DE102017004720A1 - Process and device for the production of high-purity Aquatic Scovillin Compositions (HASC) with definable sharpness and products that can be produced therewith - Google Patents

Abstract

The invention relates to a process for the preparation of high-purity Aquatic Scovillins Compositions (HASC) and products which can be produced therewith. These include compositions of organic or vegetable starting materials, from which scovillins (pungent substances) are extracted by high-pressure methods and brought into an oil-in-water compound (aquatic) by means of an emulsifier. The term "scovillin" is understood to mean non-water-soluble, pungent-tasting substances of natural origin, the degree of severity of which can be represented by the scoville scale (so-called pungent substances). With the method according to the invention, it has become possible to extract scovillins (spars) both in high purity and in high concentration and to bring them into a water-soluble form (HASC). In addition, it is possible to define the parameters necessary for the procedure by means of the "Butz-Hofferschen-Formel" with the aid of the unit of measure ASC. Thus, a use of the product is everywhere where a water solubility is desired and so far could not be realized, such. when used as a beverage or food additive.

Description

The invention relates to a process for the preparation of high-purity Aquatic Scovillins Compositions (HASC) and products which can be produced therewith. These include compositions of organic or vegetable starting materials from which are extracted by high-pressure process scovillins (sharpness) and are brought by means of an emulsifier in an oil-in-water compound (aquatic). The term "scovillin" is understood to mean non-water-soluble, pungent-tasting substances of natural origin, the degree of severity of which can be represented by the scoville scale (so-called pungent substances).

The scoville scale

The Scoville scale is a development of the British pharmacologist Wilbur L. Scoville and is still considered one of the most reliable indicators of the degree of severity of scars (scovillins), e.g. Used chilies. In the measurement process, a mixture of chili powder and alcohol is prepared and diluted with water until a tester on the tongue can no longer determine sharpness. The sharper e.g. a chilli fruit is, the more must be diluted. If e.g. For 1 ml of chilli tincture 1 liter of water (1,000 ml) is needed for dilution so that no more sharpness can be perceived, then the sharpness of this chilli is 1,000 scoville units.

Occurrence of natural sharpness

• Beispielsweise in der Familie der Nachtschattengewächse Solanaceae, wobei die Gattung Capsicum, zu denen zum Beispiel Paprika oder auch Chilischoten gehören, am bekanntesten ist.

Natural non-water-soluble pungent substances (scovillins) are found in numerous organic or vegetable sources:

• For example, in the family Solanaceae Solanaceae, the genus Capsicum, which includes, for example, peppers or chili peppers, is best known.

1. 1) Solanaceae - Capsicum - Chili
2. 2) Piperaceae - Pfeffer - schwarzer Pfeffer
3. 3) Alliaceae und Amaryllidaceae - Allium - Zwiebel, Bärlauch, Knoblauch
4. 4) Brassicaceae - Raphanus, Lepidium, Brassica - Rettich, Kresse, Senf
5. 5) Zingiberaceae - Curcuma, Zingiber, Aframomum - Turmeric, Ingwer, Melegueta-Pfeffer
6. 6) Myrtaceae - Syzygium, Pimenta - Gewürznelken, Piment
7. 7) Myristicaceae - Myristica - Muskat
8. 8) Lauraceae - Cinnamomum - Zimt
9. 9) Orchidaceae - Vanilla - Vanilla planifolia
10. 10) Iridaceae - Crocus - Crocus sativus
11. 11) Apiaceae - Pimpinella - Anis
12. 12) Russulaceae - Lactifluus - Lactarius Piperatus, Lactarius vellereus
13. 13) Boletaceae - Chalciporus - Chalciporus piperatus

Further exemplary fumigant-containing plant families, genera and species:

1. 1) Solanaceae - Capsicum - Chili
2. 2) Piperaceae - pepper - black pepper
3. 3) Alliaceae and Amaryllidaceae - Allium - onion, wild garlic, garlic
4. 4) Brassicaceae - Raphanus, Lepidium, Brassica - radish, cress, mustard
5. 5) Zingiberaceae - Curcuma, Zingiber, Aframomum - Turmeric, ginger, Melegueta pepper
6. 6) Myrtaceae - Syzygium, Pimenta - cloves, allspice
7. 7) Myristicaceae - Myristica - Nutmeg
8. 8) Lauraceae - cinnamomum - cinnamon
9. 9) Orchidaceae - Vanilla - Vanilla planifolia
10. 10) Iridaceae - Crocus - Crocus sativus
11. 11) Apiaceae - Pimpinella - anise
12. 12) Russulaceae - Lactifluus - Lactarius piperatus, Lactarius vellereus
13. 13) Boletaceae - Chalciporus - Chalciporus piperatus

capsaicinoids

Capsaicin and other plants derived from plants of the genus Capsicum, causing sharpness sensation, are referred to as capsaicinoids. The sharpness of e.g. Spice paprika and chillies are caused by the group of capsaicinoids found exclusively in the fruits of Capsicum plants. The fruits, often referred to as paprika or chili peppers, are botanically considered berries.

The capsaicinoids capsaicin and dihydrocapsaicin are the two main crop constituents in fruits of the genus Capsicum. Both substances are significantly sharper on the Scoville scale than the smaller capsaicinoids Nordihydrocapsaicin, Homodihydrocapsaicin, Homocapsaicin and others.

Capsaicin is a naturally occurring irritant that represents an evolutionary advantage over other plants for plants of the genus Capsicum, because the plant forms a natural protection against predators and parasites in this way.

The plants of the genus Capsicum are preferably cultivated in warm regions.

The use of chilli as a spice is widespread, mainly because of the pungent taste that comes from capsaicinoids. A number of physiological effects are also attributed to this spice, for example against colic, circulatory problems and also against neurogenic pain.

It has an antibacterial and fungicidal effect and therefore has a preservative effect on living tissue. The spectrum of action ranges from a slight sensation of warmth at the nerve end on contact, to real pain and even burns of the surrounding tissue. This depends very much on the dosage, which is why the consumption of special spicy species of the genus Capsicum should be done with care. Capsaicin also has a relaxing effect on the blood vessels and promotes blood circulation, which is why regular consumption can be quite stimulating for the circulation and good for the general well-being. Other uses of the irritant can be found in acupuncture, heat patches and biological repellents, e.g. Irritant gas against dogs. Capsaicinoids can also help with: throat and nose problems, circulatory problems, arteriosclerosis, asthma, shingles, chickenpox or thrombosis. Revolutionary is the use of capsaicin in cancer research. American scientists found out in 2006 that the targeted use of chili can reduce the growth of cancer cells by up to 80%.

Extraction of capsaicinoids

Capsaicin is a lipophilic and largely hydrophobic vanillylamide. Thus capsaicinoid substances are in fact water insoluble. The ingredients of chili can therefore be obtained by solvent extraction using ethanol. An extraction of capsaicinoiden substances is carried out in a previously known manner by pressing, to then further fractionate the presscake and these oils using organic solvents. Problems arise from the fact that the extracts obtained are very rich in oil. The unsaturated fatty acids contained therein are oxidized by the atmospheric oxygen, which is why there is a risk that the extract will have a rancid odor. In addition, in the extracts contain undesirable impurities such as sulfur compounds, phenols and bitter substances, which also have an unpleasant odor. For a desired use in food or pharmaceutical applications, the final product obtained must be free from residues. This is problematic in solvent extraction because the solvents are not readily completely removable. A major disadvantage of this type of extraction is also that the dissolved or extracted substances are not water-soluble.

HD extraction with supercritical gases, super and subcritical fluid extraction

High-pressure extraction (HD extraction), also called Super and Subcritical Fluid Extraction or "Critical Gas Extraction", uses a gas where the temperature and pressure exceed or fall short of the critical parameters. Since extraction with supercritical and subcritical gas readily separates the extractant from a solution and can be carried out in relatively low temperature ranges, it is an effective separation method for thermally unstable or heat sensitive materials. High pressure extraction offers opportunities to selectively and selectively produce materials with the utmost care of the materials involved to separate.

The extraction of ingredients by means of carbon dioxide is already an established method on an industrial scale. If a gas is heated above the so-called critical point and set below the critical pressure, it will become supercritical. Then it is no longer possible to distinguish whether it is gaseous or liquid, because supercritical fluids possess the high density of a liquid and the low viscosity of a gas. In the transition to this state, the solvent power increases abruptly.
It is used industrially for the extraction of hop bittering substances for beer production, for the decaffeination of coffee and tea and for the production of spice extracts and flavorings on a large scale worldwide. For example, for decaffeination, carbon dioxide is used as an extractant in high pressure processes to dissolve caffeine without affecting other components.
The extraction of ingredients of the neem tree is for example from the DE 196 01 482 A1 known.

Suitable fluids used for HD extraction are very different. Trifluoromethanes, chlorodifluoroethanes, methanol, ethane, nitrous oxide, propane, butane, benzene and carbon dioxide are known. Mostly carbon dioxide is used for supercritical fluid extraction. The gas reaches its critical point already at 31 degrees Celsius and a pressure of 74 bar. The material to be processed only needs to be heated slightly above room temperature. This is not only a significant advantage of this gas with sensitive plant products. After extraction, it is completely evaporated and can then be used again as a solvent in a closed circuit.

task

It is an object of the invention to provide a process for the preparation of high purity Aquatic Scovillin Compositions (HASC) and products that can be produced therewith with a high active ingredient content, with improved quality, in which the water solubility of the final product is given. Furthermore, an apparatus for carrying out the method should be specified.

Inventive solution

In high purity Aquatic Scovillins Compositions (HASC) of the type described above, the object is achieved by the features specified in the claims.

Fractionated separation in high-pressure carbon dioxide extraction

Due to the different solution behavior of essential oils and fuels in supercritical carbon dioxide, there is the possibility of separate recovery of these two components by appropriate selection of the parameters in the extraction process.

The biomass to be extracted must have the following characteristics:

The fruits, such as the genus Capsicum, are harvested ripe and ideally dried to 20 percent residual moisture. The starting materials to be extracted, e.g. Chili fruits are preferably cultivated in organic farming. After harvest, the fruits are dried and minced. Drying with a spray or vacuum process is advantageous because it is quick and, moreover, largely frees the fruits of bacteria, viruses, fungi and the like.

The value-determining constituents of the fruits of the genus Capsicum are capsaicin, dihydrocapsaicin, Nordihydrocapsaicn, Nornordihydrocapsaicin I, Nornordihydrocapsaicin II, N-vanillylnonanamide, N-vanillyldecanamide, Homocapsaicin I, Homocapsaicin II, Homodihydrocapsaicin I, Homodihydrocapsaicin II, Nonivamide. Type of capsaicinoid Proportion of the total amount of capsaicinoids Scoville units capsaicin 69% 16,000,000 dihydrocapsaicin 22% 15,000,000 Nordihydrocapsaicn 7% 9100000 Nornordihydrocapsaicin I & II <1% 9000000 Homocapsaicin I & II 1 % 8600000 Homodihydrocapsaicin I & II <1% 8600000 Nonivamide <1% 9200000

• Möglicher Wirkungsbereich:
  • Extraktionstemperatur: 10 °C bis 120 °C
  • Extraktionsdruck: 50 bar bis 2500 bar
• Effektiver Wirkungsbereich:
  • Extraktionstemperatur: 40 °C bis 80 °C
  • Extraktionsdruck: 100 bar bis 400 bar
• Idealer Wirkungsbereich am Beispiel von Capsaicinoiden:
  • Extraktionstemperatur: 38 °C bis 42 °C
  • Extraktionsdruck: 380 bar bis 420 bar

The dried fruit is preferably extracted by means of HD extraction using the following action ranges and parameters:

• Possible range of effect:
  • Extraction temperature: 10 ° C to 120 ° C
  • Extraction pressure: 50 bar to 2500 bar
• Effective range of action:
  • Extraction temperature: 40 ° C to 80 ° C
  • Extraction pressure: 100 bar to 400 bar
• Ideal range of action for the example of capsaicinoids:
  • Extraction temperature: 38 ° C to 42 ° C
  • Extraction pressure: 380 bar to 420 bar

The extracted material is then brought in the next step by means of an oil-in-water emulsion with the addition of a natural, semi-synthetic or synthetic emulsifier in water-soluble form.

• Lecithin - E322 -; Polyoxyethylen-sorbitan-monopalmitat - E434 -; Polyoxyethylen-sorbitanmonostearat - E435 -; Polyoxyethylen-sorbitan-tristearat - E436 -; Triphosphate, Phosphat - E451 -; Polyphosphaste - E452 -; Natrium-; Kalium- und Calciumsalze von Speisefettsäuren, Salze von Speisefettsäuren - E470A -; Magnesiumsalze von Speisefettsäuren, Salze von Speisefettsäuren - E470B -; Mono- und Diglyceride von Speisefettsäuren - E471 -; Essigsäureester von Mono- und Diglyceriden von Speisefettsäuren - E472A -; Milchsäureester von Mono- und Diglyceriden von Speisefettsäuren - E472B -; Citronensäureester von Mono- und Diglyceriden von Speisefettsäuren - E472C -; Mono- und Diacetylweinsäurester von Mono- und Diglyceriden von Speisefettsäuren - E572E - Zuckerester von Speisefettsäuren - E473 -; Zuckerglyceride - E474 -; Polyglycerinester von Speisefettsäuren - E475 -; Polyglycerin-Polyricinoleat - E476 -; Propylenglycolester von Speisefettsäuren - E477 -; Thermooxidiertes Sojaöl mit Mono- und Diglyceriden von Speisefettsäuren - E479 -; Natriumstearoyl-2-lactylat - E481 -; Calciumstearoyl-2-lactylat - E482 -; Sorbitanmonostearat - E491 -; Sorbitantristearat - E492 -; Sorbitanmonolaureat, Sorbitanmonooleat - E493 -; Sorbitanmonopalmitat - E495 -; Fettsäuren, Speisefettsäuren - E570; Polysorbat 20; Polysorbat 40; Polysorbat 60; Polysorbat 80; etc.

Examples of emulsifiers are:

• Lecithin - E322 -; Polyoxyethylene sorbitan monopalmitate - E434 -; Polyoxyethylene sorbitan monostearate - E435 -; Polyoxyethylene sorbitan tristearate - E436 -; Triphosphates, phosphate - E451 -; Polyphosphates - E452 -; Sodium-; Potassium and calcium salts of fatty acids, salts of fatty acids - E470A -; Magnesium salts of fatty acids, salts of fatty acids - E470B -; Mono- and diglycerides of fatty acids - E471 -; Acetic acid esters of mono- and diglycerides of fatty acids - E472A -; Lactic acid esters of mono- and diglycerides of fatty acids - E472B -; Citric acid esters of mono- and diglycerides of fatty acids - E472C -; Mono- and diacetyltartaric acid esters of mono- and diglycerides of fatty acids - E572E - sugar esters of fatty acids - E473 -; Sugar glycerides - E474 -; Polyglycerol esters of fatty acids - E475 -; Polyglycerol polyricinoleate - E476 -; Propylene glycol esters of fatty acids - E477 -; Thermooxidised soybean oil with mono- and diglycerides of fatty acids - E479 -; Sodium stearoyl-2-lactylate - E481 -; Calcium stearoyl-2-lactylate - E482 -; Sorbitan monostearate - E491 -; Sorbitan tristearate - E492 -; Sorbitan monolaurate, sorbitan monooleate - E493 -; Sorbitan monopalmitate - E495 -; Fatty acids, fatty acids - E570; Polysorbate 20; Polysorbate 40; Polysorbate 60; Polysorbate 80; Etc.

• „Butz-Hoffersche-Formel“: $$1-\left(\frac{x\ast ASC}{SHU}+\frac{x\ast ASC}{SHU}\ast EG\right)=AnteilWasser$$
  
  $$\frac{x\ast ASC}{SHU}\ast EG=AnteilEmulgator$$
  
  $$\frac{x\ast ASC}{SHU}=Anteil\text{ Ö}l$$
  

The "Butz-Hoffersche formula", which is mentioned below, applies to all emulsions which are brought into contact with scovillins on the basis of natural, semisynthetic or synthetic emulsifiers. It determines the proportion of water in the finished emulsion (final product) as a function of the degree of severity of the extracted high-purity scovillin (SHU) and the desired degree of severity of the final emulsion (x * ASC):

• "Butz-Hoffersche formula": $$1-\left(\frac{x*ASC}{SHU}+\frac{x*ASC}{SHU}*eG\right)=AnteilWasser$$
  
  $$\frac{x*ASC}{SHU}*eG=AnteilemulGatOr$$
  
  $$\frac{x*ASC}{SHU}=Anteil\text{Ö}l$$
  

• ASC = Aquatisches Scovillin, eine Schärfeeinheit für Hochreine Aquatische Scovilline Compositionen (HASC) mit einem Schärfemaß von 1.000 Scoville
• x = Faktor, der multipliziert mit dem Wert ASC die gewünschte Endschärfe des fertigen Produkts angibt
• SHU = Scoville Heat Unit, d.h. Schärfemaß des extrahierten hochreinen Scovillin
• EG = Verhältnis von Emulgator zum ölhaltigen Extrakt

Where:

• ASC = Aquatic Scovillin, a Sharpness Unit for High Purity Aquatic Scovillin Compositions (HASC) with a Thickness of 1000 Scoville
• x = factor which, multiplied by the value ASC, indicates the desired final sharpness of the finished product
• SHU = Scoville Heat Unit, ie the sharpness of the extracted high purity scovillin
• EG = ratio of emulsifier to oil-containing extract

The application of the formula is shown by the following calculation:

10 kilograms of the final product are produced. Based on the example given below, the following quantities were determined for a desired target acutance of 1,000,000 Scoville or 1,000 ASC for a functioning oil-in-water emulsion. In addition, it is believed that a natural Emulsifier, eg lecithin is used, which is supplied in the ratio of one to ten of the mixed amount of oil (scovillin).

Calculation example:

$$\begin{array}{l}1-\left(\left(1000*\text{ASC}/\mathrm{16,000,000}\right)+\left(1000*\text{ASC / 16}\text{.000}\text{.000}\right)*\left(1/10\right)\right)\hfill \\ =1-\left(\left(1000000/\mathrm{16,000,000}\right)+\left(1000000\text{/ 16}\text{.000}\text{.000}\right)*\left(1/10\right)\right)\hfill \\ =1-\left(\left(1/16\right)+\left(1+160\right)\right)\hfill \\ =1-\left(0.0625+0.00625\right)\hfill \\ =0.93125\hfill \end{array}$$

Result:

1. 1) Capsaicin (16,000,000 Scoville) $$0.625\text{kg}=625\text{G}=6.25\%$$
   
2. 2) Emulsifier (lecithin) $$0.0625\text{kg}=62.5\text{G}=0.625\%$$
   
3. 3) water (H2O at a density of 1.0) $$9.3125\text{kg}=9.3125\text{l}=93.125\%$$
   

For the production of 10 kilograms of the desired end product, 9,312.5 g or 9.3125 l of water are required when using 625 g of capsaicin and 62.5 g of emulsifier (lecithin).

For synthetic emulsifiers, the HLB value (HLB stands for hydrophilic-lipophilic balance) of greater than or equal to 13 must be achieved with the finished emulsion. For this purpose, emulsifiers such as polysorbate 20, polysorbate 40, polysorbate 60 or polysorbate 80 are used.

Advantages of the invention

With the method according to the invention, it has become possible to extract scovillins (spars) both in high purity and in high concentration and to bring them into a water-soluble form (HASC). In addition, it is possible to define the parameters necessary for the procedure by means of the "Butz-Hofferschen-Formel" with the aid of the unit of measure ASC. Thus, a use of the product is everywhere where a water solubility is desired and so far could not be realized, such. when used as a beverage or food additive.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• DE 19601482 Al [0013]

Claims (13)

Process for the preparation of high-purity Aquatic Scovillin Compositions (HASC) from ingredients of organic substances containing in-mold, comprising the following process steps: Crushing the biomass, High-pressure extraction of biomass ingredients by means of a supercritical or subcritical gas extracting agent. Adding water to the extracted material with addition of an emulsifier to produce an oil-in-water emulsion. Method according to Claim 1 characterized in that the proportion of water, emulsifier and oil in the finished emulsion is calculated according to the following formula ("Butz-Hoffersche formula"): $$1-\left(\frac{x*ASC}{SHU}+\frac{x*ASC}{SHU}*eG\right)=AnteilWasser$$

$$\frac{x*ASC}{SHU}*eG=AnteilemulGatOr$$

$$\frac{x*ASC}{SHU}=Anteil\text{Ö}l$$

The following applies: ASC = Aquatic Scovillin, a Sharpness Unit for High Purity Aquatic Scovillin Compositions (HASC) with a severity of 1.000 Scoville x = Factor, multiplied by the value ASC indicating the desired final acuity of the finished product SHU = Scoville Heat Unit, ie extracted high purity scovillin EG = ratio of emulsifier to oil-containing extract Method according to one of the preceding claims, characterized in that carbon dioxide is used in the supercritical state as the extraction agent. Method according to one of the preceding claims, characterized in that the extraction temperature: 10 ° C to 120 ° C and the extraction pressure: 50 bar to 2500 bar. Method according to one of the preceding claims, characterized in that the extraction temperature: 40 ° C to 80 ° C and the extraction pressure: 100 bar to 400 bar. Method according to one of the preceding claims, characterized in that the extraction temperature: 38 ° C to 42 ° C and the extraction pressure: 380 bar to 420 bar. Method according to one of the preceding claims, characterized in that the water content of the carbon dioxide is at most 1000 ppm. Method according to one of the preceding claims, characterized in that lecithin is used as emulsifier. Method according to one of the preceding claims, characterized in that as an emulsifier lecithin obtained from organically grown soybean is used. Method according to one of the preceding claims, characterized in that an optionally necessary drying by means of spraying or vacuum process takes place. Method according to one of the preceding claims, characterized by the use of biomass from biological cultivation. Apparatus for carrying out the method according to one of the preceding claims, in particular Claim 2 , Use of the substance produced by the process for the following applications: medicine, admixture of composite materials, cosmetics industry, textile industry, filter technology, construction industry, antifungal, fungicide, repellent, animal defense, crop protection, protective coatings, paints, food, dietary supplements or beverages.