CN112973190B - Method for removing heavy metal in traditional Chinese medicine extracting solution - Google Patents
Method for removing heavy metal in traditional Chinese medicine extracting solution Download PDFInfo
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Abstract
The invention belongs to the technical field of traditional Chinese medicine heavy metal removal, and discloses a method for removing heavy metal in traditional Chinese medicine extract, which comprises the following steps: (1) decocting the Chinese medicinal materials in water solution, filtering to remove residue, and collecting filtrate; decocting the residue with water again, filtering to obtain filtrate; (2) the two filtrates are combined, CuS @ magnetic chitosan composite adsorbent is added, stirring is carried out, and separation is carried out to obtain traditional Chinese medicine extract with low heavy metal content.
Description
Technical Field
The invention relates to the technical field of heavy metal adsorbents, and particularly relates to a method for removing heavy metals in a traditional Chinese medicine extracting solution.
Background
The traditional Chinese medicine is an important component of the world traditional medicine, is a treasure of Chinese nationality, has the characteristics of unique curative effect, rich resources and the like, and simultaneously shows unique advantages in the development of medicine and health and the promotion of human health. However, the excessive heavy metal content in the traditional Chinese medicine becomes a focus of influencing human health (such as multiple organ function damage, influencing the central nervous system, inhibiting the immune system and the like) and forms a green trade barrier of the traditional Chinese medicine export, and is also a bottleneck for restricting the traditional Chinese medicine from going to modernization and internationalization.
Heavy metals are harmful to human bodies, damage to the nervous system, the digestive system, the hematopoietic system, the liver and kidney functions can be caused, and normal metabolism of cells can be affected, wherein the harm of lead (Pb), cadmium (Cd), arsenic (As), mercury (Hg) and copper (Cu) is more prominent. The sources of the heavy metals in the traditional Chinese medicine are related to the growing environment (such as soil, industrial three wastes pollution, pesticide and chemical fertilizer pollution and the like), so that the heavy metal ions of the traditional Chinese medicine, particularly the roots of the traditional Chinese medicine are more accumulated; secondly, the inevitable contact of the traditional Chinese medicines with metal containers or equipment during collection, transportation, storage and processing can also introduce heavy metal ions (such as containers or auxiliary materials used for processing the traditional Chinese medicines); it is also related to the genetic characteristics of plants, so that the production of Chinese medicines involves multiple links, and the heavy metals are difficult to be completely controlled from the source.
The Chinese patent medicine is generally a compound preparation and comprises a plurality of Chinese medicines, mixed extraction operation is involved in the production process, and the mutual superposition of heavy metals contained in the Chinese medicines is likely to cause the total amount of the heavy metals in the compound to exceed the standard, so that Chinese patent medicine production enterprises can strictly monitor the heavy metals, monitor the heavy metals in various ways such as supplier management, Chinese medicine decoction piece incoming material detection, finished product heavy metal detection and the like, destroy of finished products which do not meet the indexes, and have huge cost of manpower and material resources, and research and development personnel in the field need to develop a method suitable for removing the heavy metals in the Chinese patent medicine preparation process so as to reduce the cost of the enterprises in the aspect of controlling the content of the heavy metals in the Chinese medicines.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention mainly aims to provide a method for removing heavy metal in a traditional Chinese medicine extracting solution.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for removing heavy metals in traditional Chinese medicine extract comprises the following steps:
(1) decocting the Chinese medicinal materials in water solution, filtering to remove residue, and retaining filtrate; decocting the residue with water again, filtering to obtain filtrate;
(2) and combining the two filtrates, adding a CuS @ magnetic chitosan composite adsorbent, stirring, and separating to obtain the traditional Chinese medicine extracting solution with low heavy metal content.
Further, in the step (1), the traditional Chinese medicinal materials can be traditional Chinese medicinal materials of a nose comforting tablet; the traditional Chinese medicinal materials of the nose comforting tablet comprise fructus Xanthii, flos Chrysanthemi Indici, herba Centipedae, radix Angelicae Dahuricae, radix Saposhnikoviae, Ecliptae herba, radix Paeoniae alba, Glycyrrhrizae radix, and fructus Tribuli.
Further, the preparation method of the CuS @ magnetic chitosan composite adsorbent in the step (2) comprises the following steps:
s1: dissolving chitosan in acetic acid solution to obtain chitosan acidAdding magnetic Fe into the solution 3 O 4 Carrying out ultrasonic dispersion on the nano particles to obtain a mixed solution;
s2: adding cetyl trimethyl ammonium bromide into the mixed solution, stirring, separating, cleaning and drying to obtain magnetic chitosan microspheres;
s3: adding the magnetic chitosan microspheres into an ethanol solution, and uniformly stirring to obtain a magnetic chitosan microsphere dispersion liquid;
s4: adding sodium citrate into the magnetic chitosan microsphere dispersion, stirring uniformly, adding ammonia water to adjust the pH value to 8.0-8.5, continuously adding copper chloride, heating and stirring, finally adding thiourea, stirring for reaction, separating and drying to obtain the CuS @ magnetic chitosan composite adsorbent.
Further, the concentration of the acetic acid solution in S1 is 1-3%.
Further, the concentration of chitosan in the chitosan acidic solution in S1 is 0.01-0.05 g/mL.
Further, Fe in the mixed solution described in S1 3 O 4 The concentration of the nano particles is 0.01-0.03 g/mL.
Further, the cetyltrimethylammonium bromide in S2 was added to the mixed solution in an amount of 0.001-0.002 g/mL.
Further, in S2, the stirring is carried out for 12-24h under the conditions of 800-1200 r/min.
Further, the separation in S2 may be performed using a magnet.
Further, the washing in S2 may be performed with water for a plurality of times; the drying may be by conventional freeze drying.
Further, the concentration of the ethanol solution in S3 is 75-85%.
Further, the addition amount of the magnetic chitosan microspheres in S3 to the ethanol solution is 0.1-1 g/mL.
Further, the concentration of the copper chloride in the magnetic chitosan microsphere dispersion liquid in S4 is 0.01-0.05 mol/L; the molar ratio of the sodium citrate to the cupric chloride to the thiourea is (2-3): 1: (1-1.5).
Further, the conditions of heating and stirring after adding the copper chloride in the S4 are 50-80 ℃, and stirring at the speed of 300-800r/min for 20-30 min.
Further, the stirring reaction condition after the thiourea is finally added in the S4 is that the stirring is carried out for 6 to 12 hours at the temperature of between 50 and 80 ℃ and at the speed of between 300 and 800 r/min.
Further, the separation in S4 may be performed using a magnet.
Further, the drying in S4 can be carried out for 12h at 60-80 ℃.
Further, in the step (2), the addition amount of the CuS @ magnetic chitosan composite adsorbent is 2-5 g/L.
Further, in the step (2), the stirring is carried out for 1-3h under the conditions of 300-600 r/min.
Further, in the step (2), the separation may be performed by using a magnet to separate the CuS @ magnetic chitosan microspheres.
Compared with the prior art, the invention has the following advantages and technical effects:
(1) the method for removing the heavy metals in the traditional Chinese medicine extracting solution has the advantages of simple process, high heavy metal removal rate and the like, can simultaneously remove five heavy metal elements of lead (Pb), cadmium (Cd), arsenic (As), mercury (Hg) and copper (Cu) in the traditional Chinese medicine extracting solution, and the removal rates can respectively reach 96% (Pb), 95% (Cd), 92% (As), 99% (Hg) and 86% (Cu).
(2) The invention adopts a CuS @ magnetic chitosan composite adsorbent to adsorb heavy metals in a traditional Chinese medicine extracting solution, the CuS @ magnetic chitosan composite adsorbent is of a three-layer structure, and Fe 3 O 4 -chitosan-CuS structure with magnetic Fe 3 O 4 The magnetic Fe is coated by chitosan with the nano particles as the core 3 O 4 The nano particles form microspheres with a porous net structure, and finally the microspheres are coated by CuS through a deposition method to finally prepare the CuS @ magnetic chitosan composite adsorbent.
(3) The chitosan is a natural high molecular polymer, a molecular chain contains a large amount of amino and hydroxyl groups, and after the chitosan is prepared into microspheres, the interior of the microspheres is of a porous net structure, so that the chitosan has good effect on heavy metalsHowever, chitosan is unstable in acidic solution and separation is difficult after the reaction is completed, so magnetic Fe is used in the invention 3 O 4 The nano particles are used as the core, the solid-liquid separation of the traditional Chinese medicine extracting solution and the composite adsorbent can be effectively realized through an external magnetic field, and simultaneously, the surface of the microsphere is coated with the CuS, so that the stability of the composite adsorbent is greatly enhanced due to the extremely stable property of the CuS, and the composite adsorbent still has a good adsorption effect under an acidic condition.
(4) The invention provides a CuS @ magnetic chitosan composite adsorbent, which adopts chitosan to react with magnetic Fe 3 O 4 Nanoparticles of reduced magnetic Fe 3 O 4 The agglomeration phenomenon of the nano particles enables the composite adsorbent to have magnetism and be easy to separate, and meanwhile, the composite adsorbent also has the characteristic of being easy to disperse and not easy to agglomerate.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited thereto. All the raw materials and reagents used in the present invention are commercially available raw materials and reagents, unless otherwise specified. In the examples, the components are used in g and mL in parts by mass.
Example 1
(1) Preparing a CuS @ magnetic chitosan composite adsorbent:
s1: dissolving 3 parts by mass of chitosan in 100 parts by volume of 2% acetic acid solution to obtain chitosan acidic solution, and continuously adding 2 parts by mass of Fe 3 O 4 Carrying out ultrasonic dispersion on the nano particles to obtain a mixed solution;
s2: adding 0.1 part by mass of hexadecyl trimethyl ammonium bromide into the mixed solution, stirring for 12 hours under the condition of 1000r/min, carrying out magnetic separation, washing for three times by using water, and carrying out freeze drying to obtain magnetic chitosan microspheres;
s3: adding 0.5 part by mass of magnetic chitosan microspheres into 100 parts by volume of 80% ethanol solution, and stirring for 25min at the speed of 1000r/min to obtain magnetic chitosan microsphere dispersion liquid;
s4: adding sodium citrate (with the concentration of 0.06mol/L) into the magnetic chitosan microsphere dispersion, stirring at 500r/min for 30min, then adding ammonia water to adjust the pH of the dispersion to 8.0, continuously adding copper chloride (with the concentration of 0.03mol/L), stirring at 60 ℃ and 500r/min for 30min, finally adding thiourea (with the concentration of 0.03mol/L) and stirring at 60 ℃ and 500r/min for 12h, carrying out magnetic separation, and drying at 80 ℃ for 12h to obtain the CuS @ magnetic chitosan composite adsorbent.
(2) Decocting 10 parts by mass of traditional Chinese medicine raw materials of the nasal comforting tablets (wherein the proportion of cocklebur fruit, wild chrysanthemum, centipeda minima, angelica dahurica, divaricate saposhnikovia root, eclipta, white paeony root, liquorice and tribulus terrestris is executed according to the ministerial standard traditional Chinese medicine prescription preparation WS 3-B-1454-93) with 200 parts by volume of water, filtering out dregs, and reserving filtrate; decocting the dregs with 200 parts by volume of water again, filtering the dregs, and keeping the filtrate;
(3) mixing the two filtrates, adding CuS @ magnetic chitosan composite adsorbent (the addition amount is 3g/L), stirring for 1h at the speed of 600r/min, and performing magnetic separation to obtain the traditional Chinese medicine extract with low heavy metal content.
Example 2
(1) Preparing a CuS @ magnetic chitosan composite adsorbent:
s1: dissolving 5 parts by mass of chitosan in 100 parts by volume of 1% acetic acid solution to obtain chitosan acidic solution, and continuously adding 1 part by mass of Fe 3 O 4 Carrying out ultrasonic dispersion on the nano particles to obtain a mixed solution;
s2: adding 0.2 part by mass of hexadecyl trimethyl ammonium bromide into the mixed solution, stirring for 24 hours under the condition of 800r/min, carrying out magnetic separation, washing with water for three times, and carrying out freeze drying to obtain magnetic chitosan microspheres;
s3: adding 0.1 part by mass of magnetic chitosan microspheres into 100 parts by volume of 85% ethanol solution, and stirring for 20min at the speed of 800r/min to obtain magnetic chitosan microsphere dispersion;
s4: adding sodium citrate (with the concentration of 0.15mol/L) into the magnetic chitosan microsphere dispersion, stirring for 20min at 300r/min, then adding ammonia water to adjust the pH of the dispersion to 8.2, continuously adding copper chloride (with the concentration of 0.05mol/L), stirring for 20min at 80 ℃ and 300r/min, finally adding thiourea (with the concentration of 0.075mol/L) and stirring for 8h at 80 ℃ and 300r/min, and carrying out magnetic separation and drying for 12h at 60 ℃ to obtain the CuS @ magnetic chitosan composite adsorbent.
(2) Decocting 10 parts by mass of traditional Chinese medicine raw materials of the nasal comforting tablets (wherein the proportion of cocklebur fruit, wild chrysanthemum, centipeda minima, angelica dahurica, divaricate saposhnikovia root, eclipta, white paeony root, liquorice and tribulus terrestris is executed according to the ministerial standard traditional Chinese medicine prescription preparation WS 3-B-1454-93) with 200 parts by volume of water, filtering out dregs, and reserving filtrate; decocting the dregs with 200 parts by volume of water again, filtering the dregs, and keeping the filtrate;
(3) mixing the two filtrates, adding CuS @ magnetic chitosan composite adsorbent (the addition amount is 3g/L), stirring for 1h at the speed of 600r/min, and performing magnetic separation to obtain the traditional Chinese medicine extract with low heavy metal content.
Example 3
(1) Preparing a CuS @ magnetic chitosan composite adsorbent:
s1: dissolving 1 part by mass of chitosan in 100 parts by volume of 3% acetic acid solution to obtain chitosan acidic solution, and continuously adding 3 parts by mass of Fe 3 O 4 Carrying out ultrasonic dispersion on the nano particles to obtain a mixed solution;
s2: adding 0.15 part by mass of hexadecyl trimethyl ammonium bromide into the mixed solution, stirring for 18 hours under the condition of 1200r/min, carrying out magnetic separation, washing for three times by using water, and carrying out freeze drying to obtain magnetic chitosan microspheres;
s3: adding 1 part by mass of magnetic chitosan microspheres into 100 parts by volume of 75% ethanol solution, and stirring for 30min at the speed of 1200r/min to obtain magnetic chitosan microsphere dispersion liquid;
s4: adding sodium citrate (with the concentration of 0.025mol/L) into the magnetic chitosan microsphere dispersion, stirring for 30min at the speed of 500r/min, then adding ammonia water to adjust the pH value of the dispersion to 8.5, continuously adding copper chloride (with the concentration of 0.01mol/L), stirring for 30min at the temperature of 50 ℃ and 300r/min, finally adding thiourea (with the concentration of 0.015mol/L) and stirring for 8h at the temperature of 50 ℃ and 300r/min, and carrying out magnetic separation and drying for 12h at the temperature of 70 ℃ to obtain the CuS @ magnetic chitosan composite adsorbent.
(2) Decocting 10 parts by mass of traditional Chinese medicine raw materials of the nasal comforting tablets (wherein the proportion of cocklebur fruit, wild chrysanthemum, centipeda minima, angelica dahurica, divaricate saposhnikovia root, eclipta, white paeony root, liquorice and tribulus terrestris is executed according to the ministerial standard traditional Chinese medicine prescription preparation WS 3-B-1454-93) with 200 parts by volume of water, filtering out dregs, and reserving filtrate; decocting the dregs with 200 parts by volume of water again, filtering out the dregs, and keeping the filtrate;
(3) mixing the two filtrates, adding CuS @ magnetic chitosan composite adsorbent (the addition amount is 3g/L), stirring for 1h at the speed of 600r/min, and performing magnetic separation to obtain the traditional Chinese medicine extract with low heavy metal content.
Example 4
(1) Preparing a CuS @ magnetic chitosan composite adsorbent:
s1: dissolving 3 parts by mass of chitosan in 100 parts by volume of 2% acetic acid solution to obtain chitosan acidic solution, and continuously adding 2 parts by mass of Fe 3 O 4 Carrying out ultrasonic dispersion on the nano particles to obtain a mixed solution;
s2: adding 0.1 part by mass of hexadecyl trimethyl ammonium bromide into the mixed solution, stirring for 12 hours under the condition of 1000r/min, carrying out magnetic separation, washing for three times by using water, and carrying out freeze drying to obtain magnetic chitosan microspheres;
s3: adding 0.5 part by mass of magnetic chitosan microspheres into 100 parts by volume of 80% ethanol solution, and stirring for 25min at the speed of 1000r/min to obtain magnetic chitosan microsphere dispersion;
s4: adding sodium citrate (with the concentration of 0.06mol/L) into the magnetic chitosan microsphere dispersion, stirring at 500r/min for 30min, then adding ammonia water to adjust the pH of the dispersion to 8.0, continuously adding copper chloride (with the concentration of 0.03mol/L), stirring at 60 ℃ and 500r/min for 30min, finally adding thiourea (with the concentration of 0.075mol/L) and stirring at 60 ℃ and 500r/min for 12h, carrying out magnetic separation, and drying at 80 ℃ for 12h to obtain the CuS @ magnetic chitosan composite adsorbent.
(2) Decocting 10 parts by mass of traditional Chinese medicine raw materials of the nasal comforting tablets (wherein the proportion of cocklebur fruit, wild chrysanthemum, centipeda minima, angelica dahurica, divaricate saposhnikovia root, eclipta, white paeony root, liquorice and tribulus terrestris is executed according to the ministerial standard traditional Chinese medicine prescription preparation WS 3-B-1454-93) with 200 parts by volume of water, filtering out dregs, and reserving filtrate; decocting the dregs with 200 parts by volume of water again, filtering the dregs, and keeping the filtrate;
(3) mixing the two filtrates, adding CuS @ magnetic chitosan composite adsorbent (the addition amount is 5g/L), stirring for 2h at 300r/min, and performing magnetic separation to obtain the traditional Chinese medicine extract with low heavy metal content.
Example 5
(1) Preparing a CuS @ magnetic chitosan composite adsorbent:
s1: dissolving 3 parts by mass of chitosan in 100 parts by volume of 2% acetic acid solution to obtain chitosan acidic solution, and continuously adding 2 parts by mass of Fe 3 O 4 Carrying out ultrasonic dispersion on the nano particles to obtain a mixed solution;
s2: adding 0.1 part by mass of hexadecyl trimethyl ammonium bromide into the mixed solution, stirring for 12 hours under the condition of 1000r/min, carrying out magnetic separation, washing for three times by using water, and carrying out freeze drying to obtain magnetic chitosan microspheres;
s3: adding 0.5 part by mass of magnetic chitosan microspheres into 100 parts by volume of 80% ethanol solution, and stirring for 25min at the speed of 1000r/min to obtain magnetic chitosan microsphere dispersion liquid;
s4: adding sodium citrate (with the concentration of 0.06mol/L) into the magnetic chitosan microsphere dispersion, stirring at 500r/min for 30min, then adding ammonia water to adjust the pH of the dispersion to 8.0, continuously adding copper chloride (with the concentration of 0.03mol/L), stirring at 60 ℃ and 500r/min for 30min, finally adding thiourea (with the concentration of 0.075mol/L) and stirring at 60 ℃ and 500r/min for 12h, carrying out magnetic separation, and drying at 80 ℃ for 12h to obtain the CuS @ magnetic chitosan composite adsorbent.
(2) Decocting 10 parts by mass of traditional Chinese medicine raw materials of the nasal comforting tablets (wherein the proportion of cocklebur fruit, wild chrysanthemum, centipeda minima, angelica dahurica, divaricate saposhnikovia root, eclipta, white paeony root, liquorice and tribulus terrestris is executed according to the ministerial standard traditional Chinese medicine prescription preparation WS 3-B-1454-93) with 200 parts by volume of water, filtering out dregs, and reserving filtrate; decocting the dregs with 200 parts by volume of water again, filtering the dregs, and keeping the filtrate;
(3) mixing the two filtrates, adding CuS @ magnetic chitosan composite adsorbent (the addition amount is 2g/L), stirring for 3h under the condition of 400r/min, and performing magnetic separation to obtain the traditional Chinese medicine extract with low heavy metal content.
Comparative example 1
(1) Preparing a CuS @ magnetic chitosan composite adsorbent:
s1: dissolving 3 parts by mass of chitosan in 100 parts by volume of 2% acetic acid solution to obtain chitosan acidic solution, and continuously adding 2 parts by mass of Fe 3 O 4 Carrying out ultrasonic dispersion on the nano particles to obtain a mixed solution;
s2: adding 0.1 part by mass of hexadecyl trimethyl ammonium bromide into the mixed solution, stirring for 12 hours under the condition of 1000r/min, carrying out magnetic separation, washing for three times by using water, and carrying out freeze drying to obtain magnetic chitosan microspheres;
(2) decocting 10 parts by mass of traditional Chinese medicine raw materials of the nasal comforting tablets (wherein the proportion of cocklebur fruit, wild chrysanthemum flower, centipeda minima, angelica dahurica, divaricate saposhnikovia root, yerbadetajo herb, white paeony root, liquorice and tribulus terrestris is executed according to WS3-B-1454-93 of a ministerial standard traditional Chinese medicine prescription preparation) with 200 parts by volume of water, filtering out dregs, and reserving filtrate; decocting the dregs with 200 parts by volume of water again, filtering the dregs, and keeping the filtrate;
(3) mixing the two filtrates, adding magnetic chitosan microsphere (with addition amount of 3g/L), stirring at 600r/min for 1 hr, and magnetic separating to obtain Chinese medicinal extractive solution.
Comparative example 2
(1) Preparing a CuS @ magnetic chitosan composite adsorbent:
s1: dissolving 3 parts by mass of chitosan in 100 parts by volume of 2% acetic acid solution to obtain chitosan acidic solution, and continuously adding 2 parts by mass of Fe 3 O 4 Carrying out ultrasonic dispersion on the nano particles to obtain a mixed solution;
s2: adding 0.1 part by mass of hexadecyl trimethyl ammonium bromide into the mixed solution, stirring for 12 hours under the condition of 1000r/min, carrying out magnetic separation, washing for three times by using water, and carrying out freeze drying to obtain magnetic chitosan microspheres;
s3: adding 0.5 part by mass of magnetic chitosan microspheres into 100 parts by volume of 80% ethanol solution, and stirring for 25min at the speed of 1000r/min to obtain magnetic chitosan microsphere dispersion;
s4: adding sodium citrate (with the concentration of 0.06mol/L) into the magnetic chitosan microsphere dispersion, stirring at 500r/min for 30min, then adding ammonia water to adjust the pH of the dispersion to 9.0, continuously adding copper chloride (with the concentration of 0.03mol/L), stirring at 60 ℃ and 500r/min for 30min, finally adding thiourea (with the concentration of 0.03mol/L) and stirring at 60 ℃ and 500r/min for 12h, carrying out magnetic separation, and drying at 80 ℃ for 12h to obtain the CuS @ magnetic chitosan composite adsorbent.
(2) Decocting 10 parts by mass of traditional Chinese medicine raw materials of the nasal comforting tablets (wherein the proportion of cocklebur fruit, wild chrysanthemum, centipeda minima, angelica dahurica, divaricate saposhnikovia root, eclipta, white paeony root, liquorice and tribulus terrestris is executed according to the ministerial standard traditional Chinese medicine prescription preparation WS 3-B-1454-93) with 200 parts by volume of water, filtering out dregs, and reserving filtrate; decocting the dregs with 200 parts by volume of water again, filtering the dregs, and keeping the filtrate;
(3) mixing the two filtrates, adding CuS @ magnetic chitosan composite adsorbent (addition amount of 3g/L), stirring at 600r/min for 1h, and magnetically separating to obtain Chinese medicinal extractive solution.
Comparative example 3
(1) Preparing a CuS @ magnetic chitosan composite adsorbent:
s1: dissolving 3 parts by mass of chitosan in 100 parts by volume of 2% acetic acid solution to obtain chitosan acidic solution, and continuously adding 2 parts by mass of Fe 3 O 4 Carrying out ultrasonic dispersion on the nano particles to obtain a mixed solution;
s2: adding 0.1 part by mass of hexadecyl trimethyl ammonium bromide into the mixed solution, stirring for 12 hours under the condition of 1000r/min, carrying out magnetic separation, washing for three times by using water, and carrying out freeze drying to obtain magnetic chitosan microspheres;
s3: adding 0.5 part by mass of magnetic chitosan microspheres into 100 parts by volume of 80% ethanol solution, and stirring for 25min at the speed of 1000r/min to obtain magnetic chitosan microsphere dispersion;
s4: adding sodium citrate (with the concentration of 0.03mol/L) into the magnetic chitosan microsphere dispersion, stirring at 500r/min for 30min, then adding ammonia water to adjust the pH of the dispersion to 8.0, continuously adding copper chloride (with the concentration of 0.03mol/L), stirring at 60 ℃ and 500r/min for 30min, finally adding thiourea (with the concentration of 0.09mol/L) and stirring at 60 ℃ and 500r/min for 12h, carrying out magnetic separation, and drying at 80 ℃ for 12h to obtain the CuS @ magnetic chitosan composite adsorbent.
(2) Decocting 10 parts by mass of traditional Chinese medicine raw materials of the nasal comforting tablets (wherein the proportion of cocklebur fruit, wild chrysanthemum, centipeda minima, angelica dahurica, divaricate saposhnikovia root, eclipta, white paeony root, liquorice and tribulus terrestris is executed according to the ministerial standard traditional Chinese medicine prescription preparation WS 3-B-1454-93) with 200 parts by volume of water, filtering out dregs, and reserving filtrate; decocting the dregs with 200 parts by volume of water again, filtering the dregs, and keeping the filtrate;
(3) mixing the two filtrates, adding CuS @ magnetic chitosan composite adsorbent (the addition amount is 3g/L), stirring for 1h at 600r/min, and performing magnetic separation to obtain traditional Chinese medicine extract.
Comparative example 4
(1) Preparing a CuS @ magnetic chitosan composite adsorbent:
s1: dissolving 3 parts by mass of chitosan in 100 parts by volume of 2% acetic acid solution to obtain chitosan acidic solution, and continuously adding 2 parts by mass of Fe 3 O 4 Carrying out ultrasonic dispersion on the nano particles to obtain a mixed solution;
s2: adding the mixed solution into 500 parts by volume of liquid paraffin solution (containing 2% of Span80), fully stirring and uniformly mixing, adding 20 parts by volume of formaldehyde, reacting at 40 ℃ for 1h, then adjusting the pH to 9 with NaOH, heating to 70 ℃, continuing to react for 2h, carrying out magnetic separation, washing with water for three times, and drying to obtain magnetic chitosan microspheres;
s3: adding 0.5 part by mass of magnetic chitosan microspheres into 100 parts by volume of 80% ethanol solution, and stirring for 25min at the speed of 1000r/min to obtain magnetic chitosan microsphere dispersion;
s4: adding sodium citrate (with the concentration of 0.06mol/L) into the magnetic chitosan microsphere dispersion, stirring at 500r/min for 30min, then adding ammonia water to adjust the pH of the dispersion to 8.0, continuously adding copper chloride (with the concentration of 0.03mol/L), stirring at 60 ℃ and 500r/min for 30min, finally adding thiourea (with the concentration of 0.03mol/L) and stirring at 60 ℃ and 500r/min for 12h, carrying out magnetic separation, and drying at 80 ℃ for 12h to obtain the CuS @ magnetic chitosan composite adsorbent.
(2) Decocting 10 parts by mass of traditional Chinese medicine raw materials of the nasal comforting tablets (wherein the proportion of cocklebur fruit, wild chrysanthemum, centipeda minima, angelica dahurica, divaricate saposhnikovia root, eclipta, white paeony root, liquorice and tribulus terrestris is executed according to the ministerial standard traditional Chinese medicine prescription preparation WS 3-B-1454-93) with 200 parts by volume of water, filtering out dregs, and reserving filtrate; decocting the dregs with 200 parts by volume of water again, filtering the dregs, and keeping the filtrate;
(3) mixing the two filtrates, adding CuS @ magnetic chitosan composite adsorbent (the addition amount is 3g/L), stirring for 1h at 600r/min, and performing magnetic separation to obtain traditional Chinese medicine extract.
The extracts of the chinese herbs of examples 1-3 and comparative examples 1-4 were treated with five heavy metals of lead (Pb), cadmium (Cd), arsenic (As), mercury (Hg), and copper (Cu) before and after the addition of the adsorbent, respectively, and the removal rates of the five heavy metals were calculated, and the specific results are shown in table 1.
Table 1 results of the removal rate of heavy metals in five Chinese medicinal extracts of each group
| Group of | Pb/％ | Cd/％ | As/％ | Hg/％ | Cu/％ |
| Example 1 | 96.8 | 95.2 | 92.3 | 99.2 | 86.7 |
| Example 2 | 97.2 | 95.8 | 93.4 | 99.0 | 88.4 |
| Example 3 | 96.3 | 96.8 | 93.6 | 99.5 | 86.8 |
| Comparative example 1 | 82.1 | 75.1 | 76.8 | 67.3 | 75.1 |
| Comparative example 2 | 83.4 | 81.4 | 82.4 | 76.8 | 72.8 |
| Comparative example 3 | 86.7 | 83.8 | 86.7 | 75.4 | 73.9 |
| Comparative example 4 | 78.9 | 81.4 | 85.2 | 84.9 | 73.8 |
As can be seen from the results in Table 1, examples 1 to 3 had good removal rates of heavy metals from the herb extracts, wherein the removal rates were 96% (Pb), 95% (Cd), 92% (As), 99% (Hg) and 86% (Cu), respectively.
Compared with the embodiment 1, the adsorbent of the comparative example 1 is not coated by CuS, the adsorption effect on five metal elements is obviously reduced, particularly the removal rate of mercury is reduced to 67.3%, mainly because the CuS layer in the composite adsorbent can specifically adsorb mercury ions, and the CuS layer can improve the structural stability of the composite adsorbent, so that the composite adsorbent can keep a stable adsorption effect in a long-time stirring process.
Comparative examples 2-3 compared with example 1, the ammonia water of step S4 in comparative example 2 is adjusted to pH 9.0, the molar ratio of sodium citrate, copper chloride and thiourea in comparative example 3 is 1:1:3, the deposition of CuS on the magnetic chitosan microspheres is directly influenced due to different conditions, so that the adsorption effect of CuS on heavy metals is influenced, specifically, when the pH is too high, the decomposition speed of thiourea is accelerated, and S is 2- Fast release with Cu 2+ The reaction speed is accelerated, more CuS exists in a precipitation mode, and CuS deposited and coated on the surface of the magnetic chitosan is reduced; sodium citrate is used as complexing agent, and when the concentration of the complexing agent is increased, Cu is enabled 2+ The complex is more compact, so that the release is slowed down, and the deposition of CuS on the surface of the microsphere is facilitated; when the addition amount of thiourea is increased, S 2- Greater concentration in solution with Cu 2+ The bonding rate is accelerated, so that Cu 2+ And S 2- Generated in solution as a precipitate, resulting in a reduction of the CuS that is ultimately deposited on the microsphere surface.
Compared with the example 1, the method for preparing the magnetic chitosan microspheres in the step S2 is different, the invention adopts cetyl trimethyl ammonium bromide to prepare the microspheres for chitosan, wherein the cetyl trimethyl ammonium bromide is used as a precipitator and can be used as a modifier to have a synergistic adsorption effect with the magnetic chitosan microspheres, so that the adsorption effect of the composite adsorbent on heavy metals is improved, and the preparation method of the comparative example 4 has no effect, so that the adsorption effect is obviously reduced compared with the example 1.
Fe in CuS @ magnetic chitosan composite adsorbent provided by the invention 3 O 4 The nano particles, the chitosan and the CuS are synergistic, and meanwhile, the CuS @ magnetic chitosan composite adsorbent shows a good adsorption effect on five heavy metals in the traditional Chinese medicine extracting solution by adopting a suitable preparation method.
The above embodiments are the best mode for carrying out the present invention, but the embodiments of the present invention are 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 regarded as equivalent substitutions and are included in the scope of the present invention.
Claims (9)
1. A method for removing heavy metals in traditional Chinese medicine extract is characterized by comprising the following steps:
(1) decocting the Chinese medicinal materials in water solution, filtering to remove residue, and collecting filtrate; decocting the residue with water again, filtering to obtain filtrate;
(2) mixing the two filtrates, adding CuS @ magnetic chitosan composite adsorbent, stirring, and separating to obtain traditional Chinese medicine extract with low heavy metal content;
the preparation method of the CuS @ magnetic chitosan composite adsorbent in the step (2) comprises the following steps:
s1: dissolving chitosan in acetic acid solution to obtain chitosan acidic solution, and continuously adding magnetic Fe 3 O 4 Carrying out ultrasonic dispersion on the nano particles to obtain a mixed solution;
s2: adding cetyl trimethyl ammonium bromide into the mixed solution, stirring, separating, cleaning and drying to obtain magnetic chitosan microspheres;
s3: adding the magnetic chitosan microspheres into an ethanol solution, and uniformly stirring to obtain a magnetic chitosan microsphere dispersion liquid;
s4: adding sodium citrate into the magnetic chitosan microsphere dispersion, stirring uniformly, adding ammonia water to adjust the pH value to 8.0-8.5, continuously adding copper chloride, heating and stirring, finally adding thiourea, stirring for reaction, separating and drying to obtain a CuS @ magnetic chitosan composite adsorbent;
in S4, the concentration of the copper chloride in the magnetic chitosan microsphere dispersion liquid is 0.01-0.05 mol/L; the molar ratio of the sodium citrate to the cupric chloride to the thiourea is (2-3): 1: (1-1.5).
2. The method for removing heavy metals in traditional Chinese medicine extracting solution according to claim 1, which is characterized by comprising the following steps: in the step (1), the traditional Chinese medicinal materials are traditional Chinese medicinal materials of a nose comforting tablet; the traditional Chinese medicinal materials of the nose comforting tablet comprise fructus Xanthii, flos Chrysanthemi Indici, herba Centipedae, radix Angelicae Dahuricae, radix Saposhnikoviae, Ecliptae herba, radix Paeoniae alba, Glycyrrhrizae radix, and fructus Tribuli.
3. The method for removing heavy metals in traditional Chinese medicine extracting solution according to claim 1, which is characterized by comprising the following steps: in the step (2), the addition amount of the CuS @ magnetic chitosan composite adsorbent is 2-5 g/L.
4. The method for removing heavy metals in traditional Chinese medicine extracting solution according to claim 1, which is characterized by comprising the following steps: in the step (2), the stirring is performed for 1-3h under the conditions of 300-600 r/min.
5. The method for removing heavy metals in traditional Chinese medicine extracting solution according to claim 1, which is characterized by comprising the following steps: in the step (2), the CuS @ magnetic chitosan microspheres are separated by adopting a magnet.
6. The method for removing heavy metals in traditional Chinese medicine extracting solution according to claim 1, which is characterized by comprising the following steps: the concentration of chitosan in the chitosan acid solution in S1 is 0.01-0.05 g/mL; fe in the mixed solution 3 O 4 The concentration of the nano particles is 0.01-0.03 g/mL.
7. The method for removing heavy metals in traditional Chinese medicine extracting solution according to claim 1, which is characterized by comprising the following steps: the concentration of the ethanol solution in the S3 is 75-85%; the addition amount of the magnetic chitosan microspheres to the ethanol solution is 0.1-1 g/mL.
8. The method for removing heavy metals in traditional Chinese medicine extracting solution according to claim 1, which is characterized by comprising the following steps: the concentration of the copper chloride in the magnetic chitosan microsphere dispersion liquid in S4 is 0.01-0.05 mol/L.
9. The method for removing heavy metals in traditional Chinese medicine extracting solution according to claim 1, which is characterized by comprising the following steps: the stirring reaction condition after the thiourea is finally added in the S4 is that the stirring is carried out for 6 to 12 hours at the temperature of between 50 and 80 ℃ and at the speed of between 300 and 800 r/min.
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