CN110878093B - Preparation method of high-purity silybin - Google Patents
Preparation method of high-purity silybin Download PDFInfo
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Abstract
The invention discloses a preparation method of high-purity silibinin, which comprises the following steps: (1) superfine grinding: micronizing herba Silybi Mariani, pulverizing to 70-120 mesh, and sieving to obtain pulverized material; (2) countercurrent extraction: adding the crushed material into ethyl acetate, heating to 50-80 ℃, circularly extracting for 1-3h, and concentrating after extraction to obtain a crude silymarin product; (3) and (3) recrystallization: adding the crude silymarin into acetone, dissolving to obtain silymarin acetone solution, adding the silymarin acetone solution into water, and filtering to obtain wet silybin; (4) drying and crushing. The method has simple operation, short time consumption, high extraction rate of silibinin, less solvent residue, and high purity.
Description
Technical Field
The present invention belongs to the field of natural organic chemistry technology. More particularly relates to a preparation method of high-purity silibinin.
Background
Silibinin is a flavonoid extracted and separated from fruit of Silybum marianum (Silybum marianum) of Compositae, has obvious effects of protecting and stabilizing liver cell membrane, improving liver function, reducing enzyme, and preventing enzyme rebound. Silibinin is the main active component of silymarin, which can stabilize hepatic cell membrane, maintain integrity of hepatic cell, prevent toxin from penetrating to destroy liver, accelerate synthesis of DNA (deoxyribonucleic acid) of hepatic cell, prevent liver cirrhosis, fatty liver, cholangitis, psoriasis, etc., and inhibit growth and differentiation of hepatocarcinoma, prostatic cancer, breast cancer and cervical cancer cell. Therefore, silibinin has the effects of protecting normal liver cells and promoting the recovery of damaged cell membranes, and is the flavonoid which is found to have the most curative effect on liver diseases in the world at present.
In the prior art, the industrial extraction method of silybin mainly comprises reflux extraction in an extraction tank, concentration, macroporous resin adsorption and elution. However, the purity of the silybin obtained by the method is not high, and the yield is not high. For example, patent CN107793402A discloses a method for extracting silybin, which comprises dissolving, heating and refluxing, washing with macroporous resin, cooling and crystallizing, and vacuum drying twice to obtain silybin; however, the method has complex operation steps, long extraction time, low yield and low purity of the obtained silybin.
In addition, patent CN102746283A discloses a method for preparing high purity silybin, which comprises dissolving crude silybin in acetone, filtering, concentrating, adding alcohol, cooling, stirring, crystallizing, filtering, washing with alcohol, and drying. However, the method is mainly a refining and purifying process of the silybin, and the obtained product is influenced by the quality of a crude product.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a preparation method of high-purity silibinin aiming at the defects of the prior art, the method is simple and convenient to operate, short in time consumption, and high in extraction rate and purity of the obtained product.
The invention aims to provide a preparation method of high-purity silibinin.
The above purpose of the invention is realized by the following technical scheme:
the invention provides a preparation method of high-purity silibinin, which adopts a preparation process combining superfine grinding and countercurrent extraction and specifically comprises the following steps:
(1) superfine grinding: micronizing herba Silybi Mariani, pulverizing to 70-120 mesh, and sieving to obtain pulverized material;
(2) countercurrent extraction: adding the crushed material into ethyl acetate, heating to 50-80 ℃, circularly extracting for 1-3h, and concentrating after extraction to obtain a crude silymarin product;
(3) and (3) recrystallization: adding the crude silymarin into acetone, dissolving, adding activated carbon for decolorization to obtain silymarin acetone solution, adding the silymarin acetone solution into water, and filtering to obtain wet silybin;
(4) drying and crushing: and drying and crushing the silybin wet product to obtain the silybin.
The method combines superfine grinding and countercurrent extraction, superfine grinding can contact with solvent as much as possible, extraction rate is improved, countercurrent extraction can reduce solvent usage amount, circulation extraction can reduce extraction time, and the obtained silybin has higher purity by using a simpler recrystallization mode.
In order to realize the best extraction effect, the extraction method comprises the following steps:
preferably, the step (1) is performed by crushing to 110-120 meshes.
Preferably, the step (1) is carried out by crushing with 120 meshes.
Preferably, the feed-liquid ratio of the crushed material to the ethyl acetate in the step (2) is 1:1-3(kg: L).
More preferably, the feed-liquid ratio of the crushed material to the ethyl acetate in the step (2) is 1:1.5-2.5(kg: L).
Preferably, the heating in step (2) is to 60 ℃.
Preferably, the step (2) is circularly extracted for 2 h.
Preferably, said step (2) is carried out in a tank-packed counter-current extraction apparatus.
Preferably, in the step (3), the addition amount of the activated carbon is 0.1-0.2 times of the crude silymarin.
Preferably, in the step (3), activated carbon is added for decolorization for 0.5-1 h.
Preferably, the feed-to-liquid ratio of the crude silymarin in the step (3) to the acetone is 1: 5-7.
Preferably, the amount of the water used in the step (3) is 6-8 times of that of the silymarin acetone dissolving solution.
The invention has the following beneficial effects:
in the method for preparing the high-purity silybin, the silybum marianum is subjected to superfine grinding, so that a solvent can be fully contacted with the silybum marianum during extraction, the aim of improving the yield is fulfilled, the wall breaking effect can be achieved through the superfine grinding, and great help is brought to the extraction of the traditional Chinese medicine. Compared with the traditional extraction, the countercurrent extraction has the characteristics of high extraction speed, high extraction yield, low solvent consumption, low temperature requirement and the like, so that the energy is saved, and the environmental pollution is low. The combination of superfine grinding and countercurrent extraction can more fully contact the traditional Chinese medicinal materials with the solvent, the time consumption is short, and a better extraction effect is achieved. Meanwhile, the invention adopts a simpler recrystallization mode, firstly uses activated carbon to adsorb some pigments, and then carries out recrystallization, so that the obtained silybin has higher purity and less solvent residue.
The method for preparing the high-purity silybin has the advantages that each link is precisely controlled, the method system coordinates, the whole method is simple and short in time, more importantly, the purity of the obtained silybin is not easily improved to nearly 99%, and the extraction rate is improved by about 1.5 times compared with the proportion.
Drawings
FIG. 1 is a high performance liquid chromatogram of silybin of example 1;
FIG. 2 is the HPLC chromatogram of Silibinin in example 2.
Detailed Description
The invention is further described with reference to the drawings and the following detailed description, which are not intended to limit the invention in any way. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Unless otherwise indicated, reagents and materials used in the following examples are commercially available.
Example 1
1. Superfine grinding: adding 30kg of silybum marianum into an ultrafine grinder for ultrafine grinding, and sieving by a 120-mesh sieve after grinding to obtain a ground material.
2. Countercurrent extraction: adding the pulverized material into a tank-group type countercurrent extraction device, heating to 60 deg.C with 60L ethyl acetate for cyclic extraction for 2h, and concentrating the extractive solution to obtain crude silymarin 2.52 kg.
3. And (3) recrystallization: dissolving 2.52kg of crude silymarin with 15L of acetone under heating while stirring until completely dissolved, adding 0.252kg of activated carbon, decolorizing for 0.5h, and cooling to obtain silymarin acetone solution. Adding silymarin acetone solution into 100L water, stirring, standing, and filtering to obtain silybin wet product.
4. Drying and crushing: drying the silybin wet product in a vacuum drying oven, and then crushing to obtain 1.96kg of silybin, wherein the extraction rate is 6.5%, and the purity is 98.8%.
Example 2
1. Superfine grinding: adding 30kg of silybum marianum into an ultrafine grinder for ultrafine grinding, and sieving by a 70-mesh sieve after grinding to obtain a ground material.
2. Countercurrent extraction: adding the pulverized material into a tank-group type countercurrent extraction device, heating to 80 deg.C with 45L ethyl acetate for cyclic extraction for 3h, and concentrating the extractive solution to obtain crude silymarin 2.46 kg.
3. And (3) recrystallization: dissolving 2.46kg of crude silymarin with 17L of acetone under heating while stirring until completely dissolved, adding 0.492kg of activated carbon, decolorizing for 0.5h, and cooling to obtain silymarin acetone solution. Adding silymarin acetone solution into 102L water, stirring, standing, and filtering to obtain silybin wet product.
4. Drying and crushing: drying the silybin wet product in a vacuum drying oven, and then crushing to obtain 1.89kg of silybin, wherein the extraction rate is 6.3%, and the purity is 98.2%.
Example 3
1. Superfine grinding: adding 30kg of silybum marianum into an ultrafine grinder for ultrafine grinding, and sieving by a 120-mesh sieve after grinding to obtain a ground material.
2. Countercurrent extraction: adding the pulverized material into a tank-group type countercurrent extraction device, heating to 50 deg.C with 75L ethyl acetate for cyclic extraction for 1h, and concentrating the extractive solution to obtain crude silymarin 2.54 kg.
3. And (3) recrystallization: dissolving 2.54kg of crude silymarin with 13L of acetone under heating while stirring until completely dissolved, adding 0.254kg of activated carbon, decolorizing for 1h, and cooling to obtain silymarin acetone solution. Adding silymarin acetone solution into 104L water, stirring, standing, and filtering to obtain silybin wet product.
4. Drying and crushing: drying the silybin wet product in a vacuum drying oven, and then crushing to obtain 1.91kg of silybin, wherein the extraction rate is 6.4%, and the purity is 97.3%.
Example 4
1. Superfine grinding: adding 30kg of silybum marianum into an ultrafine grinder for ultrafine grinding, and sieving by a 110-mesh sieve after grinding to obtain a ground material.
2. Countercurrent extraction: adding the pulverized material into a tank-group type countercurrent extraction device, heating to 60 deg.C with 60L ethyl acetate for cyclic extraction for 2h, and concentrating the extractive solution to obtain crude silymarin 2.52 kg.
3. And (3) recrystallization: dissolving 2.52kg of crude silymarin with 15L of acetone under heating while stirring until completely dissolved, adding 0.252kg of activated carbon, decolorizing for 0.5h, and cooling to obtain silymarin acetone solution. Adding silymarin acetone solution into 100L water, stirring, standing, and filtering to obtain silybin wet product.
4. Drying and crushing: drying the silybin wet product in a vacuum drying oven, and then crushing to obtain 1.93kg of silybin, wherein the extraction rate is 6.4%, and the purity is 98.5%.
The products prepared in the above examples 1-2 were subjected to localization detection, and the obtained high performance liquid chromatograms are shown in fig. 1 and 2. As can be seen from the parameters in the figures 1 and 2, the data of the tests of the silibinin products obtained in the examples 1 and 2 are very small, which shows that the silibinin prepared by the method of the invention is very stable in positioning.
Comparative example 1
1. Adding 30kg of silybum marianum into a 100L extraction tank, adding 80L of ethyl acetate, refluxing (80 ℃) for extraction for 4 hours, and concentrating the extracting solution to obtain 2.15kg of crude silymarin.
2. Dissolving 2.15kg of crude silymarin with 13L of acetone under heating while stirring until completely dissolved, adding 0.2kg of activated carbon, decolorizing for 0.5h, and cooling to obtain silymarin acetone solution. Adding silymarin acetone solution into 100L water, stirring, standing, and filtering to obtain silybin wet product.
3. Drying the silybin wet product in a vacuum drying oven, and then crushing to obtain 1.47kg of silybin, wherein the extraction rate is 4.9%, and the purity is 95.3%.
Comparative example 2
1. Countercurrent extraction: adding 30kg of silybum marianum into a tank-group type countercurrent extraction device, heating to 60 ℃ by using 60L of ethyl acetate for cyclic extraction for 2h, and concentrating the extracting solution after extraction to obtain 1.95kg of crude silymarin.
2. And (3) recrystallization: dissolving the crude silymarin with 15L acetone under stirring while heating until completely dissolved, adding 0.252kg activated carbon for decolorizing for 0.5 hr, and cooling to obtain silymarin acetone solution. Adding silymarin acetone solution into 100L water, stirring, standing, and filtering to obtain silybin wet product.
3. Drying and crushing: drying the silybin wet product in a vacuum drying oven, and then crushing to obtain 1.34kg of silybin, wherein the extraction rate is 4.5%, and the purity is 96.4%.
Comparative example 3
1. Superfine grinding: adding 30kg of silybum marianum into an ultrafine grinder for ultrafine grinding, and sieving by a 120-mesh sieve after grinding to obtain a ground material.
2. Reflux extraction: adding the pulverized material into 100L extraction tank, adding 80L ethyl acetate, reflux extracting at 80 deg.C for 4 hr, and concentrating the extractive solution to obtain crude silymarin 2.02 kg.
3. And (3) recrystallization: dissolving the crude silymarin with 15L acetone under stirring while heating until completely dissolved, adding 0.2kg activated carbon for decolorizing for 0.5 hr, and cooling to obtain silymarin acetone solution. Adding silymarin acetone solution into 100L water, stirring, standing, and filtering to obtain silybin wet product.
4. Drying and crushing: drying the silybin wet product in a vacuum drying oven, and then crushing to obtain 1.57kg of silybin, wherein the extraction rate is 5.2%, and the purity is 95.9%.
Comparative example 4
The influence relationship between the superfine grinding mesh number of the silybum marianum and the extraction method and the extraction rate is explored by taking the superfine grinding mesh number of the silybum marianum as a single-factor variable experiment.
Experimental group 1: the experiment was performed in the same manner as in example 1, using the ultrafine pulverization mesh of silybum marianum as a single factor variable.
Experimental group 2: in the same way as the method of the comparative example 3, the experiment is carried out by taking the superfine grinding mesh number of the silybum marianum as a single-factor variable.
The result shows that the influence of the superfine grinding mesh number of the silybum marianum on the extraction rate and the purity of the silybin has certain relevance to the extraction method. In the experimental group 1, the extraction rate of silibinin is higher when the superfine grinding mesh number of the silibinin is larger and the purity of the silibinin is also influenced in the range of 70-150 meshes, and the purity is highest when the superfine grinding mesh number of the silibinin is about 110-120 meshes, but the larger the grinding mesh number is, the better the purity is. In the experimental group 2, the extraction rate of silibinin is higher when the superfine grinding mesh number of the silibinin is larger in the range of 70-150 meshes, and the influence on the purity of the silibinin is little.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (8)
1. A preparation method of high-purity silibinin is characterized by comprising the following steps:
(1) superfine grinding: carrying out superfine grinding on the silybum marianum, crushing to 110-fold and 120-mesh, and sieving to obtain a crushed material;
(2) countercurrent extraction: adding the crushed material into ethyl acetate, heating to 50-80 ℃, circularly extracting for 1-3h, and concentrating after extraction to obtain a crude silymarin product;
(3) and (3) recrystallization: adding the crude silymarin into acetone, dissolving, adding activated carbon for decolorization to obtain silymarin acetone solution, adding the silymarin acetone solution into water, and filtering to obtain wet silybin;
(4) drying and crushing: drying and crushing the silybin wet product to obtain silybin;
the feed-liquid ratio of the crushed material to the ethyl acetate in the step (2) is 1: 1-3.
2. The method according to claim 1, wherein the pulverization in the step (1) is carried out in a 120-mesh size.
3. The method of claim 1, wherein the heating in step (2) is to 60 ℃.
4. The method according to claim 1, wherein the step (2) is performed by circulating extraction for 2 h.
5. The process of claim 1, wherein step (2) is carried out in a tank-packed counter-current extraction apparatus.
6. The method according to claim 1, wherein in the step (3), the time for decoloring by adding activated carbon is 0.5-1 h.
7. The method as claimed in claim 1, wherein the stock-to-liquid ratio of crude silymarin to acetone in step (3) is 1: 5-7.
8. The method as claimed in claim 1, wherein the amount of water used in step (3) is 6-8 times that of the silymarin acetone solution.
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