Extraction method for removing heavy metal residues in traditional Chinese medicinal materials and application of extraction method in preparation of pure white capsules

Abstract

The invention belongs to the technical field of traditional Chinese medicinal materials, and particularly relates to an extraction method for removing heavy metal residues in traditional Chinese medicinal materials and application of the extraction method in preparation of pure white capsules. In the extraction process of the traditional Chinese medicinal materials, a dendritic polyamide-amine modified zinc oxide / spiral carbon nanofiber composite adsorbent and a mesoporous silica / traditional Chinese medicinal residue charcoal composite adsorbent are adopted to adsorb heavy metals in the traditional Chinese medicinal materials, and the removal rates of lead, cadmium, arsenic, mercury and copper in the traditional Chinese medicinal material extracting solution are all greater than or equal to 95% under the combined action of the two adsorbents; the heavy metal content in the traditional Chinese medicinal materials is reduced, and the medication safety of the pure white capsule is guaranteed.

Description

Technical Field

[0001] The invention belongs to the technical field of traditional Chinese medicines, and particularly relates to an extraction method for removing heavy metal residues from traditional Chinese medicines and an application thereof in preparing white capsules. Background Art

[0002] Due to the presence of heavy metals in the soil and atmosphere and the use of pesticides, heavy metals are inevitably present in Chinese medicinal materials. In addition, the fumigants used in the storage process of Chinese medicinal materials to prevent mildew, insect pests and rodent pests will also lead to an increase in the heavy metal content in Chinese medicinal materials.

[0003] Heavy metals can interact strongly with proteins and various enzymes in the human body, causing them to lose their activity. They may also accumulate in certain organs of the human body. If the amount exceeds the limit that the human body can tolerate, it can cause acute poisoning, subacute poisoning, chronic poisoning and other hazards.

[0004] The main source of heavy metals in traditional Chinese medicines is the heavy metals in Chinese medicinal materials. If there are excessive amounts of heavy metals in traditional Chinese medicines, they will have toxic side effects that cause disease while playing a therapeutic role. Therefore, removing heavy metal residues in Chinese medicinal materials is one of the prerequisites for ensuring the safety of traditional Chinese medicines.

[0005] The main methods for removing heavy metal residues in traditional Chinese medicines include supercritical fluid extraction, macroporous resin chelation and chitosan adsorption. The supercritical fluid extraction method has high instrumentation and equipment prices, resulting in high costs; the macroporous resin chelation method is complex to operate and requires high process technology conditions; the chitosan adsorption method has limitations because chitosan itself has certain pharmacological effects and has a certain impact on certain active ingredients in traditional Chinese medicine.

[0006] There are also some other methods in the prior art. For example, the Chinese patent with publication number CN 116116045 A discloses a treatment method for removing heavy metals in the process of extracting traditional Chinese medicine. This technical solution is a method for simultaneously removing five heavy metals, Cu, Cd, As, Hg, and Pb, using sodium alginate in the process of extracting traditional Chinese medicine. The heavy metal content can be reduced to below the safety limit, and the purpose of eliminating the safety hazards of heavy metals in traditional Chinese medicine preparations can be achieved. However, this technical solution has a higher removal rate for Cd, Hg, and Pb, but a lower removal rate for Cu and As.

[0007] The Chinese patent with publication number CN103505905B discloses a method for removing heavy metals from traditional Chinese medicine by using a chelating resin and an ion exchange resin composition, comprising the following steps: step 1, the Chinese medicinal material is subjected to solvent extraction treatment to finally obtain a Chinese medicinal extract with alcohol as a dispersion system; step 2, preparation of a resin composition; step 3, the Chinese medicinal extract is passed through a resin composition column. The preparation of the resin composition in step 2 is a process of mixing a chelating resin with an ion exchange resin to obtain a mixed resin; this technical solution can simultaneously remove Cu, Cd, As, Hg, and Pb in a balanced manner, but this technical solution not only uses a chelating resin, but also uses an ion exchange resin, resulting in increased costs.

[0008] Jiebai Capsule is a Chinese patent medicine with the effects of strengthening the spleen and stomach, relieving pain and vomiting, and separating the clear from the turbid. It is used to treat symptoms such as chest and abdominal distension, epigastric pain, indigestion, vomiting, diarrhea, and difficulty urinating. The prescription is Terminalia chebula (braised), nutmeg, cardamom kernel, cardamom, agarwood, clove, wulingzhi paste, safflower, pomegranate seeds, papaya, inulin, cold water stone (processed flat), pterocarpus, travertine, and honey (refined).

[0009] Due to the presence of multiple Chinese medicinal materials in Jiebai Capsules, the excessive heavy metal content will not only affect the safety of medication, but also affect its quality. However, there is currently no prior art report on methods for removing metal residues in Chinese medicinal materials. Summary of the invention

[0010] In view of the above problems, the present invention provides an extraction method for removing heavy metal residues in traditional Chinese medicines and an application of the method in preparing white capsules. In the process of extracting traditional Chinese medicines, the present invention adopts a dendritic polyamide-amine modified zinc oxide / spiral nanocarbon fiber composite adsorbent and a mesoporous silica / traditional Chinese medicine residue biochar composite adsorbent to adsorb heavy metals in the traditional Chinese medicines. The two work together to remove lead, cadmium, arsenic, mercury and copper in the traditional Chinese medicine extract at a removal rate of ≥95%, thereby reducing the heavy metal content in the traditional Chinese medicines and ensuring the safety of the white capsules.

[0011] The term "material-liquid ratio" used in the technical solution of the present invention refers to the volume ratio (mg / mL) of the amount of medicinal material, i.e., "material", to the extraction solution, i.e., "liquid". For example, a material-liquid ratio of 1:10 means that 10 times the amount of extraction solvent is added to 1 g of medicinal material.

[0012] To achieve the above purpose, the technical solution adopted by the present invention is as follows:

[0013] The first aspect of the present invention provides an extraction method for removing heavy metal residues from traditional Chinese medicine, comprising the following steps:

[0014] (1) crushing the Chinese medicinal materials to obtain a powder mixture; adding the powder mixture to ethanol, performing heating reflux extraction 2-3 times, filtering, and combining the filtrate to obtain an alcohol extract 1 and a Chinese medicinal residue 1;

[0015] (2) adding a dendritic polyamide-amine modified zinc oxide / helical nanocarbon fiber composite adsorbent to the alcohol extract 1, stirring, and filtering to obtain an alcohol extract 2;

[0016] (3) adding water to the Chinese medicinal residue 1 and decocting the mixture twice, filtering and combining the filtrate to obtain a decoction and the Chinese medicinal residue 2;

[0017] (4) The alcohol extract 2 and the decoction solution are combined to obtain a combined solution, and a mesoporous silica / TCM drug residue biochar composite adsorbent is added, stirred, and filtered to obtain a TCM extract solution, and the TCM extract solution is concentrated to obtain a TCM extract with low heavy metal residues.

[0018] In some preferred embodiments, the Chinese medicinal materials in step (1) are the Chinese medicinal materials raw materials for Jiebai Capsules; the Chinese medicinal materials raw materials for Jiebai Capsules include Terminalia chebula, nutmeg, cardamom kernel, cardamom, agarwood, cloves, safflower, pomegranate seeds, papaya, inulin, calcite, pterygium wilfordii and travertine.

[0019] In some preferred embodiments, the solid-liquid ratio of the powder mixture to ethanol in step (1) is 1:20-30.

[0020] Preferably, in step (1), the solid-liquid ratio of the powder mixture to ethanol is 1:25.

[0021] In some preferred embodiments, in step (2), the mass volume ratio of the dendritic polyamide-amine modified zinc oxide / helical carbon nanofiber composite adsorbent and the alcohol extract 1 is 1 g: 300-500 mL.

[0022] Preferably, in step (2), the mass volume ratio of the dendritic polyamide-amine modified zinc oxide / helical carbon nanofiber composite adsorbent and the alcohol extract 1 is 1 g:400 mL.

[0023] In some preferred embodiments, the stirring in step (2) and step (4) is performed at 300-600 r / min for 80-100 min.

[0024] In some preferred embodiments, during the first decoction in step (3), the solid-liquid ratio of the Chinese medicinal residue 1 to water is 1:6-15; the decoction temperature is 70-90°C, and the decoction time is 60-90 min.

[0025] Preferably, during the first decoction in step (3), the solid-liquid ratio of the Chinese medicinal residue 1 to water is 1:10, the decoction temperature is 80° C., and the decoction time is 90 min.

[0026] In some preferred embodiments, during the second decoction in step (3), the amount of water added is 5-10 times the amount of the Chinese medicine residue obtained after the first decoction, the decoction temperature is 70-90° C., and the decoction time is 50-80 min.

[0027] Preferably, during the second decoction in step (3), the amount of water added is 8 times the amount of the Chinese medicine residue obtained after the first decoction, the decoction temperature is 80° C., and the decoction time is 60 min.

[0028] In some preferred embodiments, the mass volume ratio of the mesoporous silica / TCM residue biochar composite adsorbent and the combined liquid in step (4) is 1 g: 500-800 mL.

[0029] Preferably, in step (4), the mass volume ratio of the mesoporous silica / TCM residue biochar composite adsorbent and the combined liquid is 1 g:600 mL.

[0030] In some preferred embodiments, the preparation method of the dendritic polyamide-amine modified zinc oxide / helical carbon nanofiber composite adsorbent comprises the following steps:

[0031] S1, a hexahydrated zinc nitrate aqueous solution, hexamethylenetetramine, polyvinyl alcohol and helical nanocarbon fibers are reacted;

[0032] S2, adding 1-ethyl-(3-dimethylaminopropyl) carbodiimide and dendritic polyamide-amine to continue the reaction, filtering, washing and drying after the reaction to obtain a dendritic polyamide-amine modified zinc oxide / helical nanocarbon fiber composite adsorbent.

[0033] In some preferred embodiments, the mass ratio of the zinc nitrate hexahydrate aqueous solution, hexamethylenetetramine, polyvinyl alcohol and helical nano-carbon fibers in S1 is 5-10: 1-2: 0.5-1: 1-2.

[0034] Preferably, the mass ratio of the zinc nitrate hexahydrate aqueous solution, hexamethylenetetramine, polyvinyl alcohol and helical nano-carbon fibers in S1 is 8:1.5:0.7:1.5.

[0035] In some preferred embodiments, the mass concentration of the zinc nitrate hexahydrate aqueous solution is 5-10%.

[0036] Preferably, the mass concentration of the zinc nitrate hexahydrate aqueous solution is 10%.

[0037] In some preferred embodiments, the mass ratio of 1-ethyl-(3-dimethylaminopropyl)carbodiimide, dendritic polyamide-amine and helical nano-carbon fiber in S2 is 0.1-0.2:0.5-1:1-2.

[0038] Preferably, the mass ratio of 1-ethyl-(3-dimethylaminopropyl)carbodiimide, dendritic polyamide-amine and helical nano-carbon fiber in S2 is 0.15:0.7:1.5.

[0039] In some preferred embodiments, the reaction temperature in S1 is 70-80°C and the reaction time is 6-8h.

[0040] Preferably, the reaction temperature in S1 is 75° C. and the reaction time is 7 h.

[0041] In some preferred embodiments, the reaction temperature in S2 is 70-80°C and the reaction time is 2-4h.

[0042] Preferably, the reaction temperature in S2 is 75° C. and the reaction time is 3 h.

[0043] In some preferred embodiments, the preparation method of the mesoporous silica / traditional Chinese medicine residue biochar composite adsorbent comprises the following steps: subjecting the traditional Chinese medicine residue 2 to a thermal decomposition reaction under a nitrogen atmosphere to obtain traditional Chinese medicine residue biochar; mixing the traditional Chinese medicine residue biochar, hexadecyltrimethylammonium bromide and water to obtain a solution, adding ammonia water at a pH of 8-10; adding ethyl orthosilicate dropwise to the solution for a water bath stirring reaction, and after the water bath stirring reaction is completed, washing and calcining to obtain the mesoporous silica / traditional Chinese medicine residue biochar composite adsorbent.

[0044] In some preferred embodiments, the temperature of the thermal decomposition reaction is 400-800° C., and the time is 1-4 h.

[0045] Preferably, the temperature of the thermal decomposition reaction is 600° C. and the time is 2.5 h.

[0046] In some preferred embodiments, the mass ratio of the traditional Chinese medicine residue biochar, hexadecyltrimethylammonium bromide and water is 1:3-5:70-90.

[0047] Preferably, the mass ratio of the traditional Chinese medicine residue biochar, hexadecyltrimethylammonium bromide and water is 1:4:80.

[0048] In some preferred embodiments, the mass ratio of the traditional Chinese medicine residue biochar to tetraethyl orthosilicate is 1:1-2.

[0049] Preferably, the mass ratio of the traditional Chinese medicine residue biochar to tetraethyl orthosilicate is 1:1.5.

[0050] In some preferred embodiments, the water bath stirring reaction has a rotation speed of 300-600 r / min, a temperature of 20-40° C., and a time of 6-10 h.

[0051] Preferably, the water bath stirring reaction is carried out at a speed of 400 r / min, a temperature of 30° C., and a time of 8 h.

[0052] In some preferred embodiments, the calcination temperature is 600-700° C., and the calcination time is 1-2 h.

[0053] Preferably, the calcination temperature is 650° C. and the calcination time is 1.5 h.

[0054] The second aspect of the present invention provides the use of the Chinese herbal medicine extract with low heavy metal residue obtained by the above extraction method in the preparation of white capsules.

[0055] Compared with the prior art, the present invention has the following beneficial effects:

[0056] (1) In the process of extracting Chinese medicinal materials, the present invention uses a dendritic polyamide-amine modified zinc oxide / helical nanocarbon fiber composite adsorbent and a mesoporous silica / Chinese medicinal residue biochar composite adsorbent to adsorb heavy metals in Chinese medicinal materials. The two work together to remove lead, cadmium, arsenic, mercury, and copper from the Chinese medicinal material extract at a removal rate of ≥95%.

[0057] (2) The present invention reduces the loss of effective ingredients in medicinal materials through the addition method and extraction steps of specific dendritic polyamide-amine modified zinc oxide / helical nanocarbon fiber composite adsorbent and mesoporous silica / traditional Chinese medicine residue biochar composite adsorbent.

[0058] (3) The mesoporous silica / TCM residue biochar composite adsorbent of the present invention is prepared from the TCM residues remaining in the extraction process of TCM medicinal materials, thus achieving resource recycling. DETAILED DESCRIPTION

[0059] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as limiting the present invention, but should be understood as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0060] It should be understood that the terms described in the present invention are only for describing special embodiments and are not intended to limit the present invention. In addition, for the numerical range in the present invention, it should be understood that each intermediate value between the upper and lower limits of the scope is also specifically disclosed. Each smaller range between the intermediate value in any stated value or stated range and any other stated value or intermediate value in the described range is also included in the present invention. The upper and lower limits of these smaller ranges can be independently included or excluded in the scope.

[0061] Unless otherwise indicated, all technical and scientific terms used herein have the same meanings as those generally understood by those skilled in the art. Although the present invention describes only preferred methods and materials, any methods and materials similar or equivalent to those described herein may also be used in the implementation or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials associated with the documents. In the event of a conflict with any incorporated document, the content of this specification shall prevail.

[0062] It will be apparent to those skilled in the art that various modifications and variations may be made to the specific embodiments of the present invention description without departing from the scope or spirit of the present invention. Other embodiments derived from the present invention description will be apparent to those skilled in the art. The present application description and examples are exemplary only.

[0063] The words “include,” “including,” “have,” “contain,” etc. used in this document are open-ended terms, meaning including but not limited to.

[0064] The technical solutions described in the present invention, unless otherwise specified, are all conventional solutions in the art, and the reagents or raw materials used, unless otherwise specified, are purchased from commercial channels or are publicly available.

[0065] The sources of raw materials involved in the examples and comparative examples of the present invention are shown in Table 1.

[0066] Table 1

[0067]

[0068] Example 1

[0069] (1) Preparation of dendritic polyamide-amine modified zinc oxide / helical nanocarbon fiber composite adsorbent: zinc nitrate hexahydrate aqueous solution (the mass concentration of zinc nitrate hexahydrate aqueous solution is 10%), hexamethylenetetramine, polyvinyl alcohol and helical nanocarbon fiber are reacted in a mass ratio of 8:1.5:0.7:1.5, the reaction temperature is 75°C, and the reaction time is 7h; (1-ethyl-(3-dimethylaminopropyl) carbodiimide, dendritic polyamide-amine and helical nanocarbon fiber are added in a mass ratio of 0.15:0.7:1.5) to continue the reaction, the reaction temperature is 75°C, the reaction time is 3h, and after the reaction is completed, the dendritic polyamide-amine modified zinc oxide / helical nanocarbon fiber composite adsorbent is filtered, washed with water, and dried;

[0070] (2) The Chinese medicinal materials of Jiebai Capsule (28 g of Terminalia chebula (simmered), 2 g of nutmeg, 1.5 g of Amomum villosum kernel, 2 g of Amomum villosum, 2 g of Aquilaria sinensis, 3 g of Clove, 1.5 g of Carthamus tinctorius, 6 g of Pomegranate seed, 6 g of Papaya, 3 g of Inula officinalis, 15 g of Cold Water Stone (processed flat), 6 g of Pterocephalum truncatum and 2 g of Travertine) were crushed to obtain a powder mixture; the powder mixture was added to ethanol (the solid-liquid ratio of the powder mixture to ethanol was 1:25), and subjected to heating reflux extraction for 3 times, filtered, and the filtrates were combined to obtain an alcohol extract 1 and a Chinese medicinal residue 1;

[0071] (3) adding a dendritic polyamide-amine modified zinc oxide / helical carbon nanofiber composite adsorbent to the alcohol extract 1 (the mass volume ratio of the dendritic polyamide-amine modified zinc oxide / helical carbon nanofiber composite adsorbent to the alcohol extract 1 is 1 g: 400 mL), stirring at 400 r / min for 90 min, and filtering to obtain an alcohol extract 2;

[0072] (4) The Chinese medicinal residue 1 is decocted twice with water. In the first decoction, the solid-liquid ratio of the Chinese medicinal residue 1 to water is 1:10, the decoction temperature is 80° C., and the decoction time is 90 min. In the second decoction, the amount of water added is 8 times that of the Chinese medicinal residue obtained after the first decoction, the decoction temperature is 80° C., and the decoction time is 60 min. After filtering, the filtrate is combined to obtain a decoction liquid and the Chinese medicinal residue 2;

[0073] (5) Preparation of mesoporous silica / TCM residue biochar composite adsorbent: TCM residue 2 was thermally decomposed at 600°C for 2.5 h under a nitrogen atmosphere to obtain TCM residue biochar; TCM residue biochar, hexadecyltrimethylammonium bromide and water were mixed in a mass ratio of 1:4:80 to obtain a solution, and ammonia water was added to the solution at a pH of 9; ethyl orthosilicate was added dropwise to the solution (the mass ratio of TCM residue biochar to ethyl orthosilicate was 1:1.5), and the solution was reacted at a speed of 400 r / min, a temperature of 30°C, and a time of 8 h in a water bath. After the reaction, the solution was washed and calcined at 650°C for 1.5 h to obtain a mesoporous silica / TCM residue biochar composite adsorbent;

[0074] (6) The alcohol extract 2 and the decoction solution were combined to obtain a combined solution, and a mesoporous silica / TCM drug residue biochar composite adsorbent (the mass volume ratio of the mesoporous silica / TCM drug residue biochar composite adsorbent to the combined solution was 1 g: 600 mL) was added, and the mixture was stirred at 400 r / min for 90 min. The TCM extract was filtered to obtain the TCM extract, and the TCM extract was concentrated to obtain a TCM extract with low heavy metal residues.

[0075] Example 2

[0076] The difference from Example 1 is that in the preparation of the dendritic polyamide-amine modified zinc oxide / helical nano-carbon fiber composite adsorbent, the mass ratio of zinc nitrate hexahydrate aqueous solution, hexamethylenetetramine, polyvinyl alcohol and spiral nano-carbon fiber is 5:1:0.5:1; the mass ratio of 1-ethyl-(3-dimethylaminopropyl)carbodiimide, dendritic polyamide-amine and spiral nano-carbon fiber is 0.1:0.5:1, and the rest are the same.

[0077] Example 3

[0078] The difference from Example 1 is that in the preparation of the dendritic polyamide-amine modified zinc oxide / helical nano-carbon fiber composite adsorbent, the mass ratio of zinc nitrate hexahydrate aqueous solution, hexamethylenetetramine, polyvinyl alcohol and spiral nano-carbon fibers is 10:1.8:1:1.8; the mass ratio of 1-ethyl-(3-dimethylaminopropyl)carbodiimide, dendritic polyamide-amine and spiral nano-carbon fibers is 0.18:1:1.8, and the rest are the same.

[0079] Comparative Example 1

[0080] The difference from Example 1 is that in the preparation of the dendritic polyamide-amine modified zinc oxide / helical nanocarbon fiber composite adsorbent, the spiral nanocarbon fibers are replaced by linear nanocarbon fibers, that is, the dendritic polyamide-amine modified zinc oxide / helical nanocarbon fiber composite adsorbent is replaced by a dendritic polyamide-amine modified zinc oxide / straight nanocarbon fiber composite adsorbent, and the rest are the same.

[0081] Comparative Example 2

[0082] The difference from Example 1 is that the dendritic polyamide-amine modified zinc oxide / helical nano-carbon fiber composite adsorbent is replaced by helical nano-carbon fibers, and the rest is the same.

[0083] Comparative Example 3

[0084] The difference from Example 1 is that the dendritic polyamide-amine modified zinc oxide / spiral nano-carbon fiber composite adsorbent is replaced by a zinc oxide / spiral nano-carbon fiber composite adsorbent: a hexahydrate zinc nitrate aqueous solution (the mass concentration of the hexahydrate zinc nitrate aqueous solution is 10%), hexamethylenetetramine, polyvinyl alcohol and spiral nano-carbon fibers are reacted in a mass ratio of 8:1.5:0.7:1.5, the reaction temperature is 75°C, the time is 7h, and after the reaction is completed, the zinc oxide / spiral nano-carbon fiber composite adsorbent is filtered, washed with water, and dried, and the rest is the same.

[0085] Comparative Example 4

[0086] The difference from Example 1 is that the mesoporous silica / traditional Chinese medicine residue biochar composite adsorbent is replaced by traditional Chinese medicine residue biochar, and the rest is the same.

[0087] Comparative Example 5

[0088] The difference from Example 1 is that in the preparation of the mesoporous silica / traditional Chinese medicine residue biochar composite adsorbent: the traditional Chinese medicine residue 2 is thermally decomposed at 600°C for 2.5 hours under a nitrogen atmosphere to obtain the traditional Chinese medicine residue biochar; the traditional Chinese medicine residue biochar and mesoporous silica are mixed in a mass ratio of 1:1.5 to obtain the mesoporous silica / traditional Chinese medicine residue biochar composite adsorbent.

[0089] Comparative Example 6

[0090] The difference from Example 1 is that the mesoporous silica / traditional Chinese medicine residue biochar composite adsorbent in step (6) is replaced by a dendritic polyamide-amine modified zinc oxide / helical nanocarbon fiber composite adsorbent, and the rest is the same.

[0091] Comparative Example 7

[0092] (1) Same as step (2) of Example 1;

[0093] (2) Same as step (4) of Example 1;

[0094] (3) Preparation of mesoporous silica / traditional Chinese medicine residue biochar composite adsorbent: same as step (5) of Example 1;

[0095] (4) The alcohol extract 1 and the decoction liquid were combined to obtain a combined liquid, and a mesoporous silica / TCM drug residue biochar composite adsorbent (the mass volume ratio of the mesoporous silica / TCM drug residue biochar composite adsorbent to the combined liquid was 1 g: 600 mL) was added, and the mixture was stirred at 400 r / min for 90 min, and the TCM extract was filtered to obtain the TCM extract. The TCM extract was concentrated to obtain a TCM extract with low heavy metal residues.

[0096] Comparative Example 8

[0097] (1) Same as step (1) of Example 1;

[0098] (2) The Chinese medicinal material raw material of Jiebai Capsule (same as in Example 1) was crushed to obtain a powder mixture; the powder mixture was decocted twice with water; in the first decoction, the solid-liquid ratio of the powder mixture to water was 1:10, the decoction temperature was 80° C., and the decoction time was 90 min; in the second decoction, the amount of water added was 8 times the amount of the Chinese medicinal residue obtained after the first decoction, the decoction temperature was 80° C., and the decoction time was 60 min; after filtering, the filtrate was combined to obtain decoction liquid 1 and Chinese medicinal residue 1;

[0099] (3) adding dendritic polyamide-amine modified zinc oxide / helical nanocarbon fiber composite adsorbent to decoction 1 (the mass volume ratio of dendritic polyamide-amine modified zinc oxide / helical nanocarbon fiber composite adsorbent to decoction is 1 g:400 mL), stirring at 400 r / min for 90 min, and filtering to obtain decoction 2;

[0100] (4) adding the Chinese medicinal residue 1 to ethanol (the solid-liquid ratio of the Chinese medicinal residue to ethanol is 1:25), performing heating reflux extraction 3 times, filtering, and combining the filtrate to obtain an alcohol extract and the Chinese medicinal residue 2;

[0101] (5) Preparation of mesoporous silica / traditional Chinese medicine residue biochar composite adsorbent: same as step (5) of Example 1;

[0102] (6) The decoction 2 and the alcohol extract were combined to obtain a combined solution, and a mesoporous silica / TCM residue biochar composite adsorbent (the mass volume ratio of the mesoporous silica / TCM residue biochar composite adsorbent to the combined solution was 1 g: 600 mL) was added, and the mixture was stirred at 400 r / min for 90 min. The TCM extract was filtered to obtain the TCM extract, and the TCM extract was concentrated to obtain a TCM extract with low heavy metal residues.

[0103] Chinese herbal medicine extract without adsorbent:

[0104] (1) The Chinese medicinal material raw material of Jiebai Capsule (same as in Example 1) is crushed to obtain a powder mixture; the powder mixture is added to ethanol (the solid-liquid ratio of the powder mixture to ethanol is 1:25), and subjected to heating reflux extraction 3 times, filtered, and the filtrate is combined to obtain an alcohol extract 1 and a Chinese medicinal residue 1;

[0105] (2) The Chinese medicinal residue 1 is decocted twice with water. In the first decoction, the solid-liquid ratio of the Chinese medicinal residue 1 to water is 1:10, the decoction temperature is 80° C., and the decoction time is 90 min. In the second decoction, the amount of water added is 8 times that of the Chinese medicinal residue obtained after the first decoction, the decoction temperature is 80° C., and the decoction time is 60 min. After filtering, the filtrate is combined to obtain a decoction liquid and the Chinese medicinal residue 2;

[0106] (3) The alcohol extract 1 and the decoction solution are combined to obtain a Chinese medicinal material extract solution, and the Chinese medicinal material extract solution is concentrated to obtain a Chinese medicinal material extract.

[0107] 1. Detect the five heavy metal elements of lead, cadmium, arsenic, mercury and copper in the Chinese medicinal material extracts of Examples 1-3 and Comparative Examples 1-8 and the Chinese medicinal material extracts without using an adsorbent, and calculate the removal rates of the five heavy metals (adsorbed) in the Chinese medicinal material extracts of Examples 1-3 and Comparative Example 18 relative to the five heavy metals (non-adsorbed) in the Chinese medicinal material extracts without using an adsorbent. The removal rate calculation formula is: (non-adsorbed-adsorbed) /

[0108] No adsorption*100%. Specific results are shown in Table 2.

[0109] Table 2 Removal rates of five heavy metals in each group of Chinese herbal medicine extracts

[0110] Group lead / % cadmium / % arsenic / % mercury / % copper / % Example 1 98.6 98.2 95.8 99.2 96.1 Example 2 98.2 97.8 95.3 98.8 95.9 Example 3 98.4 97.5 95.2 98.3 95.8 Comparative Example 1 85.8 85.3 80.7 87.9 83.8 Comparative Example 2 82.7 83.1 76.7 85.5 78.9 Comparative Example 3 83.8 84.2 78.2 86.5 80.8 Comparative Example 4 87.3 86.9 83.2 89.4 86.7 Comparative Example 5 84.2 85.6 81.8 88.7 84.2 Comparative Example 6 89.7 86.4 83.9 88.1 85.3 Comparative Example 7 85.3 81.9 80.1 83.7 83.2 Comparative Example 8 96.8 96.1 93.3 98.5 93.9

[0111] As can be seen from Table 2, the extraction methods of Examples 1-3 and Comparative Example 8 have a high removal rate for the five heavy metals. Comparative Example 1 replaces the dendritic polyamide-amine modified zinc oxide / spiral nanocarbon fiber composite adsorbent with a dendritic polyamide-amine modified zinc oxide / straight-chain nanocarbon fiber composite adsorbent; Comparative Example 2 replaces the dendritic polyamide-amine modified zinc oxide / spiral nanocarbon fiber composite adsorbent with a spiral nanocarbon fiber; Comparative Example 3 replaces the dendritic polyamide-amine modified zinc oxide / spiral nanocarbon fiber composite adsorbent with a zinc oxide / spiral nanocarbon fiber composite adsorbent. Fiber composite adsorbent; Comparative Example 4 replaces the mesoporous silica / traditional Chinese medicine residue biochar composite adsorbent with traditional Chinese medicine residue biochar; Comparative Example 5 directly mixes traditional Chinese medicine residue biochar and mesoporous silica; Comparative Example 6 replaces the mesoporous silica / traditional Chinese medicine residue biochar composite adsorbent in step (6) with a dendritic polyamide-amine modified zinc oxide / helical nano-carbon fiber composite adsorbent, and Comparative Example 7 does not use a dendritic polyamide-amine modified zinc oxide / helical nano-carbon fiber composite adsorbent; The extraction methods of Comparative Examples 1-7 have reduced removal rates of the five heavy metals.

[0112] 2. The total polyphenol content in the Chinese medicinal material extracts of Examples 1-3 and Comparative Examples 1-8 and the Chinese medicinal material extracts without using an adsorbent was detected by HPLC method, and the change rate of the total polyphenol content (adsorbed) in the Chinese medicinal material extracts of Example 1 and Comparative Example 18 relative to the total polyphenol content (non-adsorbed) in the Chinese medicinal material extracts without using an adsorbent was calculated. The calculation formula for the change rate of the total polyphenol content is: (non-adsorbed-adsorbed) / non-adsorbed*100%. The specific results are shown in Table 3.

[0113] Table 3 Results of the change rate of total polyphenol content in each group of Chinese herbal medicine extracts

[0114] Group Total polyphenol content change rate / % Example 1 3.8 Example 2 4.1 Example 3 3.9 Comparative Example 1 4.2 Comparative Example 2 3.1 Comparative Example 3 3.4 Comparative Example 4 3.6 Comparative Example 5 3.5 Comparative Example 6 10.6 Comparative Example 7 4.2 Comparative Example 8 15.3

[0115] It can be seen from Table 3 that the extraction methods of Examples 1-3, Comparative Examples 1-5 and Comparative Example 7 have little effect on the total polyphenol content of the Chinese medicinal material extract. Comparative Example 6 replaces the mesoporous silica / Chinese medicinal material residue biochar composite adsorbent in step (6) with a dendritic polyamide-amine modified zinc oxide / helical nanocarbon fiber composite adsorbent, and Comparative Example 8 changes the extraction steps; the extraction methods of Comparative Examples 6 and Comparative Example 8 have a greater effect on the total polyphenol content of the Chinese medicinal material extract.

[0116] Finally, it should be noted that the above content is only used to illustrate the technical solution of the present invention, rather than to limit the scope of protection of the present invention. Simple modifications or equivalent substitutions of the technical solution of the present invention by ordinary technicians in this field do not deviate from the essence and scope of the technical solution of the present invention.

Claims

1. A method for removing heavy metal residues from traditional Chinese medicine, characterized in that: The following steps are involved: (1) crushing the Chinese medicinal materials to obtain a powder mixture; adding the powder mixture to ethanol, performing heating reflux extraction 2-3 times, filtering, and combining the filtrate to obtain an alcohol extract 1 and a Chinese medicinal residue 1; (2) adding a dendritic polyamide-amine modified zinc oxide / helical nanocarbon fiber composite adsorbent to the alcohol extract 1, stirring, and filtering to obtain an alcohol extract 2; (3) adding water to the Chinese medicinal residue 1 and decocting the mixture twice, filtering and combining the filtrate to obtain a decoction and the Chinese medicinal residue 2; (4) The alcohol extract 2 and the decoction solution are combined to obtain a combined solution, and a mesoporous silica / TCM drug residue biochar composite adsorbent is added, stirred, and filtered to obtain a TCM extract solution, and the TCM extract solution is concentrated to obtain a TCM extract with low heavy metal residues.

2. The extraction method according to claim 1, characterized in that The Chinese medicinal materials in step (1) are the Chinese medicinal materials raw materials for white capsules; the Chinese medicinal materials raw materials for white capsules include terminalia chebula, nutmeg, cardamom kernel, cardamom, agarwood, clove, safflower, pomegranate seed, papaya, inulin, hanshui stone, pterygium wilfordii and travertine.

3. The extraction method according to claim 2, characterized in that The preparation method of the dendritic polyamide-amine modified zinc oxide / helical carbon nanofiber composite adsorbent comprises the following steps: S1, a hexahydrated zinc nitrate aqueous solution, hexamethylenetetramine, polyvinyl alcohol and helical nanocarbon fibers are reacted; S2, adding 1-ethyl-(3-dimethylaminopropyl) carbodiimide and dendritic polyamide-amine to continue the reaction, filtering, washing and drying after the reaction to obtain a dendritic polyamide-amine modified zinc oxide / helical nanocarbon fiber composite adsorbent.

4. The extraction method according to claim 3, characterized in that The mass ratio of zinc nitrate hexahydrate aqueous solution, hexamethylenetetramine, polyvinyl alcohol and spiral nanocarbon fibers in S1 is 5-10:1-2:0.5-1:1-2.

5. The extraction method according to claim 3, characterized in that The mass ratio of 1-ethyl-(3-dimethylaminopropyl)carbodiimide, dendritic polyamide-amine and helical nano-carbon fibers in S2 is 0.1-0.2:0.5-1:1-2.

6. The extraction method according to claim 1, characterized in that The preparation method of the mesoporous silica / traditional Chinese medicine residue biochar composite adsorbent comprises the following steps: performing a thermal decomposition reaction on the traditional Chinese medicine residue 2 under a nitrogen atmosphere to obtain the traditional Chinese medicine residue biochar; mixing the traditional Chinese medicine residue biochar, hexadecyltrimethylammonium bromide and water to obtain a solution, adding ammonia water under the condition of pH 8-10; dropping ethyl orthosilicate into the solution to carry out a water bath stirring reaction, and washing and calcining after the water bath stirring reaction to obtain the mesoporous silica / traditional Chinese medicine residue biochar composite adsorbent.

7. The extraction method according to claim 6, characterized in that The mass ratio of the Chinese medicinal residue biochar, hexadecyltrimethylammonium bromide and water is 1:3-5:70-90; the mass ratio of the Chinese medicinal residue biochar and tetraethyl orthosilicate is 1:1-2.

8. The extraction method according to claim 1, characterized in that In step (2), the mass volume ratio of the dendritic polyamide-amine modified zinc oxide / helical nano-carbon fiber composite adsorbent and the alcohol extract 1 is 1g:300-500mL.

9. The extraction method according to claim 1, characterized in that In step (4), the mass volume ratio of the mesoporous silica / traditional Chinese medicine residue biochar composite adsorbent and the combined liquid is 1g:500-800mL.

10. Use of a Chinese herbal medicine extract with low heavy metal residue obtained by the extraction method according to any one of claims 1 to 9 in the preparation of white capsules.

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