CN1225528C - Supercritical CO2 extraction process for preparing ant oil - Google Patents

Supercritical CO2 extraction process for preparing ant oil Download PDF

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CN1225528C
CN1225528C CN 200410015825 CN200410015825A CN1225528C CN 1225528 C CN1225528 C CN 1225528C CN 200410015825 CN200410015825 CN 200410015825 CN 200410015825 A CN200410015825 A CN 200410015825A CN 1225528 C CN1225528 C CN 1225528C
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ant
extraction
oil
supercritical
powder
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CN1557924A (en
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沈立荣
任玉翠
来鸽飞
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Zhejiang University ZJU
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Zhejiang University ZJU
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Abstract

The present invention discloses a production method for extracting ant oil by supercritical CO2. The production method comprises the following steps: dry ants are pulverized into powder with the particle size of 40 to 80 meshes, continuous extraction is carried out at the temperature of 30 to 50 DEG C under the pressure of 25 to 35MPa for 1.5 to 2.5 hours by a supercritical CO2 extraction apparatus when the flow speed of CO2 is 18 kg/hr. The optimum condition comprises the following: the extraction temperature is 50 DEG C, the extraction pressure is 30Mpa, and the extraction time is 2 hours. Extracted ant oil is a red brown oily liquid with specific acid fragrance of ants at normal temperature, and the extracted ant oil has the advantages of good quality, low lead content, reservation of a certain amount of trace elements, such as zincum, manganese, etc., the reservation of natural aromatic ingredients and the bioactivity of volatile ingredients of ants, no environmental pollution, easy operation, etc. The present invention solves the problems that ant medicines and ant health foods, which are processed by the traditional method, has the long-standing disadvantages of high lead content, anaphylactic protein containing, poor mouth feel, large taken dosage, hypersensitivity and digestive tract reaction for some people, etc., and the ant oil has residual solvent when extracted by organic solvent.

Description

Supercritical CO 2The production method of extraction ant oil
Technical field
The present invention relates to a kind of supercritical CO 2The production method of extraction ant oil.
Background technology
Ant is with a long history in China as food and medicine, and document " all gift heavenly officials " and " in the Book of Rites then " record is arranged the earliest: " sandbar fish or meat paste (sauce that ant egg is made) is presented food for the emperor." claiming that ant is to claim in profound coltfoal, the Qing Dynasty's Zhao Xuemin supplementary Amplifications of the Compendium of Materia Medica that the ant ovum is a ZHUANGYUANZI in Ming Dynasty's LI Shi-Zhen Compendium of Material Medica, nature and flavor are sweet flat, can beneficial strengths, damp color (beauty treatment), lactagogue juice is used for insufficiency of vital energy and blood after being ill, puerperal hypogalactia etc.Modern " Chinese medicine voluminous dictionary " (version in 1986, Shanghai science tech publishing house) included the record that Formica fusca is used as medicine.In some places of China, the custom that eats ant as the Yunnan the Dais remains always.External Mexican, African Ghanaian also have the custom of edible ant.
Formica fusca (polyrhachis) Polyrhachis vicina Roger is the medicinal and edible ant that is distributed widely in wide geographic area and Zhejiang Province on the south China the Changjiang river.Since the 1980s, Colleges Of Traditional Chinese Medicine Of Guangxi is old to be that [old be favour to favour, medicinal research-protein and the amino acid analysis of ant, the Guangxi Chinese materia medica, the 2nd phase of nineteen eighty-three], the Wang Zhong of Air Force Aviation Medical Inst. [Wang Zhong, Wang Zhenguo, Gu Shuncai, the composition analysis of big Formica fusca chloroform extract.Chinese materia medica research, 1997 the 3rd phases], Wu Zhicheng [Wu Zhicheng, ant and ant therapy, Shanghai scientific popularization press, 1994] etc. report, Formica fusca contains protein 42～67%, amino acid/11 is more than 8 kinds, 31 kinds of trace elements such as zinc, manganese, phosphorus, iron, calcium, aluminium, magnesium, VA, VD, VE, VB 1, VB 2, and VB 12Etc. VITAMIN, formic acid, glucide, lipid acid such as oleic acid, linolic acid; Have calmness, anti-inflammatory, relieving asthma, spasmolysis, anti-stress, ease pain, protect liver, enhancing and adjusting immunologic function, delay senility, kidney invigorating and YANG supporting, pharmacological action such as promoting blood circulation and removing blood stasis; This ant is applied to disease treatments such as rheumatoid arthritis, hepatitis B, diabetes and has unusual effect.In recent years, Beihua University is old to wait [Chen Jing, Song Wengang, Zhang Xiaogang quietly, the external tumor-inhibiting action research of polyrhachis, Beihua University's journal (natural science edition), 2000 the 5th phases] do to suppress the tumour test with the alcohol extract of this ant, discovery is to the toxic effect of mouse ascites sarcoma cell, to Mouse Liver oncocyte, mouse leukemia cell DNA are synthetic obvious restraining effect arranged; Old body interior inhibition test [Chen Jing, Guo Hong, Liu Muqing, the Zhu Jianqiang of waiting quietly, tumor-inhibiting action research in the polyrhachis body, Beihua University's journal (natural science edition), 2000 the 6th phases] show that alcohol extract has the growth of tumour cell of inhibition and prolongs the effect of tumor-bearing mice mean survival time.1992, this ant is classified new resource for food as through the health ministry approval, research and development through two more than ten years, Formica fusca has been widely used in Chinese patent medicine, hospital's Chinese medicine preparation, protective foods and new resource food production, the product that with the Formica fusca is development of raw materials production at present has the profound coltfoal oral liquid of Chinese medicine three kind new medicine compounds, profound seven capsule for treating arthralgia aggravated by cold, and other has immunomodulatory, the oral liquid of functions such as antifatigue, wine, electuary, powder, healthcare products such as capsule and teabag, not only quantity is many, market is big, also has good economic benefit [Shen Lirong, Ren Yucui, China's development and use edible and medical ant make progress.Insect knowledge, 1999 the 4th phases].In recent years, the ant health product have also spread to states such as Japan, the U.S..At Zhejiang Province's Formica fusca-Formica fusca, Zhejiang Province's Chinese medicinal materials standard is listed in Zhejiang Department of Public Health approval, Drug Administration of Shanxi Province's approval in, as hospital preparation with and the prescription medicinal material.
At present, China various places have been carried out medicinal, edible research, the Insecta of development and application, Hymenoptera, Formicidae, propagate artificially or wild edible and medical ant, comprise Formica fusca Polyrhachis vicinaRoger, two prominent thorniness ant Polyrhachis dives Smith, red chest thorniness ant Polyrhachis lamellidensSmith, blood red woods ant Formica sanguinea Latreiller, formica rufa Formica rufa Linnaeus, the hunchbacked ant Camponotus japonicus Mayr Oecophylla smaragdina Oecophylla smaradina ant species such as (Fabricius) of Japan.
Yet, present commercially available ant processed goods major part is with the capsule that the rough machined ant of traditional method does, Formica fusca powder is made, honeyed bolus, cream, Ants Wine etc., complete processing falls behind, product exists content of heavy metal lead too high, contain supersensitivity albumen, mouthfeel is poor, and dose is big, and part crowd has problems such as supersensitivity and digestive tract reaction.[Wang Zhong, Wang Zhenguo, Gu Shuncai, the composition analysis of big Formica fusca chloroform extract such as Wang Zhong in addition.Chinese materia medica research, 1997 the 3rd phases] the Ceng Youyong chloroform is as the report of organic solvent extraction ant volatile oil, but owing to there is organic solvent residual, harmful and to problems such as environment can pollute, common organic solvents extraction can only be as the method for extraction experiments analysis and specimen, and should not use as production method.Patent " Formica fusca extract and preparation thereof " (application number: 92105603.6, publication number CN 1067377A) introduced the method for producing preparations such as oral liquid with the ant ethanol extraction, do not relate to supercritical CO 2The production method of extraction ant oil and preparation thereof.
Summary of the invention
The purpose of this invention is to provide a kind of supercritical CO 2The production method of extraction ant oil.
The step of method is:
1) with Insecta, Hymenoptera, Formicidae, propagate artificially or wild edible and medical ant, comprise that the dry polypide of Formica fusca, two prominent thorniness ant, red chest thorniness ant, blood red woods ant, formica rufa, Japanese hunchbacked ant is processed into dry ant powder,
2) the ant powder is placed CO 2In the supercritical extraction device, CO 2After being condensed into liquid, ice chest enters high-pressure pump, the CO after the pressurization 2Entering the extractor in the extraction plant after the heater via heating, fully contact with wherein Formica fusca powder, is that 30～50 ℃, pressure are 8～40MPa, CO in temperature 2Flow velocity is under the condition of 10～18kg/hr, carries out continuous extraction in 1～3 hour, and top condition is CO 2Flow velocity is 18kg/hr, 50 ℃ of extraction temperature, extracting pressure 30Mpa, 2 hours extraction time.The fats compound that extracts is with CO 2Fluid enters separator, after fats compound is separated, and CO 2Enter ice chest again, obtain ant oil through cycling extraction repeatedly;
Described dry ant powder, its water content are pulverized the back and are used 10～15%, and granularity is 40～80 orders, as the raw material of supercritical extraction.
The used CO of supercritical extraction 2Purity 90～99%, in extracting operation, 90% ethanolic soln that adds 50% ant grain weight in extraction plant is as " entrainment agent ", during each extraction process 2.0 hours.
Ant oil passes through preliminary treatment, batching, mixing, is molded into soft capsule or dripping pill; Perhaps dry, be molded into micro-capsule.Ant oil accounts for 78.5% of weight percent in soft capsule or the dripping pill.
Ant is oily and pass through preliminary treatment, batching, mixing, be molded into soft capsule or dripping pill; Perhaps dry, be molded into micro-capsule.Ant oil accounts for 78.5% of weight percent in soft capsule or the dripping pill.The beta-cyclodextrin of micro-capsule or pure glue are 1: 4 (g/ml) with the ratio of ant oil.
The present invention adopts CO 2Supercritical process extraction ant oil, the ant that has overcome traditional method processing does, Formica fusca powder medicine, the ubiquitous content of heavy metal lead of protective foods are too high, contain supersensitivity albumen, mouthfeel is poor, dose is big, part crowd has supersensitivity and problem such as digestive tract reaction; Dissolvent residual problem when having solved organic solvent extraction, free from environmental pollution; The biological nature that has kept natural aromatic composition and the ant class volatile component of ant makes it become new raw material, the product innovation of nutritive health-care and medicine.
Embodiment
Embodiment 1:
Formica fusca is done impurity elimination, be dried to water content below 10%, being ground into granularity is 40 purpose powder.Use equipment to be the semicontinuous supercritical extraction unit of HL-1/32-50Mpa, mainly be made up of an extractor and three grades of separators, extractor and separator all have chuck, available hot water heating and constant temperature, extractor volume 1L.The extractor charging basket can be adorned 350g ant powder at every turn, and the 600-800 eye mesh screen is housed, and puts a steel wire lump earlier on the bucket end screen cloth, and after jar was gone into Formica fusca powder, a bucket upper port was put a steel wire lump again, and steel wire lump can play when machine moves and intercept the ant fine powder and the effect of blocking pipeline.Then the screen cloth lid is compressed into bucket, in the extractor of again charging basket being packed into.Used CO 2Purity should reach 90～99%.
Selected 3 extraction temperature levels (40 ℃, 45 ℃, 50 ℃), 3 extracting pressure levels (25,30,35Mpa), 3 extraction time horizons (1.5 hours, 2 hours, 2.5 hours), according to orthogonal design method by table L9 (3 3) arrange test, serve as to investigate index with the volatile oil yield, the level of factor arrangement sees Table 1, divides and operates for 9 times, takes statistics then and data analysis is compared, and draws optimum extraction condition.The unified CO that sets of each time operation 2Flow is 18kg/hr, and the separation reactor I temperature is that 45 ℃, pressure are 8Mpa, and separator II temperature is that 40 ℃, pressure are 6Mpa, and separator III temperature is that 33 ℃, pressure are 5Mpa.Each supercritical CO 2Extraction procedure: CO 2Steel cylinder → refrigeration system → high-pressure pump → extractor → separator I → separator II → separator III → refrigeration system (circulation).After each equipment operation, earlier extraction kettle → separator is carried out preheating, basin cools off, and when temperature reaches preset temperature, opens CO 2Gas cylinder is supplied gas, and opens high-pressure pump and boost, and when reaching predetermined pressure, the beginning cycling extraction is regulated CO 2Flow, constant temperature and pressure is collected volatile oil from separation reactor I after the extraction scheduled time.After the extraction scheduled time, with the CO of fats extract 2Fluid enters separator behind throttle expansion valve, in separator, because pressure reduces, temperature raises, and fluid density reduces, and is dissolved in CO in a large number 2Lipoid material in the fluid will be separated, and CO 2Fluid is got back to ice chest behind under meter, form circulation, carries out the extraction second time again, also can carry out the extraction more than three times by that analogy, most of extract enters separator I, can open separator I valve after each extraction is finished, and ant oil is collected in the plastic containers.
Orthogonal experiments is listed in table 2,9 groups the test in, the yield of ant oil be minimum be 11.43%, the highest
Table 1 Formica fusca supercritical extraction level of factor table
Level Factor
Temperature A (℃) Pressure B (Mpa) Time C (h)
1 2 3 40 45 50 25 30 35 1.5 2.0 2.5
Table 2 Formica fusca supercritical extraction orthogonal experiments
Test number Factor Volatile oil yield (%)
A B C
1 2 3 4 5 6 7 8 9 1 2 3 1 2 3 1 2 3 1 1 1 2 2 2 3 3 3 3 1 2 2 3 1 3 1 2 11.43 14.29 13.14 12.28 13.42 13.42 13.14 13.42 14.29
K 1 K 2 K 3 38.86 39.12 40.85 36.85 41.13 40.85 38.27 40.86 39.70
k 1 k 2 k 3 12.95 13.04 13.62 12.28 13.70 13.61 12.75 13.62 13.23
R 1.99 4.28 0.87
Be 14.29%, normal temperature is the red-brown oily liquids down, and temperature is the peptone shape when being lower than 4 ℃, has fragrant smell, the free from extraneous odour grown of the distinctive acid of ant.K in the table 2 1, K 2, K 3Be the summation of respective horizontal gained volatile oil yield, k 1, k 2k 3Be respectively K 1, K 2, K 3Mean value, R is extreme difference, i.e. k Max-K MinAs seen from Table 2: (A) k 3＞k 2＞k 1, (B) k 2＞k 3＞k 1, (C) k 2＞k 3＞k 1, therefore, the best of breed extraction conditions of volatile oil is A 3B 2C 2, i.e. 50 ℃ of extraction temperature, extracting pressure 30Mpa, 2 hours extraction time; R value B＞A＞C promptly is arranged in order and is extracting pressure, extraction temperature, extraction time by the size that influences to the result.
Embodiment 2:
Operate according to the optimum extraction condition that embodiment 1 orthogonal experiments is drawn.Earlier Formica fusca is done impurity elimination, be dried to water content 10%, being ground into granularity is 80 purpose powder, use equipment to be the semicontinuous supercritical extraction unit of HL-1/32-50Mpa, this device mainly is made up of an extractor and three grades of separators, extractor and separator all have chuck, available hot water heating and constant temperature, extractor volume 1L.Getting purity ready is 90～99%CO 2350g ant powder is put into the extractor charging basket by embodiment 1 requirement, in the extractor of again charging basket being packed into.
From steel cylinder CO 2After ice chest is condensed into liquid, enter high-pressure pump, the CO after the pressurization 2Enter extractor after the heater via heating, fully contact with wherein Formica fusca powder, at CO 2Flow is 18kg/hr; Extraction temperature is that 50 ℃, extracting pressure are 30Mpa; Separator I temperature is that 45 ℃, pressure are 8Mpa, and separator II temperature is that 40 ℃, pressure are 6Mpa, and separator III temperature is that 33 ℃, pressure are under the condition of 5Mpa, extracts 2.0 hours, with the CO of fats extract 2Fluid enters separator behind throttle expansion valve, in separator, because pressure reduces, temperature raises, and fluid density reduces, and is dissolved in CO in a large number 2Lipoid material in the fluid will be separated, and CO 2Fluid is got back to ice chest behind under meter, form circulation, carries out the extraction second time again, also can carry out the extraction more than three times by that analogy, and the extraction time is 2.0 hours at every turn.Most of extract enters separator I, after finishing, extraction opens separator I valve, ant oil is collected in the plastic containers, get ant oil 52.5g, yield is 15.0% of an ant grain weight, and normal temperature is the red-brown oily liquids down, and temperature is the peptone shape when being lower than 4 ℃, have fragrant smell, the free from extraneous odour grown of the distinctive acid of ant.
The ant oil that supercritical extraction obtains adopts Agilent 6890N type chromatogram and 5973 type GC-MS (GC-MS) to detect, identify 51 compositions (seeing attached list 3), main component is followed successively by 9-18 carbon monoenoic acids [E] (45.10%), 9-alkene oleic acid-second fat (9.30%), cholesterol (6.00%), palmitinic acid (4.96%), 13,17-dimethyl hentriacontane (2.09%), 9-octyl group heptadecane (2.04%), ethyl palmitate (1.44%), 9-alkene oleic acid (1.41%), linolic acid (1.15%) etc.Wherein compositions such as 9-alkene oleic acid-second fat, cholesterol, palmitinic acid, ethyl palmitate, 9-alkene oleic acid, linolic acid do not appear in the newspapers in the past as yet in the ant
Its main component and with the ant oil base of extracted with diethyl ether this is consistent; But latter's gained composition kind is 37 (table 4), is less than the number of components of supercritical extraction ant oil.The CO that subordinate list 3 is measured for GC-MS 2The supercritical extraction ancient cooking vessel
The CO that table 3 GC-MS measures 2Supercritical extraction Formica fusca oil component
The composition sequence number Peak Peak No Retention value Retention Time (min) Compound C ompound Molecular formula Molecular formula Relative content Relative Contents (%) Degree of conformity Quality)
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 3 5 6 7 8 9 10 11 12 13 20 22 27 28 30 34 35 36 38 20.40 25.95 26.39 26.50 26.90 29.83 30.00 30.10 30.21 30.56 38.99 40.38 42.07 42.25 42.39 43.55 43.60 43.68 44.42 8-Heptadecane 8-17 alkene Hexadecenoic acid, Z-11 Z-11-16 carbon monoenoic acid n-Hexadecanoic acid palmitinic acid Ethyl 9-hexadecenoate 9-16 carbon monoenoic acid ethyl ester Hexadecanoic acid, Ethyl esert ethyl palmitate 9-Octadecenoic acid[E] 9-E-16 carbon monoenoic acids (alkene oleic acid) 9,12-Octadecadienoic acid[Z, Z] linolic acid (9,12,-Z, the Z-octadecadienoic acid) Ethyl oleate 9-alkene oleic acid-second fat Oleic acid 9-alkene oleic acid Octadecadienoic acid, Ethyl ester stearic acid second fat, Pentadecane, 8-hexyl 8-hexyl pentadecane Heptadecane, 3-methyl 3-methyl heptadecane 1-Hexacosen 1-cerotene 1-Octadecanethiol 1-nonadecane mercapto alcohol-10-Methylnonadecane 10-methyl nonadecane 9-Nonadecene 9-19 alkene-Nonacosanol triacontanol price quote 1-Docosene 1-docosene 17-(1,5-Dimethylhexyl)-10,13-dime1 C 17H 34 C 16H 30O 2 C 16H 32O 2 C 18H 34O 2 C 18H 36O 2 C 18H 34O 2 C 18H 32O 2 C 20H 38O 2 C 18H 34O 2 C 20H 40O 2 C 21H 44 C 18H 38 C 26H 52 C 19H 39SH C 20H 42 C 19H 38 C 30H 62O C 22H 44 C 27H 46O 0.12 0.44 4.96 0.78 1.44 45.10 1.15 9.30 1.41 0.43 0.58 0.17 0.53 0.24 0.33 0.28 0.37 0.51 6.00 87 98 99 98 95 99 87 99 96 96 90 91 89 97 80 92 83 91 93
20 21 22 23 24 other 27 compositions 41 42 43 44 47 45.46 46.01 46.83 47.92 48.44 -2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a] phenanthren-3-ol cholesterol Cholesta-3,5-diene 3,5-cholestadiene Nonadecane, 9-methyl 9-methyl nonadecane 1-Octadecanethiol 1-octadecane mercapto alcohol 13,17-Dimethylhentriacontane 13,17-dimethyl hentriacontane Heptadecane, 9-octyl-9-octyl group heptadecane straight chain high-carbon alkanes C 29H 46 C 20H 42 C 18H 37SH C 33H 68 C 25H 52 1.04 0.41 0.23 2.09 2.04 16.33 97 90 91 93 86
Table 4 GC-MS measures the Formica fusca oil component of extracted with diethyl ether
The composition sequence number Peak Peak No Retention value Retention Time (min) Compound C ompound Molecular formula Molecular formula Relative content Relative Contents (%) Degree of conformity Quality (%)
1 2 3 4 5 6 7 8 9 10 11 2 5 7 8 9 10 11 20 21 24 25 10.52 20.41 25.89 26.29 29.83 30.00 30.09 41.73 42.25 43.55 43.60 2-Cyclohexen-1-ol 3-Hexadecene 3-hexadecylene 9-Hexadecenoic acid. 9-16 carbon monoenoic acid n-Hexadecanoic acid palmitic acid 9-Octadecenoic acid[E] 9-E-16 carbon monoenoic acids (alkene oleic acid) Octadecadienoic acid oleic acid Ethyl 9-octadecenoate 9-alkene oleic acid-second fat Heptadecane, 9-cctyl-9-octyl group heptadecane Cyclotriacontane ring melissane 1-Nonadecene 1-19 alkene-1-Docosene 1-docosene C 6H 10O C 16H 33 C 16H 30O 2 C 16H 32O 2 C 18H 34O 2 C 18H 36O 2 C 20H 38O 2 C 25H 52 C 30H 60 C 19H 38 C 22H 45 0.33 0.41 0.30 3.30 35.70 2.63 0.91 3.74 0.24 0.44 0.56 53 90 42 96 99 70 58 93 90 89 91
12 13 14 15 16 17 18 other 19 compositions 27 30 31 32 36 37 39 44.42 45.46 46.02 46.83 48.62 49.32 52.94 17-(1,5-Dimethylhexyl)--10,13-dimethy 3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a] phenanthren-3-ol cholesterol Cholesta-3,5-diene 3,5-cholestadiene Heptadecane, 2-methyl-2-methyl heptadecane Z-5-Nonadecene Z-5-19 alkene Pentadecane, 8-hexyl-Sitosterol acetate acetate Sitosterol ester 13,17-Dimethylhentriacontane 13,17-dimethyl hentriacontane straight chain high-carbon alkanes C 27H 46O C 29H 48 C 18H 38 C 19H 38 C 21H 44 C 29H 52 C 33H 68 10.52 0.39 0.38 2.87 3.07 0.66 2.89 32.42 93 99 89 87 83 64 90
The component list of prominent thorniness ant oil, subordinate list 4 are measured the component list of extracted with diethyl ether Formica fusca oil for GC-MS.
Adopting IRIS Intrepid II type to compose plasma emission spectrometer entirely measures, the ant oil that supercritical extraction obtains contains heavy metal and becomes plumbous 0.80 μ g/g, lead tolerance is lower than limiting the quantity of of national relevant food hygienic standard regulation, reduces more than 1 times than general Formica fusca powder (about leaded 2 μ g/g); Contain zinc 0.54 μ g/g, manganese 0.15 μ g/g simultaneously, promptly kept a certain amount of trace element.
Through the CO that uses of the present invention 2After overcritical Cui gets fats compound, the Formica fusca powder raw material can carry out extraction, the enzymolysis of other effective ingredient again with other method, and and then as the raw material of processing medicine, protective foods, the ant oil that obtains through extraction has kept the biological activity of natural aromatic composition and the ant class volatile component of ant, has quality better, cost is low,, do not contain advantages such as organic dissolvent residual.
Embodiment 3:
Formica fusca is done impurity elimination, be dried to and contain the Heshui amount 10%, being ground into granularity is 40 purpose powder.Use equipment to be the semicontinuous supercritical extraction unit of HL-1/32-50Mpa, getting purity ready is 90～99%CO 2350g ant powder is put into the extractor charging basket by embodiment 1 requirement, in the extractor of again charging basket being packed into.
From steel cylinder CO 2After ice chest is condensed into liquid, enter high-pressure pump, the CO after the pressurization 2Enter extractor after the heater via heating, fully contact with wherein Formica fusca powder, at CO 2Flow is 18kg/hr; Extraction temperature is that 50 ℃, extracting pressure are 30Mpa; Separator I temperature is that 45 ℃, pressure are 8Mpa, and separator II temperature is that 40 ℃, pressure are 6Mpa, and separator III temperature is that 33 ℃, pressure are under the condition of 5Mpa, extracts.After extraction process begins 0.5 hour, in device, add percentage concentration and be 90% ethanolic soln (for ant grain weight amount 50%) as " entrainment agent ".
CO with extract 2Fluid enters separator behind throttle expansion valve, in separator, because pressure reduces, temperature raises, and fluid density reduces, and is dissolved in CO in a large number 2Extract will be separated in the fluid, and CO 2Fluid is got back to ice chest behind under meter, form circulation, carries out the extraction second time again, also can carry out the extraction more than three times by that analogy, and the extraction time is 2.0 hours at every turn.
The ant oil of collecting is handled by distillation, ethanol is reclaimed.The ant oil that supercritical extraction obtains adopts Agilent 6890N type chromatogram and 5973 type GC-MS (GC-MS) combined instruments to detect ethanol and carries the ant oil of extraction secretly, identify palmitinic acid, oleic acid, cholesterol, 3,47 compositions such as 5-cholestadiene, clionasterol, linolic acid, stearic acid second fat (see attached list 5,), its main component and with the ant oil base of extracted with diethyl ether this is consistent, but latter's gained composition kind is 37 (seeing Table 4), is less than the one-tenth mark of supercritical extraction ant oil.Subordinate list 5 is with ethanol entrainment agent CO for GC-MS mensuration 2The component list of supercritical extraction Formica fusca oil, subordinate list 4 are measured the component list of extracted with diethyl ether Formica fusca oil for GC-MS.
The usefulness ethanol that table 5 GC-MS measures is as the CO of entrainment agent 2Supercritical extraction Formica fusca oil component
The composition sequence number Peak Peak No Retention value Retention Time (min) Compound C ompound Molecular formula Molecular formula Relative content Relative Contents (%) Degree of conformity Quality (%)
1 2 3 4 5 6 7 8 9 10 11 4 6 7 8 9 10 12 13 18 25 26 20.41 25.97 26.43 26.90 29.86 30.12 30.56 32.33 38.19 40.81 40.89 3-Heptadecane 3-17 alkene Z-7-Hexadecenoic acid, Z-7-16 carbon monoenoic acid n-Hexadecanoic acid palmitinic acid Hexadecanoic acid, Ethyl esert ethyl palmitate 9-Octadecenoic acid, [E] 9-E-16 carbon monoenoic acids (alkene oleic acid) Ethyl oleate 9-alkene oleic acid-second fat 9-Octadecadienoic acid, (E) stearic acid Dodecane, 2,6,11-trimethyl 2,6,11-trimethyldodecane 17-Pentatriacontene 17-30 pentaene 1-Nonadecene 1-19 alkene 17-pentatriacontene 17-30 pentaenes C 17H 34 C 16H 20O 2 C 16H 32O 2 C 18H 36O 2 C 18H 34O 2 C 20H 38O 2 C 18H 36O 2 C 15H 32 C 35H 70 C 19H 38 C 35H 70 0.21 0.91 9.54 0.37 51.53 6.55 0.14 0.24 0.28 0.11 0.14 99 96 99 99 83 83 94 60 90 92 76
12 13 14 15 16 17 18 19 20 21 22 other 25 compositions 28 33 34 37 39 41 44 47 49 55 56 41.02 42.25 42.30 43.32 43.55 43.70 44.42 45.48 46.84 50.17 53.06 1-Docosanol tricosanol 13-Tertadecene-1-ol acetate 13-tetradecenoic acid ethyl ester 11-Metylnonacosane 11-methyl octacosane gamma,-sitosterol clionasterol 1-Nonadecene 1-19 alkene 17-Pentatriacontene 17-30 pentaene 17-(1,5-Dimethylhexyl)-10,13-dimetl-2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a] phenanthren-3-ol cholesterol Cholesta-3,5-diene 3,5-cholestadiene 1-Octadecene 1-octadecylene Octadecane, 9-ethyl-9-heptyl-9-ethyl, 9-heptyl octadecane A '-Neogammacer-22 (29)-en-ol, Acetate, (3.beta., 21.beta.) straight chain high-carbon alkanes C 23H 46O C 16H 30O 2 C 29H 60 C 29H 50O C 19H 38 C 35H 70 - C 29H 46 C 18H 36 C 27H 58 C 32H 52O 2 0.18 0.17 0.14 0.70 0.28 0.60 4.96 1.09 0.24 0.32 2.35 14.12 89 70 43 99 98 81 92 99 64 38 46
Through the supercritical CO of using of the present invention 2After Cui gets fats compound, the Formica fusca powder raw material can carry out extraction, the enzymolysis of other effective ingredient again with other method, and and then as the raw material of processing medicine, protective foods, the ant oil that obtains through extraction has quality better, cost is low, does not contain advantages such as organic dissolvent residual.
Embodiment 4:
The preparation of ant oil soft capsule (or dropping pill formulation).(1) preparation of content: ant oil is added salad oil, and salad oil accounts for 22.5% of gross weight, and vitamin-E accounts for 0.5%.In temperature is that 40 ℃, pressure are homogeneous under the condition of 6MPa, promptly gets soft capsule content.(2) join glue: sizing material is made up of 55% gelatin, 20% glycerine and 25% water.At first G ﹠ W is added in the impregnation jar, feed steam-heated cal(l)andria to 70～80 ℃, the back that stirs slowly adds gelatin, wants vigorous stirring simultaneously in order to avoid the formation agglomerate.Will continue heating when gelatin adds, when impregnation jar core temperature reaches 90～100 ℃, be incubated 3 hours, it is standby that filtration is cooled to 65 ℃ of left and right sides.(3) prepare before the pill: sizing material is placed be incubated in the appropriate vessel at 60 ℃, it is stand-by in addition content to be put into canned groove.The water dropper temperature is about 50 ℃, and room temperature remains on 10～20 ℃, and 100,000 grades of purification conditions will be arranged.(4) pill: adopt the spinning block platen press, behind the unlatching machine, glue flows through on cylinder, forms certain thickness adhesive tape, enters between wedge shape injector and the cylinder through feeding roller again.Jar is gone into semi-enclosed capsule and pill on the mold filling tube, along with the relative rotation of mold filling cylinder, capsule closed moulding.
Embodiment 5:
The preparation of ant micro-capsule (inclusion compound): take by weighing (60 ℃ in beta-cyclodextrin or pure glue, 2 hours dryings) 20g, add the 400ml aquae destillata, heating for dissolving, slowly add 5ml ant oil, mixing, stirred 1 hour with ultrasonic 20 minutes of Ultrasonic Cleaners when ultrasonic (be controlled at 20 ℃ of water temperatures) or with electric mixer regularly, put refrigerator (4 ℃) then 24 hours, suction filtration is got filter residue, or centrifugal (2500 rev/mins, 10 minutes) taking precipitate, with petroleum ether filter residue or throw out, hung 24 hours, 40 ℃ of constant temperature dryings 4 hours get product.Powdered micro-capsule can be sub-packed in capsule and make capsule or be pressed into tablet.

Claims (4)

1. supercritical CO 2The production method of extraction ant oil, it is characterized in that: the step of method is:
1) with Insecta, Hymenoptera, Formicidae, propagate artificially or wild edible and medical ant, the dry polypide that comprises Formica fusca, two prominent thorniness ant, red chest thorniness ant, blood red woods ant, formica rufa, Japanese hunchbacked ant is processed into dry ant powder, the dry ant powder water content is 10～15%, and granularity is 40～80 orders;
2) dry ant powder is placed supercritical CO 2In the extractor, CO 2After being condensed into liquid, ice chest enters high-pressure pump, the CO after the pressurization 2Entering extractor after the heater via heating, fully contact with wherein Formica fusca powder, is that 30～50 ℃, pressure are 25～35MPa, CO in temperature 2Flow velocity is under the condition of 10～18kg/hr, carries out continuous extraction in 1.5～2.5 hours, and the fats compound that extracts is with CO 2Fluid enters separator, after fats compound is separated, and CO 2Enter ice chest again, obtain ant oil through cycling extraction repeatedly; Ant oil can be measured 51 volatile constituents with the GC-MS method, the used CO of supercritical extraction 2Purity 90～99%, in extracting operation, 90% ethanolic soln that adds 50% ant grain weight in extraction plant is as " entrainment agent ".
2. a kind of supercritical CO according to claim 1 2The production method of extraction ant oil is characterized in that: described ant oil passes through preliminary treatment, batching, mixing, is molded into soft capsule or dripping pill; Perhaps dry, be molded into micro-capsule.
3. a kind of supercritical CO according to claim 2 2The production method of extraction ant oil, it is characterized in that: ant oil accounts for 78.5% of weight percent in described soft capsule or the dripping pill.
4. a kind of supercritical CO according to claim 2 2The production method of extraction ant oil, it is characterized in that: described micro-capsule, beta-cyclodextrin or pure glue are 1: 4 (g/ml) with the ratio of ant oil.
CN 200410015825 2004-01-12 2004-01-12 Supercritical CO2 extraction process for preparing ant oil Expired - Fee Related CN1225528C (en)

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CN100381128C (en) * 2006-05-29 2008-04-16 南京中山制药有限公司 Inclusion compound of ants supercritical extracts and preparation process thereof
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