedema of mouse ear (Della Loggia
et al., 1990a,b)

Substances Dose (lg per ear) Milligrams of crude druga Inhibition of edema (%)
Hydro alcoholic extract 300 1.04 9.3
600 2.08 12
1200 4.16 20

Carbon dioxide extract 75 1.79 14.5


150 3.58 30.6
300 7.16 44
600 14.3 58.7
1200 28.6 70.7

Indomethacin 30 – 37.3
120 – 73.3
a
Milligrams of dried calendula flowers.

their esters, with the faradiol mono- substantially altered during steam apy, are extrapolated from the use of
esters being the most important distillation. The dark blue colour of the whole rhizome. However, the es-
(about 20% of the total extract). German Chamomile is due to the sential oil lacks the active, less vola-
Such compounds could not be sesquiterpene hydrocarbon, cham- tile pungent phenyl propanoid
extracted by steam distillation; they azulene, which is formed from the compounds.
are found in low concentration in decomposition of the sesquiterpene The total Ginger CO2 extract
both hydro alcoholic (tinctures) lactone, matricin during distillation. contains from 25 to 33% of these
and vegetable oil extracts (infused The CO2 extract of German Chamo- pungent actives – gingerols, shogaols,
oils). mile maintains the matricin content. and zingerone. Therefore Ginger
As compared to a typical infused It has a fine, characteristic chamo- CO2 extract is therapeutically more
oil, the concentration of ‘actives’ in mile odour, yellow–green in colour. active than the essential oil, making it
the CO2 extract is approximately 180 As well, the extract of choice is de- more suitable for treating nausea,
times greater. Calendula CO2 is an rived from the a-bisabolol type Ger- travel sickness, muscular pain,
excellent anti-inflammatory and man Chamomile; a-bisabolol having cramping, arthritis, etc., as outlined in
healing extract. It is suited for con- demonstrated anti-inflammatory and both Eastern and Western herbal
ditions such as acne, eczema, allergic wound healing activity (Jakovlev and medicine (Flavex Naturextrakte,
dermatitis and the healing of burns, von Schlichtegroll, 1969). 2002).
wounds, and ulcers. It is also quite In terms of anti-inflammatory In summary, we can see that es-
non-toxic and non-sensitising; up to power, there is research demonstrat- sential oils have progressed beyond
a 10% concentration can be applied ing that matricin has significantly the stills of the ancient alchemists.
even on young infant (Quirin and stronger (10 times more active) anti- Although traditional steam distilled
Gerard, 1999). inflammatory properties than cham- oils will remain the most popular and
One study demonstrated the azulene. accessible plant extracts used in
superior anti-inflammatory activity of Hence, in the treatment of in- Aromatherapy, we can see some def-
Calendula CO2 extract versus a hydro flammatory disorders – dermatitis, inite advantages in a variety of car-
alcoholic tincture. As well, the CO2 oral mucositis, and the like — the bon dioxide extracts. As the interest
extract was as active in reducing in- CO2 extract stands superior (Della in Aromatherapy and botanical
flammation as the potent anti-in- Loggia et al., 1990a,b). medicine continues to increase, we
flammatory drug, indomethacin (see Most of the therapeutic applica- can look forward to adding more of
Table 1). tions of steam distilled Ginger these products of ‘modern alchemy’
German Chamomile (Matricaria (Zingiber officinale) essential oil listed to our working collection of health
recutita) yields an essential oil that is in numerous books on Aromather- serving extracts.

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inflammatory activity of Fluids 2000. Available from:
Acknowledgments
chamomile preparations. Planta <http://www.phasex4scf.com/scf.
With thanks to Flavex Naturetrakte Med. 56: 657–658. htm>.
of Rehlingen, Germany for their as- Flavex Naturextrakte (2002). Producers Natural Processing
sistance (www.flavex.com). Specification – ginger–ginger Inc. (2002). Edible oil
CO2 total extract. Available from: extraction: severe limitations
<http://www.flavex.com>. of hexane (solvent extrac-
References
Franchomme, P. (1984). Guarantees tion) 1999. Available from:
Amajuoyi, I.K. (2001). Behavior and on the Plant International <http://pnpi.com/hexane. htm>.
elimination of pesticide residues Phytomedical Foundation. Belv eze Quirin, K. and Gerard, D. (1999).
during supercritical carbon -du-Raz es. New aspects on calendula CO2
dioxide extraction of essential Jakovlev, J. and von Schlichtegroll, A. extract as a cosmetic ingredient.
oils of spice plants and analysis of (1969). On the inflammation Cosmetics and Toiletries, 112(4):
pesticides in high-lipid-con- inhibitory effect of ())-a- 55–58.
tent plant extracts. Doctoral bisabolol, an essential component Stahl, E. et al. (1988). Dense gases for
thesis Technische Universit€at of chamomilla oil. extraction and refining 11. Springer,
M€unchen. Arzneimettelforschung, 19(4): 615– Berlin.
Della Loggia, R. et al. (1990a). 616. Supercritical Technology Con-
Topical anti-inflammatory activity Junius, M. (1985). Practical handbook sultants (2002). About
of Calendula officinalis extracts. of plant alchemy, Inner Traditions Supercritical Fluid Technology
Planta Med. 56: 658. Ltd, New York. 2000. Available from: <http://
Della Loggia, R. et al. (1990b). Phasex Corporation (2002). www.rljdev.com/sc/about_sf_tech.
Evaluation of the anti- Introduction to Supercritical htm>.

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