CN1613987A - Method extracting onion oil by super-critical carbon dioxide - Google Patents

Abstract

A onion oil-extracting process by supercritical CO2 is carried out by: drying and chopping onions, then extracting with CO2 at the conditions of 38deg.C, 19MPa,150kg/h to obtain onion oil. Its rate of purity is above 99%.Yield is 0.31-0.39%. Operation is friendly and safety. Otherwise, lost of active ingredient is less and yield is high.

Description

The method of extracting onion oil by super-critical carbon dioxide

One, technical field

The present invention adopts the method for extracting onion oil by super-critical carbon dioxide, belongs to the agricultural byproducts processing field, is exclusively used in the deep processing of onion.

Two, technical background

Onion (Allium Cepa L.) has another name called ball green onion, round onions or Onion etc., and the Liliaceae allium is worldwide vegetables.Allium just is considered to have multiple medical active for a long time, wherein is subjected to most numerous investigators' favor with garlic, onion and shallot.The pharmaceutical use of garlic extensively confirmed, and developed sterilant in succession, medicine and healthcare products such as garlicin.Onion is described as " queen in the dish " in American-European countries, its pharmaceutical use has good DEVELOPMENT PROSPECT.Fresh onion contains a large amount of mineral substance, VITAMIN, amino acid and trace element, also contains the volatile oil with multiple effective component.Contained volatile oil mainly is various sulfide in the onion, comprises mercaptan, thioether, dimethyl disulphide etc.The traditional Chinese medical science thinks that the onion nature and flavor are sweet, hot, flat, and effects such as removing heat-phlegm, detoxifcation desinsection are arranged, and has listed onion in " Chinese medicine voluminous dictionary " as one of herbal medicine.

1. the raw material of medicine.Onion powder has sterilization, reducing blood-fat, hypoglycemic, anti-asthma, function such as anticancer.American-European many countries have classified it as the main pharmaceutical raw material of reducing blood-fat, anti-AIDS.

2. onion powder can be used as seasonings.Along with the rise of fast food, ready-to-eat, onion powder is as main non-harmful foodstuff additive, and its demand rapidly increases.Supply falls short of demand always owing to its leaching process more complicated at present domestic and international seasonings market onion powder.

3. onion powder can be used as makeup and products and health products additive agent.The sterilizing ability of onion also is eager to excel than garlic.Utilize the anti-microbial effect of onion powder to can be made into sterilised products such as capsule, the function that makes it have prevention and treat various fungal dermatosis.

Organic solvent extraction method and water at atmospheric pressure vapor distillation extraction method are adopted in the extraction of onion powder at present.The atmospheric steam distillation and extraction method need be at 100 ℃, normal atmosphere about 101kpa is distillation down, often owing to distillation temperature height (100 ℃), sulfocompounds such as active substance thiosulfinate are destroyed by high temperature and resolve into inactive substance, and yield only is about 2.0～2.6 ‰.The organic solvent extraction method is easy to inactive substance in the onion is extracted as small organic molecules such as sugar, amino acid, has brought very big difficulty for separation purification afterwards.And extract insufficient, yield is lower.

Three, summary of the invention

Technical problem: the object of the present invention is to provide a kind of method of extracting onion oil by super-critical carbon dioxide,, the active substance destruction that solution utilizes prior art extraction onion powder to exist is many, yield is low, the ropy shortcoming of onion powder.

Technical scheme:

The method of extracting onion oil by super-critical carbon dioxide comprises:

(1) raw material: yellow onion, purple skin onion, silver skin onion;

(2) drying: with onion lyophilize or seasoning below 60 ℃;

(3) supercritical CO ₂Extract: above-mentioned dried onion sample is dropped into supercritical CO ₂In the extraction plant, regulate 35～40 ℃ of extraction temperature, extracting pressure 16～20Mpa, CO ₂Flow 140～160kg/h, the time is 3-4 hour, directly collects the onion powder crude extract in the extraction kettle outlet with brown wide-necked bottle;

(4) aftertreatment: crude extract extracted 2 times under 25 ℃ of conditions with methylene dichloride in 1: 1 by volume, reclaimed methylene dichloride under 42 ℃ of conditions;

(5) use anhydrous Na ₂SO ₄Slough residual water and obtain pure onion powder.

In the extracting method of above-mentioned onion powder, its supercritical CO ₂Optimum parameter is adjusted to 38 ℃ of extraction temperature, extracting pressure 19Mpa, CO in the leaching process ₂Flow 150kg/h.

Beneficial effect: the method for extracting onion oil by super-critical carbon dioxide of the present invention compared with prior art has following advantage and positively effect:

1, supercritical CO of the present invention ₂Extraction onion powder has advantages such as noresidue, selectivity is strong, effective constituent destruction is few, has good DEVELOPMENT PROSPECT.The onion powder that utilizes technology of the present invention to extract is faint yellow, clarifying oily matter, and pungency is little, has the local flavor of fresh onion; Purity is (elaboration onion powder) more than 99%; Yield is 3.1～3.9 ‰.Concrete composition sees Table 1.

2, having selected suitable extraction conditions is 38 ℃ of extraction temperature, extracting pressure 19MPa, CO ₂Flow 150kg/h.After the onion fragmentation, active precursor material S-alkyl-halfcystine sulfoxide contacts with important katalaze enzyme allinase, and reaction generates thiosulfinate and sulfur-bearing active substances such as methyl, propyl group sulfide.Effective active composition in the onion is exactly these sulfocompounds, and especially those do not have the ruined unsaturated link(age) sulfocompound that contains.This technology has designed 32 ℃, 35 ℃, 38 ℃ three Temperature Treatment, 13 MPa, 16 MPa, three pressure treatment of 19 Mpa, 150kg/h, 200 kg/h, three CO of 250 kg/h in conjunction with pertinent literature by orthogonal experiment ₂Flow is handled, and is that to go out best extraction conditions be 38 ℃ of extraction temperature, extracting pressure 19MPa, CO to index screening with the yield ₂Flow 150kg/h, the extraction time is 3-4 hour, can promote the generation of active substance in the onion to greatest extent, has suppressed the decomposes of these materials simultaneously.

3, adopted suitable organic solvent extraction.Adopted the solvent of methylene dichloride as the purification crude extract.Evidence methylene dichloride polarity is similar to onion powder, onion powder solubleness therein big (the similar principle that mixes), and boiling point (41 ℃) is low, survivable active substance during recovery.

4, improved the yield of onion powder.Because the screening kind that is rich in onion powder adopts supercritical extraction, selectivity is strong, has reduced the destruction of active substance, extracts more thorough; Selected suitable and extraction solvent methylene dichloride like the onion powder polar phase for use, can fully purify.The yield of onion powder of the present invention has improved nearly 40% than existing technology, the yield that makes onion powder brings up to 3.1～3.9 ‰ from 2.2～2.8 ‰, has improved the benefit that onion powder is produced.

5, the quality and the commodity of onion powder have been improved.Improve the kind and the content of active substance in the onion powder, institute carries and has obtained novel substance in the onion powder, promptly 3, ethyl-1, common unsaturated sulfide such as 2 dithienes and 1-propenyl propyl trisulfide thing, diallyl thiosulfinate content has reached 1.69%, 1.86%, 1.45% respectively in addition.The onion powder of supercritical extraction is faint yellow, clarifying oily matter, and pungency is little, has the local flavor of fresh onion; Organic solvent and steam distillation gained onion powder are brown, and pungency is strong, no fresh natural onion local flavor.

6, the present invention adopts suitable onion treatment process, makes precursor substance under the catalysis of allinase, fully is converted into sulfur-bearing active substances such as thiosulfinate; Supercritical extraction has reduced extraction temperature, has reduced active substance and has been destroyed by high temperature; Adopt lower boiling dichloromethane solvent, 42 ℃ the survivable active substance of low temperature when reclaiming organic solvent.Thiosulfinate compounds in the onion powder that extracts as water at atmospheric pressure steam distillation, allyl disulfide, allyl group trisulphide isoreactivity material are destroyed.Contain a large amount of unsaturated link(age) sulfocompounds such as allyl group in the onion powder that this technology obtains, it is less to be enough to illustrate that active substance destroys.

Four, embodiment

Embodiment 1:

(1) raw material: yellow onion;

(2) drying: with onion lyophilize or seasoning below 60 ℃;

(3) supercritical CO ₂Extract: above-mentioned dried onion sample is dropped into HA420-40-96 type supercritical extraction unit (production of Huaan, Nantong supercritical extraction company limited), regulate extraction temperature, extracting pressure and CO ₂Flow makes it to reach 38 ℃ of best extraction parameter extraction temperature, extracting pressure 19Mpa, CO ₂Flow 150kg/h, the time is 3-4 hour, directly collects the onion powder crude extract in the extraction kettle outlet with brown wide-necked bottle;

(4) aftertreatment: crude extract extracted 2 times under 25 ℃ of conditions with methylene dichloride in 1: 1 by volume, reclaimed methylene dichloride under 42 ℃ of conditions;

(5) use anhydrous Na ₂SO ₄Slough residual water and obtain pure onion powder.

The onion powder that extraction obtains is faint yellow, clarifying oily matter, and pungency is little, has the local flavor of fresh onion; Purity is (elaboration onion powder) more than 99%; Yield is 3.1～3.9%.Detect through Agricultural University Of Nanjing's gas chromatography-mass spectrography (GC-MS), methyl sulfide content mass ratio is 35% in the onion powder, and the content of disulfide is 7.17%, and the content of trisulfide is 56.23%, the content of thiosulfinate is 1.69%, and concrete composition sees Table 1.

The present invention is by being that index is tested with the pyruvic acid, and the result shows that pyruvic acid will obviously descend when temperature surpasses 60 ℃.60 ℃ is the critical temperature of onion active substance in therefore definite onion processing; Pyruvic acid occupies very consequence in the onion chemistry, be certain proportionlity with sulfocompound, can be used as the sign of weighing the onion active substance.Test determination the content of pyruvic acid under 20 ℃, 40 ℃, 60 ℃, 70 ℃, 80 ℃ five Temperature Treatment.Determined that by the orthogonal experiment design supercritical extraction parameter in the extraction procedures is 38 ℃ of extraction temperature, extracting pressure 19Mpa, CO ₂Flow 150kg/h, the extraction time is 3-4 hour.

In the extracting method of the described onion powder of the foregoing description, select for use purple skin onion, silver skin onion also can obtain same effect, three kinds of onion kinds are the common variety of selling on the market, convenient and easy, equipment and technology that pre-treatment requires are also fairly simple, the onion powder of this technology extraction gained still all is better than steam distillation and organic solvent extraction onion powder in organoleptic quality on activity substance content and yield, have good market outlook.

Table 1 supercritical CO ₂The component content of extraction onion powder

Content (%)

The molecular formula title

Embodiment 1 embodiment 2 embodiment 3

C ₆H ₆S 3,4-thioxene 6.38 6.20 6.01

C ₂H ₆S ₄Dimethyl tetrasulfide 1.53 1.25 1.16

C ₄H ₁₀S ₂First propyl disulfide thing 0.61 0.85 0.74

C ₄H ₈S ₂Methacrylic based bisulfide 3.29 3.13 2.91

C ₆H ₁₂S ₂1-propenyl propiyl disulfide 2.96 3.04 3.18

C ₆H ₈S ₂3, ethyl-1,2 dithiene 23.55 20.69 22.96

C ₆H ₁₀S ₃First propyl trisulfide thing 1.09 0.91 1.22

C ₆H ₁₀OS ₂Diallyl thiosulfinate 1.69 1.86 1.45

C ₆H ₁₀S ₃Diallyl trisulfide 7.40 8.04 6.62

C ₆H ₁₂S ₃1-propenyl propyl trisulfide thing 37.82 35.73 34.97

C ₂H ₆S ₃Dimethyl trisulfide 0.34 0.28 0.39

C ₆H ₁₄S ₂Dipropyl disulphide 0.31 0.26 0.47

C ₄H ₈S ₃Methylpropenyl trisulphide 9.58 10.25 8.28

C ₃H ₆S ₂1,2-dimercaptopropane 0.41 0.51 0.32

Other (not detecting)------

Claims (2)

1. the method for extracting onion oil by super-critical carbon dioxide comprises:

(1) raw material: yellow onion, purple skin onion, silver skin onion;

(2) drying: with onion lyophilize or seasoning below 60 ℃;

(3) supercritical CO ₂Extract: above-mentioned dried onion sample is dropped into supercritical CO ₂In the extraction plant, regulate 35～40 ℃ of extraction temperature, extracting pressure 16～20Mpa, CO ₂Flow 140～160kg/h, the time is 3-4 hour, directly collects the onion powder crude extract in the extraction kettle outlet with brown wide-necked bottle;

(4) aftertreatment: crude extract extracted 2 times under 25 ℃ of conditions with methylene dichloride in 1: 1 by volume, reclaimed methylene dichloride under 42 ℃ of conditions;

(5) use anhydrous Na ₂SO ₄Slough residual water and obtain pure onion powder.

2. according to the extracting method of the described a kind of onion powder of claim 1, its supercritical CO ₂Optimum parameter is adjusted to 38 ℃ of extraction temperature, extracting pressure 19Mpa, CO in the leaching process ₂Flow 150kg/h.