CN105566187B - Method for rapidly preparing high-purity sulforaphane - Google Patents
Method for rapidly preparing high-purity sulforaphane Download PDFInfo
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- CN105566187B CN105566187B CN201510929017.XA CN201510929017A CN105566187B CN 105566187 B CN105566187 B CN 105566187B CN 201510929017 A CN201510929017 A CN 201510929017A CN 105566187 B CN105566187 B CN 105566187B
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- extraction
- solvent
- broccoli
- sulforaphen
- extractant
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C331/00—Derivatives of thiocyanic acid or of isothiocyanic acid
- C07C331/16—Isothiocyanates
- C07C331/18—Isothiocyanates having isothiocyanate groups bound to acyclic carbon atoms
- C07C331/22—Isothiocyanates having isothiocyanate groups bound to acyclic carbon atoms of an unsaturated carbon skeleton
Abstract
The invention provides a method for rapidly preparing high-purity sulforaphane, which sequentially comprises the following steps of: A. extraction: loading the broccoli seeds or seedling powder subjected to enzymolysis drying into a closed extraction tank, vacuumizing, injecting an extraction solvent to completely immerse the sample, and then extracting for multiple times; B. desolventizing: after extraction, putting an extraction solvent containing the broccoli oil into an evaporation tank, carrying out constant-temperature reduced-pressure evaporation to obtain the broccoli oil, compressing, filtering, condensing and liquefying the gasified extraction solvent, and then recovering the solvent into a solvent storage tank; C. b, countercurrent extraction, namely pumping the broccoli oil obtained in the step B and an extracting agent into a countercurrent extraction tower for extraction; D. and C, carrying out vacuum concentration on the mixed solution of the sulforaphane extracted in the step C and the extracting agent. The invention has the beneficial effects that: (1) the equipment cost is low, the sulforaphane extraction rate is high, and the product purity is high; (2) the production efficiency is improved, and the energy consumption is reduced.
Description
Technical field
The present invention relates to agricultural products field of deep, a kind of specifically quick side for preparing high-purity sulforaphane
Method.
Background technology
Sulforaphen is one of most strong natural products of the cancer-resisting ability found so far in vegetables, to a variety of cancers
Cell has obvious blocking effect, and with antibacterial, the raising pharmacological action such as antioxidant ability of organism and strengthen immunity, it is right
Human body has the potentiality for being developed to new antitumor drug or health products, has wide market prospects without obvious adverse reaction.
Because the pharmacological activity of the sulforaphen of chemical synthesis is substantially relatively low, sulforaphen is mainly derived from broccoli kind at present
Son or seedling.Existing most of researchs are all that sulforaphen precursor is directly extracted from brassicaceous vegetable, are obtained through hydrolysis
Sulforaphen.The A of Chinese patent CN 102898341 disclose a kind of method for extraction and purification of high-purity sulforaphane, and the party utilizes
Macroporous resin column chromatography technology combined aluminum oxide dry chromatography decolouring technology prepares sulforaphen sterling.Whole process needs 1 ~ 2
My god, needed in the technique time-consuming purge process high through macroreticular resin gradient elution, complex steps, cost, it is difficult to industrialized
Production.
Subcritical fluids extractive technique be using the fluid of subcritical state or the mixed solution of subcritical fluids as solvent, with
Solute, in succession by processes such as extraction, evaporation precipitation, compression, condensation recovery, extracts target group in system from natural products
A kind of new technology divided.When LPG, propane, butane, R600a, DME, R134a and sulfur hexafluoride etc. are deposited with subcritical fluids state
When, molecule diffusion enhancing, mass transfer velocity accelerate, to the permeability of low pole in natural products and apolar substance
Significantly improved with solvability.Extracted under subcritical environment, it is complete not destroy heat-sensitive ingredients, purpose thing, is considered as green ring
The property a changed technology protect, having a extensive future.And the extraction of continuous countercurrent extraction technology has applied widely, operation flexibly, soon
Speed, the advantages that preparation amount is big, expense is low, environment-friendly high-efficiency.High in order to solve current sulforaphen production technology cost, efficiency is low
Problem, the present invention combines sub-critical extraction technology and counter-current extraction techniques, greatly cost-effective, improves production efficiency, solution
The problem of sulforaphen industrialized production difficulty of having determined.
The content of the invention
The invention aims to solve the defects of sulforaphen is difficult to industrialized production in the prior art, there is provided a kind of
The quick method for preparing high-purity sulforaphane solves the above problems.
To achieve these goals, technical scheme is as follows：
A kind of quick method for preparing high-purity sulforaphane, includes step successively：
A. extract：Closed extractor will be loaded by the dry broccoli seed of enzymolysis or seedling powder, injected after vacuumizing
Sample is totally submerged by Extraction solvent, is then repeatedly extracted；
B. precipitation：After extraction terminates, the Extraction solvent containing broccoli oil is put into evaporator, constant temperature decompression is carried out and steams
Hair, broccoli oil is obtained, the Extraction solvent after gasification is compressed, filters, is recovered to solvent holding vessel after condensation liquefaction；
C. counter-current extraction, the broccoli obtained in the step B oil and extractant are pumped into counter-current extraction tower and extracted；
D. the mixed liquor of the sulforaphen being obtained by extraction in the step C and extractant is concentrated in vacuo.
Preferably, the Extraction solvent in the step A is sub-critical extraction organic solvent, including propane, butane, diformazan
One or more of mixing in ether, HFC-134a, ethanol.
Preferably, the sample and Extraction solvent mass ratio are 1:2-1:20, extraction pressure is 0.1MPa~0.9
MPa, extraction time 20min~40min, 25 DEG C~60 DEG C of Extracting temperature, extraction time 2~4 times.
Preferably, the Extraction solvent reclaimed in the step B can be recycled.
Preferably, the extractant in the step C is one or two kinds of mixing in ethanol, methanol.
Preferably, the ratio between flow velocity of the broccoli oil in the step C and extractant is 1:2~1:6,20 DEG C of extraction temperature
~30 DEG C.
Preferably, the drying temperature being concentrated in vacuo in the step D is 20 DEG C~30 DEG C.
Compared with prior art, beneficial effects of the present invention are：（1）Subcritical abstraction technology combination continuous countercurrent extraction skill
Art prepares sulforaphen, and equipment cost is low, and sulforaphen recovery rate is high, and product purity is higher；（2）Traditional extraction and purification process needs
2-3 days are taken, the present invention is no more than 3 hours at the whole technique deadline, and temperature is low in operating process, ensure that sulforaphen
Bioactivity, production efficiency is improved, reduce energy consumption, be suitable for industrialized production.
Embodiment
The effect of to make to architectural feature of the invention and being reached, has a better understanding and awareness, to preferable
Embodiment illustrates, is described as follows：
Embodiment 1
It is a kind of it is quick prepare high-purity sulforaphane method be：
（1）Extraction：Closed extractor will be loaded by the dry broccoli seed 1kg of enzymolysis, vacuumized, injection 2kg is carried
Taking solvent propane, extraction pressure is 0.1MPa, extraction time 20min, 25 DEG C of Extracting temperature, is extracted to sample is totally submerged
Number 2 times；
（2）Precipitation：After extraction terminates, the Extraction solvent containing broccoli oil is put into evaporator, constant temperature is evaporated under reduced pressure, obtained
Broccoli oil is obtained, the Extraction solvent after gasification is compressed, filters, after condensation liquefaction, is recovered to solvent holding vessel；
（3）Counter-current extraction, by step（2）In obtained broccoli oil and extractant be pumped into counter-current extraction tower and extracted,
Extractant is that the ratio between ethanol, the oily flow velocity with extractant of broccoli is 1:2,20 DEG C of extraction temperature
（4）By step（3）In 20 DEG C of vacuum concentrations of mixed liquor of the sulforaphen that is obtained by extraction and extractant, after testing
The sulforaphen purity arrived is 97.2%, recovery rate 1.21%.
Embodiment 2
It is a kind of it is quick prepare high-purity sulforaphane method be：
（1）Extraction：Closed extractor will be loaded by the dry broccoli seedling 1kg of enzymolysis, vacuumized, injection 20kg is carried
Taking solvent butane, extraction pressure is 0.9MPa, extraction time 40min, 60 DEG C of Extracting temperature, is extracted to sample is totally submerged
Number 4 times；
（2）Precipitation：After extraction terminates, the Extraction solvent containing broccoli oil is put into evaporator, constant temperature is evaporated under reduced pressure, obtained
Broccoli oil is obtained, the Extraction solvent after gasification is compressed, filters, after condensation liquefaction, is recovered to solvent holding vessel；
（3）Counter-current extraction, by step（2）In obtained broccoli oil and extractant be pumped into counter-current extraction tower and extracted,
Extractant is that the ratio between ethanol, the oily flow velocity with extractant of broccoli is 1:6,30 DEG C of extraction temperature
（4）By step（3）In 30 DEG C of vacuum concentrations of mixed liquor of the sulforaphen that is obtained by extraction and extractant, after testing
The sulforaphen purity arrived is 97.1%, and recovery rate is 2.1 ‰.
Embodiment 3
It is a kind of it is quick prepare high-purity sulforaphane method be：
（1）Extraction：Closed extractor will be loaded by the dry broccoli seed 3kg of enzymolysis, vacuumized, injection 10kg is carried
Taking solvent dimethyl ether, extraction pressure is 0.5MPa, extraction time 30min, 35 DEG C of Extracting temperature, is carried to sample is totally submerged
Take number 3 times；
（2）Precipitation：After extraction terminates, the Extraction solvent containing broccoli oil is put into evaporator, constant temperature is evaporated under reduced pressure, obtained
Broccoli oil is obtained, the Extraction solvent after gasification is compressed, filters, after condensation liquefaction, is recovered to solvent holding vessel；
（3）Counter-current extraction, by step（2）In obtained broccoli oil and extractant be pumped into counter-current extraction tower and extracted,
Extractant is methanol：Ethanol=5:5, the ratio between oily flow velocity with extractant of broccoli is 1:4,25 DEG C of extraction temperature
（4）By step（3）In 25 DEG C of vacuum concentrations of mixed liquor of the sulforaphen that is obtained by extraction and extractant.
The sulforaphen purity obtained after testing is 97.7%, recovery rate 1.25%.
Embodiment 4
It is a kind of it is quick prepare high-purity sulforaphane method be：
（1）Extraction：Closed extractor will be loaded by the dry broccoli seedling 3kg of enzymolysis, vacuumized, injection 30kg is carried
Solvent HFC-134a is taken to sample is totally submerged, extraction pressure is 0.7MPa, extraction time 35min, 40 DEG C of Extracting temperature,
Extraction time 2 times；
（2）Precipitation：After extraction terminates, the Extraction solvent containing broccoli oil is put into evaporator, constant temperature is evaporated under reduced pressure, obtained
Broccoli oil is obtained, the Extraction solvent after gasification is compressed, filters, after condensation liquefaction, is recovered to solvent holding vessel；
（3）Counter-current extraction, by step（2）In obtained broccoli oil and extractant be pumped into counter-current extraction tower and extracted,
Extractant is methanol：Ethanol=3:7, the ratio between oily flow velocity with extractant of broccoli is 1:5,27 DEG C of extraction temperature
（4）By step（3）In 25 DEG C of vacuum concentrations of mixed liquor of the sulforaphen that is obtained by extraction and extractant.
The sulforaphen extract sample high pressure liquid chromatograph that embodiment 4 is obtained detects purity, chromatographic condition：Point
Analyse post Shim-pack VP-ODS C18（φ 150mm × 4.6mm, 10 μm；）；30 DEG C of column temperature；Mobile phase：Acetonitrile：Water=7：3；
Flow velocity：0.8 mL/min；Applied sample amount is 20 μ L, Detection wavelength 254nm.
The sulforaphen purity obtained after testing is 97.4%, and recovery rate is 2.3 ‰.
General principle, principal character and the advantages of the present invention of the present invention has been shown and described above.The technology of the industry
For personnel it should be appreciated that the present invention is not limited to the above embodiments, that described in above-described embodiment and specification is the present invention
Principle, various changes and modifications of the present invention are possible without departing from the spirit and scope of the present invention, these change and
Improvement is both fallen within the range of claimed invention.The protection domain of application claims by appended claims and its
Equivalent defines.
Claims (6)
- A kind of 1. method for preparing sulforaphen, it is characterised in that comprise the following steps successively：A. extract：Closed extractor will be loaded by the dry broccoli seed of enzymolysis or seedling powder, extraction is injected after vacuumizing Sample is totally submerged by solvent, and Extraction solvent is sub-critical extraction solvent, and the sample is 1 with Extraction solvent mass ratio:2- 1:20, extraction pressure is 0.1MPa~0.9MPa, extraction time 20min~40min, 25 DEG C~60 DEG C of Extracting temperature, is extracted secondary Number 2~4 times；B. precipitation：After extraction terminates, the Extraction solvent containing broccoli oil is put into evaporator, constant temperature reduction vaporization is carried out, obtains Broccoli oil is obtained, the Extraction solvent after gasification is compressed, filters, is recovered to solvent holding vessel after condensation liquefaction；C. counter-current extraction, the broccoli obtained in the step B oil and extractant are pumped into counter-current extraction tower and extracted；D. the mixed liquor of the sulforaphen being obtained by extraction in the step C and extractant is concentrated in vacuo.
- 2. a kind of method for preparing sulforaphen according to claim 1, it is characterised in that the extraction in the step A is molten Agent includes one or more of mixing in propane, butane, dimethyl ether, HFC-134a, ethanol.
- 3. a kind of method for preparing sulforaphen according to claim 1, it is characterised in that is reclaimed in the step B carries Solvent is taken to can be recycled.
- A kind of 4. method for preparing sulforaphen according to claim 1, it is characterised in that the extractant in the step C For one or two kinds of mixing in ethanol, methanol.
- A kind of 5. method for preparing sulforaphen according to claim 1, it is characterised in that the broccoli in the step C The ratio between flow velocity of oil and extractant is 1:2~1:6,20 DEG C~30 DEG C of extraction temperature.
- 6. a kind of method for preparing sulforaphen according to claim 1, it is characterised in that be concentrated in vacuo in the step D Drying temperature be 20 DEG C~30 DEG C.
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| CN106588724A (en) * | 2016-12-02 | 2017-04-26 | 湖南农业大学 | Method for preparing sulforaphen by virtue of subcritical fluid extraction |
| CN106962972B (en) * | 2017-03-20 | 2018-03-27 | 河南中烟工业有限责任公司 | A kind of counterextraction method for lifting discarded tobacco leaf quality |
| CN110122738A (en) * | 2019-06-12 | 2019-08-16 | 合肥工业大学 | A kind of high sulforaphen content broccoli and preparation method and application |
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| CN101120948A (en) * | 2006-08-08 | 2008-02-13 | 普文英 | Compound composition with chemical protecting, cancer preventing and treating use |
| US8697150B2 (en) * | 2010-03-31 | 2014-04-15 | The Procter & Gamble Company | Process of extracting isothiocyanates |
| EP2704587B1 (en) * | 2011-05-03 | 2017-08-16 | Københavns Universitet | A process for the manufacture of products from cruciferous crops |
| CN102871066A (en) * | 2011-07-11 | 2013-01-16 | 浙江科技学院 | Preparation of food-grade natural isorhodanate by application of supercritical CO2 extraction technology |
| CN104086468A (en) * | 2014-05-22 | 2014-10-08 | 浙江大学苏州工业技术研究院 | Method for supercritical carbon dioxide extraction of sulforaphane |
| CN104059947A (en) * | 2014-06-03 | 2014-09-24 | 重庆海巨农业发展有限公司 | Method for preparing high-purity sulforaphane |
| CN104152504A (en) * | 2014-08-03 | 2014-11-19 | 重庆海巨农业发展有限公司 | New preparation method of 1-isothiocyanic acid-4-methanesulfonyl-(2-ene) butane |
| CN104372045B (en) * | 2014-11-10 | 2017-06-20 | 安徽大学 | A kind of preparation method of high-purity sulforaphane |
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Effective date of registration: 20220507 Address after: 230000 No. 188, Jiulong Road, Taohua Town, Feixi County, Hefei City, Anhui Province Patentee after: Anhui bensentang Biotechnology Co.,Ltd. Address before: 230000 Room 405, anda Science Park, No. 2, Tianda Road, high tech Zone, Hefei, Anhui Patentee before: ANHUI CHINATURE BIOLOGICAL Co.,Ltd. |
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