Method for removing heavy metal residues and application of method in preparation of eighteen-flavor rhododendron pills

Abstract

The invention provides a method for removing heavy metal residues and application of the method in preparation of eighteen-ingredient rhododendron pills, and relates to the technical field of traditional Chinese medicine processing. The method comprises the following steps: S1, preparing a modified adsorbent A by taking porous silica gel as a carrier and sodium polyacrylate, sodium alginate and ethylenediamine tetraacetic acid as modified materials; the adsorbent B is adsorbent resin; the mass ratio of the modified adsorbent A to the adsorbent B is (3-5): 1 to obtain a modified composite adsorbent; s2, adsorption and precipitation: mixing the traditional Chinese medicine extracting solution with the modified composite adsorbent, adding calcium sulfate, pressurizing, stirring and adsorbing to obtain an extracting solution without heavy metal residues. According to the method, lead, cadmium, arsenic, mercury and copper are efficiently removed, the content of effective chemical components of the traditional Chinese medicine subjected to heavy metal removal is not remarkably changed, and damage to the active components is reduced.

Description

Technical Field

[0001] The invention belongs to the technical field of traditional Chinese medicine processing, and particularly relates to a method for removing heavy metal residues and an application of the method in preparing Eighteen-flavor Dujuan Pills. Background Art

[0002] The ingredients of Eighteen-flavor Azalea Pills are: Rhododendron australis, Amomum villosum, Terminalia chebula, Sandalwood, Phyllanthus emblica, Terminalia chebula, Gentiana macrophylla, Safflower, Aquilaria sinensis, Lithospermum officinale, Dalbergia odorifera, Alumensis leaf, Travertine, Tibetan madder, Nutmeg, Clove, Licorice paste and Cardamom. The main effects of Eighteen-flavor Azalea Pills are: dispelling wind, unblocking meridians and promoting blood circulation. It is used for numbness of the limbs, tremors, muscle atrophy, tendon cramps, and crooked mouth and eyes caused by "blood vessel diseases".

[0003] Heavy metals are very harmful to the human body, causing damage to the nervous system, digestive system, hematopoietic system, liver and kidney functions, and affecting the normal metabolism of cells; among them, lead (Pb), cadmium (Cd), arsenic (As), mercury (Hg), and copper (Cu) are particularly harmful. Chinese patent medicines are generally compound preparations, composed of multiple Chinese medicines. Mixed extraction operations are involved in the production process. The heavy metals contained in each Chinese medicine are superimposed on each other, which can easily cause the total amount of heavy metals in the compound to exceed the standard. Therefore, when preparing drugs from Chinese medicine raw materials, heavy metals need to be removed.

[0004] Chinese invention patent CN117018681A discloses a method for extracting and removing heavy metal ions from Chinese herbal medicines, comprising the following steps: adding sodium polyacrylate as a coagulant to the prepared Chinese herbal medicine water extract or concentrate, wherein the content of sodium polyacrylate is 0.05-0.1% of the Chinese herbal medicine water extract or concentrate to be prepared; adding sodium alginate clarifier embedded with natural inorganic non-metallic diatomaceous earth, stirring thoroughly and evenly, and standing for 12-48 hours, wherein the content of sodium alginate is 0.1-0.6% of the Chinese herbal medicine water extract or concentrate; filtering the clarified liquid after standing and adjusting the pH to neutral to obtain the product; and recovering the filtered out failed adsorption material. In the method for extracting and removing heavy metal ions from Chinese herbal medicines, sodium alginate and diatomaceous earth form a gel network structure in which the intercalation expands the spatial structure in the gel network and reduces the steric hindrance effect of chelation, thereby making AsO4 3- and AsO3 3- It can also be adsorbed; the invention uses COO formed by sodium alginate and sodium polyacrylate - The hydrogel ratio was NH4+ formed by chitosan and acrylamide. 2+ The hydrogel has a wider complexing capacity. However, the above method, while adsorbing heavy metal ions, inevitably removes the chemical components containing hydroxyl groups in the traditional Chinese medicine, thus having a certain impact on the efficacy of the medicine.

[0005] Chinese invention patent CN103505905A discloses a method for removing heavy metals from traditional Chinese medicine using a chelating resin and an ion exchange resin composition, comprising the following steps: (1) the Chinese medicinal material is subjected to solvent extraction treatment to obtain a Chinese medicinal extract with alcohol as a dispersion system; (2) preparation of a resin composition: the volume ratio of the chelating resin to the ion exchange resin is 1:10-10:1, the resin composition is a chelating resin D401, a chelating resin D405, and an ion exchange resin D113 with a weight ratio of 1:1:1, and the volume ratio of the resin to the volume of the extract is 1-50:50; (3) the Chinese medicinal extract is passed through a resin composition column. The above method enables a heavy metal removal rate of more than 60%. In the process of removing heavy metals from a compound Danshen extract, the similarity of the fingerprint spectra of Danshen and Panax notoginseng before and after treatment is ≥0.9. However, the above method is not suitable for Chinese medicinal extracts containing volatile oil components, which is prone to cause the loss of Chinese medicinal components and has limited heavy metal removal effects.

[0006] The processing and preparation of traditional Chinese medicine and the species of traditional Chinese medicine have the effect of enriching heavy metals. Therefore, for different medicines, even if the same method of removing heavy metal residues is used, different removal effects are still achieved. In the prior art, there is no method for removing heavy metal residues from Shibawei Dujuan Pills.

[0007] In view of this, the present invention provides a method for removing heavy metal residues and its application in the preparation of Shibawei Dujuan Pills, using a modified composite adsorbent to achieve efficient removal of lead (Pb), cadmium (Cd), arsenic (As), mercury (Hg), and copper (Cu), and the content of effective chemical components in the extract after heavy metal removal changes little. The method of the present invention achieves the purpose of accurately and efficiently removing multiple heavy metals without destroying the active ingredients of traditional Chinese medicine. Summary of the invention

[0008] The invention aims at the problems existing in the prior art and provides a method for removing heavy metal residues and application of the method in preparing Eighteen-flavor Dujuan Pills.

[0009] To achieve the above purpose, the technical solution adopted by the present invention is as follows:

[0010] In one aspect, the present invention provides a method for removing heavy metal residues, comprising the steps of:

[0011] S1. Preparation of modified composite adsorbent:

[0012] Modified adsorbent A was prepared using porous silica gel as a carrier and sodium polyacrylate, sodium alginate and ethylenediaminetetraacetic acid as modification materials;

[0013] Adsorbent B is an adsorption resin;

[0014] The modified adsorbent A and the adsorbent B are mixed in a mass ratio of 3-5:1 to obtain a modified composite adsorbent;

[0015] S2. Adsorption and precipitation: Mix the Chinese medicine extract with the modified composite adsorbent, add calcium sulfate, pressurize and stir for adsorption to obtain an extract with heavy metal residues removed.

[0016] Preferably, in step S1, the porous silica gel has a particle size of 100-200 μm and an average pore size of 10-30 nm.

[0017] Further preferably, the porous silica gel has a particle size of 150 μm and an average pore diameter of 20 nm.

[0018] Preferably, in step S1, the preparation method of the modified adsorbent A is: disperse porous silica gel in water, add a mixture of sodium polyacrylate, sodium alginate and ethylenediaminetetraacetic acid, stir and react at 50-70°C for 3-6h, and dry to obtain the modified adsorbent A.

[0019] Further preferably, in step S1, the preparation method of the modified adsorbent A is: dispersing porous silica gel in water to obtain a suspension with a solid-liquid ratio of 1:20-30 g / mL; adding a mixture of sodium polyacrylate, sodium alginate and ethylenediaminetetraacetic acid, stirring and reacting at 50-70°C for 3-6 hours, and drying the modified porous silica gel to obtain modified adsorbent A.

[0020] More preferably, in step S1, the preparation method of the modified adsorbent A is: dispersing porous silica gel in water to obtain a suspension with a solid-liquid ratio of 1:25 g / mL; adding a mixture of sodium polyacrylate, sodium alginate and ethylenediaminetetraacetic acid, stirring and reacting at 60°C for 4 hours, and drying the modified porous silica gel to obtain modified adsorbent A.

[0021] Preferably, in step S1, the mass ratio of the porous silica gel to the modified material is 25-35:1.

[0022] Further preferably, in step S1, the mass ratio of the porous silica gel to the modified material is 30:1.

[0023] Preferably, in step S1, in the modified material, the mass ratio of sodium polyacrylate, sodium alginate and ethylenediaminetetraacetic acid is 1-3:4-6:0.5.

[0024] Further preferably, in step S1, the mass ratio of sodium polyacrylate, sodium alginate and ethylenediaminetetraacetic acid is 2:5:0.5.

[0025] Preferably, in step S1, the adsorption resin is a mixture of D401 chelating resin and D402 chelating resin.

[0026] Further preferably, the mass ratio of D401 to D402 is 1:3-6.

[0027] More preferably, the mass ratio of D401 to D402 is 1:4.

[0028] Preferably, in step S1, the mass ratio of the modified adsorbent A to the adsorbent B is 4:1.

[0029] Preferably, in step S2, the mass ratio of the modified composite adsorbent to calcium sulfate is 1:0.05-0.2.

[0030] Further preferably, the mass ratio of the modified composite adsorbent to calcium sulfate is 1:0.1.

[0031] Preferably, in step S2, the pressurized stirring adsorption is: 0.1-0.3MPa, 400-800rpm, stirring adsorption treatment for 30-90min.

[0032] Further preferably, in step S2, the pressurized stirring adsorption is: 0.2 MPa 600 rpm stirring adsorption treatment for 60 min.

[0033] Preferably, the added amount of the modified composite adsorbent is 35-45% of the mass of the Chinese medicine raw material.

[0034] Further preferably, the added amount of the modified composite adsorbent is 40% of the mass of the Chinese medicine raw material.

[0035] In the present invention, the Chinese medicine extract can be any water extract of Chinese medicine. In some embodiments of the present invention, the Chinese medicine extract is a Chinese medicine extract obtained by water extraction of Chinese medicine components used to prepare Shibawei Dujuan Pills.

[0036] In some embodiments of the present invention, the Chinese medicinal raw materials of Eighteen-flavor Azalea Pills include Rhododendron australis, Amomum villosum, Terminalia chebula, Sandalwood, Emblica officinalis, Terminalia chebula, Gentiana macrophylla, Safflower, Aquilaria sinensis, Lithospermum officinale, Dalbergia odorifera, Atractylodes macrocephala, Travertine, Tibetan madder, nutmeg, cloves and cardamom.

[0037] Preferably, the Chinese medicinal raw material ingredients of the Eighteen-flavor Dujuan Pills also include liquorice paste.

[0038] In some embodiments of the present invention, the preparation method of the traditional Chinese medicine extract is: add water to the traditional Chinese medicine raw material components, the solid-liquid ratio is 1:10-25g / mL, boil and decoct for 1-3h, filter, repeat decoction 2-4 times, and obtain the traditional Chinese medicine extract and residue.

[0039] In some embodiments of the present invention, the preparation method of the traditional Chinese medicine extract is: add water to the traditional Chinese medicine raw material components, the solid-liquid ratio is 1:20g / mL, boil and decoct for 2h, filter, repeat decoction twice, and obtain the traditional Chinese medicine extract and medicinal residue.

[0040] Furthermore, the present invention provides application of the above method in preparing Eighteen-flavor Dujuan Pills.

[0041] In the application of the present invention, the above-mentioned method for removing heavy metal residues is used to achieve efficient removal of heavy metal elements Pb, Cd, As, Hg, and Cu in the traditional Chinese medicine extract for preparing Eighteen-flavor Dujuan Pills, with the removal rates reaching more than 99% respectively; at the same time, the content of active ingredients is almost unchanged.

[0042] Finally, the present invention provides a low-content heavy metal 18-flavor azalea pill, the preparation method of which comprises the steps of:

[0043] (1) The Chinese medicinal raw material components of Shibawei Dujuan Pills are mixed with water, heated and extracted to obtain a Chinese medicinal extract and medicinal residues;

[0044] (2) subjecting the Chinese medicine extract to the above-mentioned treatment for removing heavy metal residues to obtain an extract from which heavy metal residues have been removed;

[0045] (3) concentrating and drying the extract from which the heavy metal residues have been removed, and mixing it with the medicinal residues to prepare Eighteen-flavor Dujuan Pills;

[0046] Or the preparation method comprises the steps of:

[0047] (1) Except for the liquorice paste, the Chinese medicinal raw material ingredients of Shibawei Dujuan Pills are mixed with water, heated and extracted to obtain a Chinese medicinal extract and medicinal residues;

[0048] (2) subjecting the Chinese medicine extract to the above-mentioned treatment for removing heavy metal residues to obtain an extract from which heavy metal residues have been removed;

[0049] (3) The extract from which the heavy metal residues have been removed is concentrated and dried, and mixed with the medicinal residues and liquorice paste to prepare Eighteen-flavor Dujuan Pills.

[0050] Compared with the prior art, the present invention has the following beneficial effects:

[0051] 1. The method of the present invention uses a modified composite adsorbent to pressurize heavy metals in a Chinese medicine extract to remove heavy metals; the modified adsorbent A and adsorbent B synergize to significantly improve the removal rate of heavy metals Pb, Cd, As, Hg, and Cu. The method of the present invention has a short action time, can effectively adsorb heavy metals at room temperature, and reduces the loss of effective component content and activity.

[0052] 2. The modified adsorbent A of the present invention uses porous silica gel with specific particle size and pore size as a carrier. The surface of the carrier contains a large number of hydroxyl groups. It is mixed with the modifying material and modified under acidic conditions. The surface of the prepared modified adsorbent A contains rich flocculants and uniform pore size, which is beneficial to the adsorption of heavy metals.

[0053] 3. The method of the present invention has mild processing conditions, so that the content of chemical components such as quercetin, kaempferol, and chebulic acid before and after treatment changes little, which can effectively protect the active ingredients in traditional Chinese medicine; the method of the present invention achieves the purpose of accurately and efficiently removing multiple heavy metals. DETAILED DESCRIPTION

[0054] The following non-limiting examples can make those of ordinary skill in the art understand the present invention more comprehensively, but do not limit the present invention in any way. The following content is merely an exemplary description of the scope of the present invention, and those skilled in the art can make various changes and modifications to the present invention according to the disclosed content, and it should also belong to the scope of the present invention. When the embodiment gives a numerical range, it should be understood that, unless otherwise specified in the present invention, the two endpoints of each numerical range and any numerical value between the two endpoints can be selected. Unless otherwise defined, all technical and scientific terms used in the present invention have the same meanings as those of ordinary skill in the technical field to which the present invention belongs.

[0055] The present invention is further described below by way of specific examples. Unless otherwise specified, the various chemical reagents used in the examples of the present invention are obtained through conventional commercial channels.

[0056] In the following embodiments, the sodium polyacrylate was purchased from Langfang Pengcai Fine Chemical Co., Ltd.; the ethylenediaminetetraacetic acid was purchased from Jinan Delan Chemical Co., Ltd.; the D401 chelating resin was purchased from Elester (Shanghai) New Material Technology Co., Ltd., with the brand YUROLITE; the D402 chelating resin was purchased from Elester (Shanghai) New Material Technology Co., Ltd., with the brand YUROLITE; and the D405 chelating resin was purchased from Jiangsu Suqing Group.

[0057] For the above components, products from different manufacturers have no significant effect on the effects.

[0058] In some embodiments of the present invention, the Chinese medicine raw material ingredients include the following components by weight: 100-200 parts of Rhododendron australis, 20-40 parts of Amomum villosum, 100-180 parts of Terminalia chebula, 40-80 parts of Santalum album, 100-150 parts of Phyllanthus emblica, 70-150 parts of Terminalia chebula, 70-130 parts of Gentiana macrophylla, 70-130 parts of Carthamus tinctorius, 70-130 parts of Aquilaria sinensis, 60-100 parts of Lithospermum officinale, 80-120 parts of Dalbergia odorifera, 60-100 parts of Alumensis leaf, 50-100 parts of Travertine, 80-120 parts of Tibetan madder, 20-40 parts of nutmeg, 30-50 parts of cloves, 20-40 parts of cardamom and / or 60-100 parts of liquorice paste.

[0059] In some embodiments of the present invention, the preparation method of the Chinese medicine extract is: mix the Chinese medicine raw material components and water with a solid-liquid ratio of 1:10-25g / mL, boil and decoct for 1-3h, filter, and repeat the decoction 2-4 times to obtain the Chinese medicine extract and the residue.

[0060] In some embodiments of the present invention, the preparation method of the Chinese medicine extract is: mix the Chinese medicine raw material ingredients (except licorice paste ingredients) and water, with a solid-liquid ratio of 1:10-25g / mL, boil and decoct for 1-3h, filter, and repeat the decoction 2-4 times to obtain the Chinese medicine extract and the residue.

[0061] Basic Example

[0062] The Chinese medicine raw material components include the following components by weight: 150 parts of Rhododendron australis, 30 parts of Amomum villosum, 140 parts of Terminalia chebula, 60 parts of Santalum album, 120 parts of Phyllanthus emblica, 100 parts of Terminalia chebula, 100 parts of Gentiana macrophylla, 100 parts of Carthamus tinctorius, 100 parts of Aquilaria sinensis, 80 parts of Lithospermum officinale, 100 parts of Dalbergia odorifera, 80 parts of Asteraceae leaves, 75 parts of Travertine, 100 parts of Tibetan madder, 30 parts of Myristica fragrans, 40 parts of Cloves, and 30 parts of Cardamom. The preparation method of the Chinese medicine extract is as follows: the above Chinese medicine raw material components are mixed with water at a solid-liquid ratio of 1:20 g / mL, boiled and decocted for 2 hours, filtered, and decocted 3 times to obtain the Chinese medicine extract and the residue.

[0063] The preparation method of Eighteen-flavor Azalea Pills comprises the following steps: (1) treating a Chinese medicine extract to remove heavy metal residues, thereby obtaining an extract from which heavy metal residues have been removed; and (2) concentrating and drying the extract from which heavy metal residues have been removed, and mixing the extract with the medicine residue and licorice paste to prepare Eighteen-flavor Azalea Pills.

[0064] Example 1

[0065] A method for removing heavy metal residues:

[0066] The Chinese medicine extract and the medicinal residues were prepared according to the method of Basic Example 1;

[0067] S1. Preparation of modified composite adsorbent:

[0068] Modified materials: sodium polyacrylate, sodium alginate and ethylenediaminetetraacetic acid in a mass ratio of 2:5:0.5;

[0069] Porous silica gel (particle size 150 μm, average pore size 20 nm) was dispersed in water to obtain a suspension with a solid-liquid ratio of 1:25 g / mL; a modifying material was added, and the mixture was stirred at 60° C. for 4 h for modification, and the modified porous silica gel was dried at 50° C. for 4 h to obtain a modified adsorbent A; the mass ratio of the porous silica gel to the modifying material was 30:1;

[0070] Adsorbent B: D401 and D402 in a mass ratio of 1:4;

[0071] Modified composite composite adsorbent: modified adsorbent A and adsorbent B in a mass ratio of 4:1;

[0072] S2. Adsorption and precipitation: The Chinese medicine extract was mixed with the modified composite adsorbent, calcium sulfate was added, and the adsorption treatment was stirred at 0.2MPa600rpm for 60min to obtain an extract with heavy metal residues removed;

[0073] The mass ratio of the modified composite adsorbent to calcium sulfate is 1:0.1; the added amount of the modified composite adsorbent is 40% of the mass of the traditional Chinese medicine component.

[0074] Example 2

[0075] A method for removing heavy metal residues:

[0076] The Chinese medicine extract and the medicinal residues were prepared according to the method of Basic Example 1;

[0077] S1. Preparation of modified composite adsorbent:

[0078] Modified materials: sodium polyacrylate, sodium alginate and ethylenediaminetetraacetic acid in a mass ratio of 1:4:0.5;

[0079] Porous silica gel (particle size 150 μm, average pore size 20 nm) was dispersed in water to obtain a suspension with a solid-liquid ratio of 1:25 g / mL; a modifying material was added, and the mixture was stirred at 50° C. for 6 h for modification, and the modified porous silica gel was dried at 50° C. for 4 h to obtain a modified adsorbent A; the mass ratio of the porous silica gel to the modifying material was 25:1;

[0080] Adsorbent B: D401 and D402 in a mass ratio of 1:3;

[0081] Modified composite composite adsorbent: modified adsorbent A and adsorbent B in a mass ratio of 5:1;

[0082] S2. Same as Example 1.

[0083] Example 3

[0084] A method for removing heavy metal residues:

[0085] The Chinese medicine extract and the medicinal residues were prepared according to the method of Basic Example 1;

[0086] S1. Preparation of modified composite adsorbent:

[0087] Modified materials: sodium polyacrylate, sodium alginate and ethylenediaminetetraacetic acid in a mass ratio of 3:6:0.5;

[0088] Porous silica gel (particle size 150 μm, average pore size 20 nm) was dispersed in water to obtain a suspension with a solid-liquid ratio of 1:25 g / mL; a modifying material was added, and the mixture was stirred at 70° C. for 3 h for modification, and the modified porous silica gel was dried at 50° C. for 4 h to obtain a modified adsorbent A; the mass ratio of the porous silica gel to the modifying material was 35:1;

[0089] Adsorbent B: D401 and D402 in a mass ratio of 1:6;

[0090] Modified composite composite adsorbent: modified adsorbent A and adsorbent B in a mass ratio of 3:1;

[0091] S2. Same as Example 1.

[0092] Example 4

[0093] A method for removing heavy metal residues:

[0094] The Chinese medicine extract and the medicinal residues were prepared according to the method of Basic Example 1;

[0095] S1. Same as Example 1;

[0096] S2. Adsorption and precipitation: The Chinese medicine extract was mixed with the modified composite adsorbent, calcium sulfate was added, and the adsorption treatment was stirred at 0.1MPa800rpm for 90min to obtain an extract with heavy metal residues removed;

[0097] The mass ratio of the modified composite adsorbent to calcium sulfate is 1:0.05; the added amount of the modified composite adsorbent is 35% of the mass of the traditional Chinese medicine component.

[0098] Example 5

[0099] A method for removing heavy metal residues:

[0100] The Chinese medicine extract and the medicinal residues were prepared according to the method of Basic Example 1;

[0101] S1. Same as Example 1;

[0102] S2. Adsorption and precipitation: The Chinese medicine extract was mixed with the modified composite adsorbent, calcium sulfate was added, and the adsorption treatment was stirred at 0.3MPa400rpm for 30min to obtain an extract with heavy metal residues removed;

[0103] The mass ratio of the modified composite adsorbent to calcium sulfate is 1:0.2; the added amount of the modified composite adsorbent is 45% of the mass of the traditional Chinese medicine component.

[0104] Comparative Example 1

[0105] The difference from Example 1 is that the adsorbent B is not used in the method for removing heavy metal residues. That is, only the modified adsorbent A is used for adsorption and precipitation to obtain an extract from which heavy metal residues are removed.

[0106] Comparative Example 2

[0107] The difference from Example 1 is that the modified adsorbent A is not used in the method for removing heavy metal residues. That is, only adsorbent B is used for adsorption and precipitation to obtain an extract from which heavy metal residues are removed.

[0108] Comparative Example 3

[0109] The difference from Example 1 is that the mass ratio of modified adsorbent A to adsorbent B is 1:4. The rest is the same as Example 1.

[0110] Comparative Example 4

[0111] The difference from Example 1 is that adsorbent B is only one component of D401 chelating resin. The rest is the same as Example 1.

[0112] Comparative Example 5

[0113] The difference from Example 1 is that adsorbent B is a mixture of D401 and D405 in a mass ratio of 1:4. The rest is the same as Example 1.

[0114] Comparative Example 6

[0115] Different from Example 1, calcium sulfate is not added for precipitation treatment in step S2.

[0116] Step S1 is the same as in Example 1;

[0117] Step S2: Adsorption: The Chinese medicine extract is mixed with the modified composite adsorbent, and the mixture is stirred and adsorbed at 0.2 MPa and 600 rpm for 60 min to obtain an extract from which heavy metal residues are removed; the amount of the modified composite adsorbent added is 40% of the mass of the Chinese medicine raw material component.

[0118] Comparative Example 7

[0119] Different from Example 1, step S2 does not perform pressurization treatment.

[0120] Step S1 is the same as in Example 1;

[0121] Step S2: adsorption and precipitation: the Chinese medicine extract is mixed with the modified composite adsorbent, calcium sulfate is added, and the mixture is stirred and adsorbed at 600 rpm at normal pressure for 60 minutes to obtain an extract from which heavy metal residues are removed;

[0122] The mass ratio of the modified composite adsorbent to calcium sulfate is 1:0.1; the added amount of the modified composite adsorbent is 40% of the mass of the raw material components of the traditional Chinese medicine.

[0123] Test 1: Method for detecting the content of active ingredients before and after treatment

[0124] According to the high performance liquid chromatography method (General Rule 0512), the content of active ingredients in the extract before and after the removal of heavy metals was detected, and the loss rate of the active ingredients was calculated.

[0125] The solutions of Pb, Cd, As, Hg and Cu were added to the Chinese medicine extract in Basic Example 1, so that the mass content of each metal ion in the Chinese medicine extract was: 7.5 μg / g lead, 1.5 μg / g cadmium, 3 μg / g arsenic, 0.3 μg / g mercury, and 30 μg / g copper, and the mixture was fully mixed to obtain a reference substance. Then, the methods of each embodiment and Comparative Examples 1 to Comparative Examples 5 were used to remove heavy metal residues.

[0126] The calculation method of the loss rate is: (M1-M2) / M1×100%; wherein M1 is the active ingredient content of the reference substance, and M2 is the active ingredient content after heavy metals are removed; the loss rate results are shown in Table 1.

[0127] Table 1

[0128] Quercetin loss rate, % Kaempferol loss rate, % Chebulinic Acid loss rate, % Example 1 6.8 13.5 9.9 Example 2 8.7 14.2 12.3 Example 3 12.5 17.8 16.6 Example 4 10.9 12.9 11.8 Example 5 11.6 15.3 14.5 Comparative Example 1 22.3 15.2 18.0 Comparative Example 2 38.5 44.9 55.6 Comparative Example 3 33.7 40.1 42.8 Comparative Example 4 28.8 22.2 34.4 Comparative Example 5 18.6 24.9 43.9

[0129] It can be seen from Table 1 that the method for removing heavy metal residues in the embodiment of the present invention has a small loss rate of the active ingredients quercetin, kaempferol and chebulic acid, which is less than 18%.

[0130] According to Comparative Examples 1, 2 and 3, when the adsorbent is only a single adsorbent or the proportion of a certain adsorbent is too large, the loss of active ingredients of traditional Chinese medicine is too large. According to Comparative Examples 4 and 5, the type and ratio of chelating resin have a great influence on the content of active ingredients in the extract. If a resin with a strong adsorption effect on the active ingredients is used, the active ingredients will be removed along with the adsorbent, and the removal effect of heavy metals will also be affected.

[0131] Test 2: Detection of heavy metal content

[0132] The heavy metal content in the Chinese medicine extract was determined using the "General Chapter 2321 Determination of Lead, Cadmium, Arsenic, Mercury and Copper of the Pharmacopoeia 2020 Edition", and the heavy metal removal rate results were recorded in Table 2.

[0133] Reference substance: Chinese herbal extract without heavy metal removal treatment: Add solutions of Pb, Cd, As, Hg and Cu to the Chinese herbal extract in the basic example, so that the mass content of each metal ion in the Chinese herbal extract is: 7.5 μg / g lead, 1.5 μg / g cadmium, 3 μg / g arsenic, 0.3 μg / g mercury and 30 μg / g copper, and mix thoroughly.

[0134] The heavy metal residues were removed from the above-mentioned traditional Chinese medicine extracts enriched with heavy metals by using the methods of the embodiments and comparative examples 1 to 7.

[0135] Heavy metal removal rate (%) = (m1-m2) / m1×100%; where m1 is the heavy metal content in the reference sample, and m2 is the heavy metal content in the extract after the heavy metal removal operation. The heavy metal removal rate results are shown in Table 2.

[0136] Table 2

[0137] Lead removal rate, % Cadmium removal rate, % Arsenic removal rate, % Mercury removal rate, % Copper removal rate, % Example 1 100 100 100 100 100 Comparative Example 1 46.3 52.8 55.4 62.5 39.3 Comparative Example 2 30.0 41.6 36.9 40.8 30.8 Comparative Example 3 75.3 78.1 82.0 80.7 78.4 Comparative Example 4 77.5 82.6 81.1 82.3 80.0 Comparative Example 5 89.2 86.3 85.0 86.2 90.6 Comparative Example 6 90.4 93.3 88.8 90.1 92.7 Comparative Example 7 78.9 80.5 86.7 85.2 80.3

[0138] The method for removing heavy metal residues in the embodiment of the present invention reduces the contents of five metals, namely, lead, cadmium, arsenic, mercury, and copper, to below the detection limit, and the heavy metal removal rate is regarded as 100%.

[0139] According to Comparative Examples 1, 2 and 6, when adsorbent A, adsorbent B or precipitant is missing, the effect of undetected heavy metals described in the embodiments of the present invention cannot be achieved, and the heavy metal removal effect is not ideal; it can be seen that adsorbent A, adsorbent B and precipitant are indispensable for the removal of heavy metals, and modified adsorbent A and chelating resin adsorb heavy metal ions to form insoluble precipitates, thereby stably removing heavy metals.

[0140] According to Comparative Example 3, when the ratio of modified modified adsorbent A and adsorbent B is not within the ratio range of the present invention, the removal effect of heavy metals is not ideal. According to Comparative Examples 4 and 5, although chelating resin has a certain effect of removing heavy metals, the chelating resin of the type and ratio described in the present invention can ensure that the removal rate of heavy metals reaches 100%, and improves the adsorption of heavy metals.

[0141] Therefore, the method for removing heavy metal residues of the present invention can not only make the heavy metal content below the detection limit, but also retain the active ingredients to the maximum extent, thereby ensuring the therapeutic efficacy of the traditional Chinese medicine preparation.

[0142] 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, characterized in that: Includes steps: S1. Preparation of modified composite adsorbent: Modified adsorbent A was prepared using porous silica gel as a carrier and sodium polyacrylate, sodium alginate and ethylenediaminetetraacetic acid as modification materials; Adsorbent B is an adsorption resin; The modified adsorbent A and the adsorbent B are mixed in a mass ratio of 3-5:1 to obtain a modified composite adsorbent; S2. Adsorption and precipitation: Mix the Chinese medicine extract with the modified composite adsorbent, add calcium sulfate, pressurize and stir for adsorption to obtain an extract with heavy metal residues removed.

2. The method according to claim 1, characterized in that In step S1, the porous silica gel has a particle size of 100-200 μm and an average pore size of 10-30 nm; the mass ratio of the porous silica gel to the modified material is 25-35:

1.

3. The method according to claim 1, characterized in that In step S1, the preparation method of the modified adsorbent A is: disperse porous silica gel in water, add a mixture of sodium polyacrylate, sodium alginate and ethylenediaminetetraacetic acid, stir and react at 50-70°C for 3-6h, and dry to obtain the modified adsorbent A.

4. The method according to claim 1, characterized in that: In step S1, in the modified material, the mass ratio of sodium polyacrylate, sodium alginate and ethylenediaminetetraacetic acid is 1-3:4-6:0.

5.

5. The method according to claim 1, characterized in that In step S1, the adsorption resin is a mixture of D401 chelating resin and D402 chelating resin.

6. The method according to claim 5, characterized in that The mass ratio of D401 to D402 is 1:3-6.

7. The method according to claim 1, characterized in that In step S1, the mass ratio of the modified adsorbent A to the adsorbent B is 4:

1.

8. The method according to claim 1, characterized in that In step S2, the mass ratio of the modified composite adsorbent to calcium sulfate is 1:0.05-0.2; In step S2, the pressurized stirring adsorption is: 0.1-0.3MPa 400-800rpm stirring adsorption treatment for 30-90min; In step S2, the added amount of the modified composite adsorbent is 35-45% of the mass of the Chinese medicine raw material.

9. Use of the method according to any one of claims 1 to 8 in the preparation of Eighteen-flavor Dujuan Pills.

10. A low-content heavy metal 18-flavor azalea pill, characterized in that: The preparation method comprises the steps of: (1) The Chinese medicinal raw material components of Shibawei Dujuan Pills are mixed with water, heated and extracted to obtain a Chinese medicinal extract and medicinal residues; (2) treating the Chinese medicine extract to remove heavy metal residues, thereby obtaining an extract from which heavy metal residues have been removed; the treating method is the method according to any one of claims 1 to 8; (3) concentrating and drying the extract from which the heavy metal residues have been removed, and mixing it with the medicinal residues to prepare Eighteen-flavor Dujuan Pills; Or the preparation method comprises the steps of: (1) Except for the liquorice paste, the Chinese medicinal raw material ingredients of Shibawei Dujuan Pills are mixed with water, heated and extracted to obtain a Chinese medicinal extract and medicinal residues; (2) treating the Chinese medicine extract to remove heavy metal residues, thereby obtaining an extract from which heavy metal residues have been removed; the treating method is the method according to any one of claims 1 to 8; (3) The extract from which the heavy metal residues have been removed is concentrated and dried, and mixed with the medicinal residues and liquorice paste to prepare Eighteen-flavor Dujuan Pills.