CN105566187A - Method for rapidly preparing high-purity sulforaphane - Google Patents
Method for rapidly preparing high-purity sulforaphane Download PDFInfo
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- CN105566187A CN105566187A CN201510929017.XA CN201510929017A CN105566187A CN 105566187 A CN105566187 A CN 105566187A CN 201510929017 A CN201510929017 A CN 201510929017A CN 105566187 A CN105566187 A CN 105566187A
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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 prods field of deep, specifically a kind of quick method preparing high-purity sulforaphane.
Background technology
Sulforaphen is one of natural product that the cancer-resisting ability that finds in vegetables is up to now the strongest, obvious blocking effect is had to multiple cancer cells, and there is antibacterial, pharmacological action such as raising antioxidant ability of organism and strengthening immunity etc., to human body without obvious untoward reaction, there are the potentiality being developed to new antitumor drug or healthcare products, there are wide market outlook.
Because the pharmacologically active of the sulforaphen of chemosynthesis is obviously on the low side, current sulforaphen is mainly derived from broccoli seed or seedling.Existing great majority research is all extracting directly sulforaphen precursor from brassicaceous vegetable, obtains sulforaphen through hydrolysis.Chinese patent CN102898341A discloses a kind of extracting and purifying method of high-purity sulforaphane, and the party utilizes macroporous resin column chromatography combine with technique alumina dry column chromatography decolouring technology to prepare sulforaphen sterling.Whole process need 1 ~ 2 day, need through macroporous resin gradient elution in this technique long purge process consuming time, complex steps, cost is high, is difficult to carry out suitability for industrialized production.
Subcritical fluids extractive technique is for solvent with the mixing solutions of the fluid of subcritical state or subcritical fluids, with solute in system in succession through lixiviate, evaporate the processes such as precipitation, compression, condensation recovery, from natural product, extract a kind of new technology of target components.When LPG, propane, butane, R600a, DME, R134a and sulfur hexafluoride etc. exist with subcritical fluids state, the diffusion of molecule strengthens, mass transfer velocity is accelerated, and significantly improves the perviousness of low-pole in natural product and apolar substance and dissolving power.Extract under subcritical environment, do not destroy heat-sensitive ingredients, object is complete, the property the changed technology be regarded as environmental protection, having a extensive future.And the extraction of continuous countercurrent extraction technology have applied widely, flexible operation, fast, the advantage such as preparation amount is large, expense is low, environment-friendly high-efficiency.High in order to solve current sulforaphen production technique cost, inefficient problem, the present invention combines sub critical extraction technology and counter-current extraction techniques, greatly cost-saving, enhances productivity, solves the problem of sulforaphen suitability for industrialized production difficulty.
Summary of the invention
The object of the invention is the defect being difficult to suitability for industrialized production in order to solve sulforaphen in prior art, providing a kind of quick method preparing high-purity sulforaphane to solve the problems referred to above.
To achieve these goals, technical scheme of the present invention is as follows:
The quick method preparing high-purity sulforaphane, comprises step successively:
A. extract: load airtight extractor by through the broccoli seed of enzymolysis drying or seedling powder, vacuumize rear injection Extraction solvent by complete for sample submergence, then repeatedly extract;
B. precipitation: extract after terminating, the Extraction solvent containing Caulis et Folium Brassicae capitatae oil is put into evaporating pot, carries out constant temperature reduction vaporization, obtains Caulis et Folium Brassicae capitatae oil, the Extraction solvent after gasification is compressed, filtration, is recovered to solvent storage tank after condensation liquefaction;
C. counter-current extraction, pumps into counter-current extraction tower by the Caulis et Folium Brassicae capitatae obtained in described step B oil and extraction agent and extracts;
D. the mixed solution extracting sulforaphen and the extraction agent obtained in described step C is carried out vacuum concentration.
Preferably, the Extraction solvent in described steps A is sub critical extraction organic solvent, comprises the mixing of one or more in propane, butane, dme, Tetrafluoroethane, ethanol.
Preferably, described sample and Extraction solvent mass ratio are 1:2-1:20, and extraction pressure is 0.1MPa ~ 0.9MPa, extraction time 20min ~ 40min, Extracting temperature 25 DEG C ~ 60 DEG C, extraction time 2 ~ 4 times.
Preferably, the Extraction solvent reclaimed in described step B can be recycled.
Preferably, the extraction agent in described step C is the mixing of a kind of in ethanol, methyl alcohol or two kinds.
Preferably, the ratio of the Caulis et Folium Brassicae capitatae oil in described step C and the flow velocity of extraction agent is 1:2 ~ 1:6, extraction temperature 20 DEG C ~ 30 DEG C.
Preferably, in described step D, the drying temperature of vacuum concentration is 20 DEG C ~ 30 DEG C.
Compared with prior art, beneficial effect of the present invention is: (1) subcritical abstraction technology prepares sulforaphen in conjunction with continuous countercurrent extraction technology, and equipment cost is low, and sulforaphen extraction yield is high, and product purity is higher; (2) traditional extraction and purification process needs 2-3 days, and the present invention is no more than 3 hours the whole technique deadline, and in operating process, temperature is low, ensure that the biological activity of sulforaphen, improves production efficiency, reduce energy consumption, be suitable for suitability for industrialized production.
Embodiment
For making to have a better understanding and awareness constitutional features of the present invention and effect of reaching, illustrating in order to preferred embodiment, being described as follows:
Embodiment 1
A kind of quick method preparing high-purity sulforaphane is:
(1) extract: the broccoli seed 1kg through enzymolysis drying is loaded airtight extractor, vacuumizes, inject 2kg Extraction solvent propane extremely by complete for sample submergence, extraction pressure is 0.1MPa, extraction time 20min, Extracting temperature 25 DEG C, extraction time 2 times;
(2) precipitation: extract after terminating, the Extraction solvent containing Caulis et Folium Brassicae capitatae oil is put into evaporating pot, constant temperature reduction vaporization, obtains Caulis et Folium Brassicae capitatae oil, the Extraction solvent after gasification is compressed, filtration, after condensation liquefaction, is recovered to solvent storage tank;
(3) counter-current extraction, the Caulis et Folium Brassicae capitatae obtained in step (2) oil and extraction agent are pumped into counter-current extraction tower and extracts, extraction agent is ethanol, and the ratio of the flow velocity of Caulis et Folium Brassicae capitatae oil and extraction agent is 1:2, extraction temperature 20 DEG C
(4) will extract the mixed solution 20 DEG C of vacuum concentration of sulforaphen and the extraction agent obtained in step (3), the sulforaphen purity obtained after testing is 97.2%, and extraction yield is 1.21%.
Embodiment 2
A kind of quick method preparing high-purity sulforaphane is:
(1) extract: the Caulis et Folium Brassicae capitatae seedling 1kg through enzymolysis drying is loaded airtight extractor, vacuumizes, inject 20kg Extraction solvent butane extremely by complete for sample submergence, extraction pressure is 0.9MPa, extraction time 40min, Extracting temperature 60 DEG C, extraction time 4 times;
(2) precipitation: extract after terminating, the Extraction solvent containing Caulis et Folium Brassicae capitatae oil is put into evaporating pot, constant temperature reduction vaporization, obtains Caulis et Folium Brassicae capitatae oil, the Extraction solvent after gasification is compressed, filtration, after condensation liquefaction, is recovered to solvent storage tank;
(3) counter-current extraction, the Caulis et Folium Brassicae capitatae obtained in step (2) oil and extraction agent are pumped into counter-current extraction tower and extracts, extraction agent is ethanol, and the ratio of the flow velocity of Caulis et Folium Brassicae capitatae oil and extraction agent is 1:6, extraction temperature 30 DEG C
(4) will extract the mixed solution 30 DEG C of vacuum concentration of sulforaphen and the extraction agent obtained in step (3), the sulforaphen purity obtained after testing is 97.1%, and extraction yield is 2.1 ‰.
Embodiment 3
A kind of quick method preparing high-purity sulforaphane is:
(1) extract: the broccoli seed 3kg through enzymolysis drying is loaded airtight extractor, vacuumizes, inject 10kg Extraction solvent dme extremely by complete for sample submergence, extraction pressure is 0.5MPa, extraction time 30min, Extracting temperature 35 DEG C, extraction time 3 times;
(2) precipitation: extract after terminating, the Extraction solvent containing Caulis et Folium Brassicae capitatae oil is put into evaporating pot, constant temperature reduction vaporization, obtains Caulis et Folium Brassicae capitatae oil, the Extraction solvent after gasification is compressed, filtration, after condensation liquefaction, is recovered to solvent storage tank;
(3) counter-current extraction, the Caulis et Folium Brassicae capitatae obtained in step (2) oil and extraction agent are pumped into counter-current extraction tower and extracts, extraction agent is methyl alcohol: ethanol=5:5, and the ratio of the flow velocity of Caulis et Folium Brassicae capitatae oil and extraction agent is 1:4, extraction temperature 25 DEG C
(4) the mixed solution 25 DEG C of vacuum concentration of sulforaphen and the extraction agent obtained will be extracted in step (3).
The sulforaphen purity obtained after testing is 97.7%, and extraction yield is 1.25%.
Embodiment 4
A kind of quick method preparing high-purity sulforaphane is:
(1) extract: the Caulis et Folium Brassicae capitatae seedling 3kg through enzymolysis drying is loaded airtight extractor, vacuumizes, inject 30kg Extraction solvent Tetrafluoroethane extremely by complete for sample submergence, extraction pressure is 0.7MPa, extraction time 35min, Extracting temperature 40 DEG C, extraction time 2 times;
(2) precipitation: extract after terminating, the Extraction solvent containing Caulis et Folium Brassicae capitatae oil is put into evaporating pot, constant temperature reduction vaporization, obtains Caulis et Folium Brassicae capitatae oil, the Extraction solvent after gasification is compressed, filtration, after condensation liquefaction, is recovered to solvent storage tank;
(3) counter-current extraction, the Caulis et Folium Brassicae capitatae obtained in step (2) oil and extraction agent are pumped into counter-current extraction tower and extracts, extraction agent is methyl alcohol: ethanol=3:7, and the ratio of the flow velocity of Caulis et Folium Brassicae capitatae oil and extraction agent is 1:5, extraction temperature 27 DEG C
(4) the mixed solution 25 DEG C of vacuum concentration of sulforaphen and the extraction agent obtained will be extracted in step (3).
Sulforaphen extract sample high pressure liquid chromatograph embodiment 4 obtained detects purity, chromatographic condition: analytical column Shim-packVP-ODSC18(φ 150mm × 4.6mm, 10 μm; ); Column temperature 30 DEG C; Moving phase: acetonitrile: water=7:3; Flow velocity: 0.8mL/min; Applied sample amount is 20 μ L, determined wavelength 254nm.
The sulforaphen purity obtained after testing is 97.4%, and extraction yield is 2.3 ‰.
More than show and describe ultimate principle of the present invention, principal character and advantage of the present invention.The technician of the industry should understand; the present invention is not restricted to the described embodiments; the just principle of the present invention described in above-described embodiment and specification sheets; the present invention also has various changes and modifications without departing from the spirit and scope of the present invention, and these changes and improvements all fall in claimed scope of the present invention.The protection domain of application claims is defined by appending claims and equivalent thereof.
Claims (7)
1. prepare a method for high-purity sulforaphane fast, it is characterized in that, comprise step successively:
A. extract: load airtight extractor by through the broccoli seed of enzymolysis drying or seedling powder, vacuumize rear injection Extraction solvent by complete for sample submergence, then repeatedly extract;
B. precipitation: extract after terminating, the Extraction solvent containing Caulis et Folium Brassicae capitatae oil is put into evaporating pot, carries out constant temperature reduction vaporization, obtains Caulis et Folium Brassicae capitatae oil, the Extraction solvent after gasification is compressed, filtration, is recovered to solvent storage tank after condensation liquefaction;
C. counter-current extraction, pumps into counter-current extraction tower by the Caulis et Folium Brassicae capitatae obtained in described step B oil and extraction agent and extracts;
D. the mixed solution extracting sulforaphen and the extraction agent obtained in described step C is carried out vacuum concentration.
2. the quick method preparing high-purity sulforaphane according to claim 1, it is characterized in that, Extraction solvent in described steps A is sub critical extraction organic solvent, comprises the mixing of one or more in propane, butane, dme, Tetrafluoroethane, ethanol.
3. the quick method preparing high-purity sulforaphane according to claim 1, is characterized in that, described sample and Extraction solvent mass ratio are 1:2-1:20, extraction pressure is 0.1MPa ~ 0.9MPa, extraction time 20min ~ 40min, Extracting temperature 25 DEG C ~ 60 DEG C, extraction time 2 ~ 4 times.
4. the quick method preparing high-purity sulforaphane according to claim 1, it is characterized in that, the Extraction solvent reclaimed in described step B can be recycled.
5. the quick method preparing high-purity sulforaphane according to claim 1, is characterized in that, the extraction agent in described step C is the mixing of a kind of in ethanol, methyl alcohol or two kinds.
6. the quick method preparing high-purity sulforaphane according to claim 1, is characterized in that, the ratio of the Caulis et Folium Brassicae capitatae oil in described step C and the flow velocity of extraction agent is 1:2 ~ 1:6, extraction temperature 20 DEG C ~ 30 DEG C.
7. the quick method preparing high-purity sulforaphane according to claim 1, is characterized in that, in described step D, the drying temperature of vacuum concentration is 20 DEG C ~ 30 DEG C.
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Cited By (3)
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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 |
| CN106962972A (en) * | 2017-03-20 | 2017-07-21 | 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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| 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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