DE2336637A1 - PROCESS FOR THE EXTRACTION OF FRAGRANCE AND FLAVORS FROM VEGETABLE MATERIAL - Google Patents

Description

Process for the extraction of fragrances and flavors from

vegetable material.

The invention relates to the extraction of flavor and Fragrance components from plant material e.g. fruits, vegetables or spices. - -

The extraction of juices with fluorinated hydrocarbons for the extraction of fragrances and aromas from plant material is known. Fluorocarbons are relatively odorless, non-toxic and essentially non-flammable, they are available with wide boiling ranges, with a corresponding low boiling point, the extraction and the separation can be carried out at a low temperature, so that one receives better products than with conventional high-temperature steam distillations.

It has now been found that the use of fluorinated Hydrocarbons as solvents for fragrances and aromas

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substances leads to even better results if the whole plant material and not a prepared juice is extracted. The "advantage of treating unseparated material is that certain water-insoluble fragrance and Flavorings are also extracted, so that one obtains a fuller and more authentic organoleptisch.es spectrum, in particular when the extraction takes place with multiple solvents. Eventually, less water-soluble material remains in the residue than if it were eaten a juice.

A further improvement in the process using fluorinated hydrocarbons is that a non-polar fluorocarbon is used in conjunction with a second polar solvent, such as water, acetone or a polar fluorocarbon. The effect of the combination of a non-polar and polar solvent leads to a better extract yield and better organoleptic properties than when only a non-polar fluorocarbon is used alone.

It was further found that except by extraction ^ n preferably with a combination of one not polar fluorocarbon with a polar solvent also obtains satisfactory results in certain cases with a single fluorocarbon. In one of those If you use a fluorocarbon with two or more carbon atoms, the plant material is im essentially not roasted or not fermented.

The extraction is successful according to the process according to the invention of fragrances and flavorings from plant material by the plant material with a non-polar fluorinated carbon

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hydrogen containing two or more carbon atoms, is extracted. If necessary, a polar solvent can be used at the same time or subsequently, which forms Layers are separated and the solvent or solvents are removed by controlled evaporation, so that the desired Receives scents or aromas. If necessary, the extract can also be decolorized in the polar solvent.

The invention further relates to the treatment of essentially unroasted or unfermented natural Plant material for the extraction of the fragrance or flavoring substances by adding the plant material with a non-polar Fluorocarbon is only off, containing two or more carbon atoms, is extracted, after which the solvent can be removed by controlled evaporation.

It is possible that these measures are carried out in a closed system so that the fluorocarbons: hydrogen

condensed - if necessary with a heat exchanger _-_ and

can be reused.

When carrying out the method according to the invention with a non-polar fluorocarbon and water, the entire non-aqueous extract is separated from the aqueous layer and the fluorocarbon evaporated.

The method according to the invention can be used with particular advantage on fruits and vegetables with high proportions fused oils like coffee, nutmeg, and cloves. After separating the non-aqueous extract from the aqueous Layer, the main amount of fixed oil is isolated by controlled evaporation of the fluorocarbon, since the fixed

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oil is less soluble ". The combined effect of reducing the solvent temperature as a result of regulated evaporation and the increase in the extract concentration leads to preferential precipitation of the fixed oils, which can then be easily separated. Optimal temperature and concentration can be easily determined depending on the raw material used. In addition to the extraction of a relatively pure and concentrated essential oil with comparatively none fixed oil, it is possible to use special fixed oil extracts, e.g. for use in cosmetics.

In addition to or instead of the regulated evaporation of the solvent, it is possible to remove the fixed oil from the essential to separate oil after all the fluorocarbon removed by adding to the total oil extract a surfactant or detergent and again Extraction with a fluorocarbon. Although both the fixed as well as the essential oils are usually included are easily miscible with the fluorocarbon, the

Effectiveness of the detergent in delaying or modifying

the balance in favor of the essential oil, possibly by migration of the detergent to the oil / fluorocarbon interface. When performing the extraction under suitable conditions, experimentally for each material can be determined, it is possible to determine the fluorocarbon containing the essential oil, to be separated from a comparatively pure layer of fixed oil.

Examples of usable fluorocarbons are 1,2-dichlorotetrafluoroethane (CClF ₂ GClF ₂ ), which is a non-polar solvent with a boiling point of 355 ° C | or dichlorofluoromethane CHCl ₂ E ¹ , which is a polar solvent with a boiling point of 8.9 ° C. The boiling point of the former

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Solvent makes this "particularly suitable for the application in normal laboratory equipment. Spruce polar solvents are more volatile than polar solvents because they do not have a polar or hydrogen bond to increase their boiling point. For this reason it delivers an extract of a plant material, such as pepper, with the help of a non polar fluorocarbon a product similar to a common essential oil made by steam distillation, However, better than the latter due to the lower extraction temperature. The two-solvent system according to the invention is advantageous for the extraction of spices, since a non-polar fluorocarbon can be used to first extract the volatile flavoring agents, whereupon-a polar fluorocarbon applied is used to extract the less volatile and pungent components, such as piperine.

The invention is illustrated by the following examples. The examples are only approximate amounts of fluorocarbons. specified. Under-JLaboratory conditions -is. -The exact Measurement impractical due to rapid evaporation.

example 1

A series of tests was carried out by heating 200 g of ground Kenya coffee (moisture content 2.2 %) with varying amounts of boiling water between 0 and 600 cnr (boiling water was used to give the oil obtained the usual aroma of boiled coffee) «In each experiment, the coffee or the coffee / water mixture was extracted twice with an excess of 1,2-dichlorotetrafluoroethane. Then the coffee grounds were sieved and

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optionally the fluorocarbon from the remaining water separated. In the experiment with a coffee: water ratio of 1: 1, a clear solution was obtained. By the others Attempts were the solutions .cloudy, they were over magnesium sulfate dried and filtered. The solutions were then evaporated and the oil yield determined. One 4 / ul sample each Oil was analyzed by vapor phase chromatography.

coffee
S. Cook
of
V / aas he
cm Oil -
Stress
te Sum of
Areas in
stop it
Peaks Yield of cursed
oil 200 0 8.0 7.544 60,352 200 100 5.6 34.983 195.904 200 200 4.8 51.271 246,100 200 300 4.2 36.703 154,152 200 400 - 4.0 -36 -, - 083- ~ ^ 44,332 200 600 2.0 33.852 67.704

The yield of volatile oil is the product of the oil yield and the sum of the area of the peaks.

This series of tests shows that the extraction at a ratio of eg-toff-: water 1: 1 highest concentration of volatile oils per unit fixed oil and the highest yield of volatile oils.

Changed ^ "p?

Received on .iT _t .A.:. iJ , / _M · ^ ' t · Χ

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Example 2 (a)

200 g of ground Kenya coffee were mixed with 200 cnr of boiling water and then extracted with 1,2-dichlorotetrafluoroethane as in Example 1. After the fluorocarbon was evaporated, all of the oil was shaken 1% by volume of a detergent and then an excess (about 20 cm x ^) of the fluorocarbon was added. 10 % of the total oil was extracted by the fluorocarbon. The residue was essentially odorless, indicating that essentially all of the essential oil had passed into the fluorocarbon phase. The fluorocarbon was evaporated and the extraction repeated. In this second extraction, 25 % of the enriched oil was extracted, giving a total essential oil versus fixed oil concentration of 40: 1.

Example 2 (b)

I? 2Ö g of coffee were added to 200 cnr of boiling water Example 1 mixed, fluorocarbon was evaporated in vacuo while the temperature was lowered from 3 ° to -25 ° C became. 3 cm ^ of colorless frozen fixed oil was removed and 0.25 cnr concentrated essential oil obtained

Example 3

A series of tests was carried out with 600 g samples of mixed Indian, Ceylonese and East African teas carried out, the proportions of cold or boiling water varying between 0 and 2.4 liters. In every attempt it was

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After about 30 minutes the tea or the tea and water mixture is extracted with an excess of 1, ^ - dichlorotetrafluoroethane.
After a short time the organic layer separated, was dried with magnesium sulfate, filtered and the solvent was evaporated. A small amount of oil was obtained, the presence of solids in the oil made the determination of the yield uncertain, but 4 / μl samples were analyzed by gas chromatography. The table below shows that with cold water the optimum concentration was achieved with a water: tea ratio of 2: 1 and with hot water of 3.5 '· 1.

Tabel

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- D- LA O CM CJN O KN V- it - V- Ä O O O KN CQ CJN CJN CJN O α IA KN CO ^ t KN D- CJN v- CJN CM vO H- CJN LA O CO CJN LA co ^ j. ί CM CM
LA V
LA V CO ^ ~ KJ
a • KN CD IA D- CO KN KN LA O • -9 OLi
• Η CM LA co V H- CJN O. M. LA CM O ^ D- LA V- v-
CJN V (T οΓ ιθ CJN CJN. Λ " CM LA -P CJN K ^ D-
CM VO D- v- O IA O CJN KN O VD CM VD O D- O O
9 KN
LA D-
- VO D-
D- IA $ VO
D- VO He3 ^ V LA .CO CM • Η ν- KN CM Φ VO D-
LA ä " CM
V lÄ
CM D- IA KN CJN CM O D- LA O οΓ V IA VD VO CO KN : en < V V V O φ ^ CJN KN CJN D- V " O O ω VD
O V
D- CM -ä KN
CM ω KN KN
I. D- H; D- LA v- KN KN I.
rrt ^ ". D- CO D- D- i UU
•H • Η j. IA O KN LA O Φ CM LA D- KN CO ^ D- ' KN CO LA IA CJN CM \ + V CO -P
t KN CM KN KN KN -4 = - Ό— D- α H- IA 5 ^ · V CJN O V LA O D- CM O 00 O CO .3 CJN O CO CJN V CJN KN D- t IA V " IA CJN H CCj V " D- CO V SJ • rl
Φ V- CM D- LA O § CM VD $ V VD CO O •G IA 00 V " CO V " D- VO CM O"* CM CM KN cvT Ql VfT VfT CM O KN IA O _H CM D- V V O φ O O O VD OK
IQ O O O O O O O O O to O O VD O LA KN CJN CM V φ 60 O ^ O O φ
egg O O O O O O O O O O O VD O O VD VD VD VD VO VD

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Example 4-

This example explains the application of the method according to the invention to a natural product which is already optimal Contains amount of water.

Orange peel with a moisture content of about 72% by weight was carefully removed from the fruit and mixed with 1,2-diehlortetrafluoroethane. The organic layer was then separated off, the residue was extracted again with fresh fluorocarbon, the two extracts were combined and evaporated. Yield about 20 % high quality oil.

Similar experiments were carried out with lemon and cementines Grapef ruitr and lime peel.

Example 5

Ground cinnamon leaves with a moisture content of 6.5% by weight were extracted with 1,2-dichlorotetrafluoroethane, the organic layer separated and evaporated.

The moisture content of a second sample of cinnamon leaves was determined by adding 2 parts by weight of boiling water brought to 68.8%. The leaves were then extracted with 1,2-dichlorotetrafluoroethane, the organic layer stripped off, dried with magnesium sulphate, filtered off and evaporated. 0.5 / µl samples of each oil were analyzed by gas chromatography. The areas of the two main peaks were

6.5% moisture - 522,771 and at 66.8% moisture - 1676,701.

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Example 6

This example hesitates to use a non-polar one Fluorocarbon for the production of a clear mobile essential oil from a spice and the influence of the Moisture on the yield.

1 kg samples of old, ground Malabar pepper were made adjusted to different moisture contents and then 10 min with 2 1 1 ^ -Dichlorotetrafluoräthan at the boiling point of Solution extracted. The extract was drawn off and the pepper was extracted twice more, in each case for 5 minutes with 2 liters of solvent. The combined extracts from the individual samples were determined Moisture content was evaporated to give a yellowish-orange mobile oil.

Moisture content% Example 7 Yield % 3 2.94 8.85 3.29 15th 3.65 19.75 3.42 32 2.25 73 1.25

This example shows a two-solvent system for Manufacture of a high quality, decolorized, semi-solid mixture of the resin and oil of pepper.

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Ground Malabar pepper was extracted with 1,2-dichlorotetrafluoroethane according to Example 6 and gave a first product in a yield of 6.6 %. The pepper residue was extracted in a similar manner with dichlorofluoromethane to yield a dark green paste as a second product in a yield of 6.9%, "This paste was mixed with 400% of its weight of petroleum ether (boiling range 60 to 80 ⁰ C) and acetone (ratio 1: 1) treated and the yellow precipitate filtered off. This precipitate was further extracted with a 2: 1 mixture of petroleum ether and acetone to give a pale yellow powder as the third product in a 1.5% yield on the original pepper. Mixing products 1 to 3 gave a high quality decolorized product Pepper extract.

Example 8

According to Example 7, ground Malabar pepper was extracted

with 1,2-dichlorotetrafluoroethane. Then nit Acejton

extracted further, a dark green paste was obtained with a yield of 6%. This material in a small amount of acetone was passed through a column filled with activated carbon. The orange-yellow eluate was freed from the solvent and left 2.4 % yellow powder (calculated on pepper). The two extracts were mixed according to Example 7

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Claims (5)

Pat ent * of sayings 1. Procedure for extracting the fragrances and flavorings from Plant material, characterized in that the plant material is fluorinated with a non-polar one Hydrocarbon, containing or more carbon atoms, "treated, possibly simultaneously or subsequently with a polar solvent, whereupon the layers obtained separated, the solvents are removed by controlled evaporation and the smells and flavors are extracted. 2. The method according to claim 1, characterized in that g e k e η η that one uses 1,2-Dicnlortetrafluoräthan as the extraction agent used. 3. ^ The method according to claim 1 or 2, characterized in that g e k e η η - that water, dichlorofluoromethane or acetone is used as the polar solvent. 4. The method according to claim 1 "to 3» thereby g e k e η η draws that the extract of the polar solvent is decolorized. 5. Application of the method according to claim 1 to 4- for im essential unroasted or unfermented plant material, in particular spices. 81XXV 309885/1340