A ganoderma lucidum spore powder heavy metal removal process

Abstract

The present application relates to ganoderma spore powder production field, specifically to a kind of ganoderma spore powder heavy metal removal process, comprising the following steps: (1) composite complexing agent, ganoderma spore powder and anhydrous ethanol are placed into extractor, microwave treatment is assisted in sealing process, and pretreated liquor is obtained;(2) composite surfactant and ethanol solution are mixed and added into supercritical CO2 fluid phase, and supercritical CO2 solubilizing fluid is obtained;(3) pretreated liquor is extracted using supercritical CO2 solubilizing fluid.The present application adds composite surfactant and ethanol solution in supercritical CO2 fluid, forms microemulsion in fluid phase, after microemulsion penetrates to the inside of ganoderma spore powder, it competes with heavy metal for adsorption active point, weakens the bondage of matrix to heavy metal ion, also be conducive to heavy metal ion and complexing agent complex, and play the role of solubilization and acceleration to heavy metal and its complex, improve the extraction effect of heavy metal in ganoderma spore powder.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of ganoderma lucidum spore powder production, and particularly relates to a heavy metal removal process for ganoderma lucidum spore powder. BACKGROUND

[0002] Ganoderma spores are extremely small oval reproductive cells ejected from the gills of ganoderma during the growth and maturation period, i.e. the seeds of ganoderma, which condense the essence of ganoderma and have good health care effects. However, since the ganoderma spores do not have a complete cell wall structure, they lack selectivity in absorbing various substances in the environment, which leads to a high content of heavy metals in the ganoderma spore powder. Therefore, it is necessary to remove these heavy metals during the processing of the ganoderma spore powder.

[0003] At present, a complexing agent is used to complex the heavy metal ions in the ganoderma spores, and then supercritical CO2 is used to extract the heavy metal complexes. However, part of the heavy metals are combined with the matrix relatively firmly, and the complexing agent cannot complex these heavy metals, and the supercritical CO2 fluid phase also cannot extract them. Therefore, the present application provides a heavy metal removal process for ganoderma spore powder. SUMMARY

[0004] (1) In view of the deficiencies in the prior art, the present application provides a heavy metal removal process for ganoderma spore powder, which overcomes the problem of general extraction effect in the heavy metal removal process in the prior art, and improves the extraction effect by solubilizing and accelerating the heavy metals and their complexes.

[0005] (2) To achieve the above purpose, the present application is implemented by the following technical scheme: a heavy metal removal process for ganoderma spore powder, specifically comprising the following steps:

[0006] (1) Put the composite complexing agent, ganoderma spore powder and anhydrous ethanol into an extractor, mix and seal, and assist with microwave treatment during the sealing process to obtain a pretreated liquid; the ganoderma spore powder is pretreated by rinsing with clean water before supercritical CO2 extraction, and then dried.

[0007] (2) Mix the composite surfactant and the ethanol solution, then add the mixed solution into the supercritical CO2 fluid phase to obtain a supercritical CO2 solubilizing fluid.

[0008] (3) Use the supercritical CO2 solubilizing fluid to extract the heavy metal complexes in the pretreated liquid, and after the extraction is completed, take out the material in the extractor and dry it.

[0009] Preferably, in step (1), the complexing agent comprises tetrabutylammonium bromide and sodium diethyldithiocarbamate, and the mass ratio of tetrabutylammonium bromide and sodium diethyldithiocarbamate is 1:3. The mass ratio of the complexing agent and ganoderma spore powder is 1:8, and the solid-liquid ratio of the complexing agent and anhydrous ethanol is 1:10 g / ml. The sealing time is 1 h; the microwave power is 200-250 W, and the microwave time is 60-80 s. More preferably, the microwave power is 220 W, and the microwave time is 70 s.

[0010] Preferably, in step (2), the complex surfactant comprises sodium bis(2-ethylhexyl) sulfosuccinate and Span 80, and the mass ratio of sodium bis(2-ethylhexyl) sulfosuccinate and Span 80 is (1-5):1. More preferably, the mass ratio of sodium bis(2-ethylhexyl) sulfosuccinate and Span 80 is 3.5:1. The mass fraction of the ethanol solution is 90%; and the mass ratio of the ethanol solution, anhydrous ethanol and the complex surfactant is 1:1:0.1.

[0011] Preferably, in step (3), the supercritical CO2 extraction pressure is 25 MPa, the temperature is 55℃, and the time is 2.5 h.

[0012] (Three) The present application provides a ganoderma spore powder heavy metal removal process, which has the following beneficial effects:

[0013] 1. The present application adds a complex surfactant and an ethanol solution to the supercritical CO2 fluid to form a microemulsion in the fluid phase. After the microemulsion penetrates into the ganoderma spore powder, it competes with heavy metals for adsorption active sites, weakens the binding of the matrix to heavy metal ions, and is also beneficial to the complexation of heavy metal ions with complexing agents, which enhances the solubilization and accelerates the effect of heavy metals and their complexes, thereby improving the extraction effect of heavy metals in the ganoderma spore powder.

[0014] 2. The present application mixes sodium bis(2-ethylhexyl) sulfosuccinate and Span 80 and controls the mass ratio to be 3.5:1. The end charge of sodium bis(2-ethylhexyl) sulfosuccinate is shielded by Span 80, making it electrically neutral, which can be better dissolved in the supercritical CO2 fluid phase, improving the stability of the microemulsion formed and ensuring the solubilization effect on heavy metals.

[0015] 3. The present application first complexes the heavy metal ions in the spore powder with a complexing agent, then adds a complex surfactant and an ethanol solution to the supercritical CO2 fluid phase to form a solubilizing fluid, and extracts the heavy metal complexes in a flow state, further improving the extraction effect.

[0016] 4. In the process of complexation, the present invention applies microwave treatment, which can break down some of the heavy metals that are relatively stable in combination with the matrix. These heavy metals can be complexed by the complexing agent, and the resulting heavy metal complexes will dissolve in the supercritical CO2 fluid phase and be carried out, further improving the extraction effect. Attached Figure Description

[0017] Figure 1 This is a graph showing the relationship between the composition ratio of the composite surfactant of this invention and the heavy metal removal rate. Detailed Implementation

[0018] The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments.

[0019] Example 1

[0020] A process for removing heavy metals from Ganoderma lucidum spore powder specifically includes the following steps:

[0021] (1) The composite ligand, rinsed and dried Ganoderma lucidum spore powder, and anhydrous ethanol were placed in an extractor, mixed thoroughly, and sealed. Microwave treatment was applied during the sealing process to obtain a pretreated solution. The composite ligand included tetrabutylammonium bromide and sodium diethyldithiocarbamate, with a mass ratio of 1:3. The mass ratio of the composite ligand to Ganoderma lucidum spore powder was 1:8, and the ratio of the composite ligand to anhydrous ethanol was 1:10 g / ml. The sealing time was 1 hour; the microwave power was 200W, and the microwave time was 60 seconds.

[0022] (2) The composite surfactant and ethanol solution are mixed, and then the mixture is added to the supercritical CO2 fluid phase to obtain a supercritical CO2 solubilized fluid. The composite surfactant includes sodium bis(2-ethylhexyl)sulfosuccinate and Span 80, with a mass ratio of 1:1. The ethanol solution has a mass fraction of 90%, and the mass ratio of the ethanol solution, anhydrous ethanol, and composite surfactant is 1:1:0.1.

[0023] (3) The heavy metal complexes in the pretreated solution are extracted using supercritical CO2 solubilizing fluid. After extraction, the material in the extractor is removed and dried. The supercritical CO2 extraction pressure is 25 MPa, the temperature is 55 °C, and the time is 2.5 h.

[0024] Example 2

[0025] A process for removing heavy metals from Ganoderma lucidum spore powder specifically includes the following steps:

[0026] (1) Put the complex coordination agent, the rinsed and dried Ganoderma lucidum spore powder and anhydrous ethanol into an extractor, mix well and seal, and assist with microwave treatment during the sealing process to obtain a pretreated feed liquid. The complex coordination agent includes tetrabutylammonium bromide and sodium diethyldithiocarbamate, and the mass ratio of tetrabutylammonium bromide to sodium diethyldithiocarbamate is 1:3. The mass ratio of the complex coordination agent to the Ganoderma lucidum spore powder is 1:8, and the feed liquid ratio of the complex coordination agent to anhydrous ethanol is 1:10 g / ml. The sealing time is 1 h; the microwave power is 200 W, and the microwave time is 60 s.

[0027] (2) Mix the complex surfactant and the ethanol solution, and then add the mixture into a supercritical CO2 fluid phase to obtain a supercritical CO2 solubilizing fluid. The complex surfactant includes sodium bis(2-ethylhexyl) sulfosuccinate and Span 80, and the mass ratio of sodium bis(2-ethylhexyl) sulfosuccinate to Span 80 is 3.5:1. The mass fraction of the ethanol solution is 90%; and the mass ratio of the ethanol solution, anhydrous ethanol and the complex surfactant is 1:1:0.1.

[0028] (3) Use the supercritical CO2 solubilizing fluid to extract the heavy metal complexes in the pretreated feed liquid, and after the extraction is completed, take out the material in the extractor and dry it to obtain the product. The pressure of the supercritical CO2 extraction is 25 MPa, the temperature is 55°C, and the time is 2.5 h.

[0029] Example 3

[0030] A Ganoderma lucidum spore powder heavy metal removal process, specifically comprising the following steps:

[0031] (1) Put the complex coordination agent, the rinsed and dried Ganoderma lucidum spore powder and anhydrous ethanol into an extractor, mix well and seal, and assist with microwave treatment during the sealing process to obtain a pretreated feed liquid. The complex coordination agent includes tetrabutylammonium bromide and sodium diethyldithiocarbamate, and the mass ratio of tetrabutylammonium bromide to sodium diethyldithiocarbamate is 1:3. The mass ratio of the complex coordination agent to the Ganoderma lucidum spore powder is 1:8, and the feed liquid ratio of the complex coordination agent to anhydrous ethanol is 1:10 g / ml. The sealing time is 1 h; the microwave power is 200 W, and the microwave time is 60 s.

[0032] (2) Mix the complex surfactant and the ethanol solution, and then add the mixture into a supercritical CO2 fluid phase to obtain a supercritical CO2 solubilizing fluid. The complex surfactant includes sodium bis(2-ethylhexyl) sulfosuccinate and Span 80, and the mass ratio of sodium bis(2-ethylhexyl) sulfosuccinate to Span 80 is 5:1. The mass fraction of the ethanol solution is 90%; and the mass ratio of the ethanol solution, anhydrous ethanol and the complex surfactant is 1:1:0.1.

[0033] (3) using supercritical CO2 solubilizing fluid to extract heavy metal complexes in the pretreated feed liquid, after extraction is completed, the material in the extractor is taken out, and after drying, it is ready for use. The pressure of supercritical CO2 extraction is 25 MPa, the temperature is 55°C, and the time is 2.5 h.

[0034] Example 4

[0035] The same as example 2, the difference is that the microwave power is 220 W, and the microwave time is 70 s.

[0036] Comparative example 1

[0037] A heavy metal removal process for ganoderma spore powder, specifically comprising the following steps:

[0038] (1) Put the composite complexing agent, the rinsed and dried ganoderma spore powder and anhydrous ethanol into the extractor, mix and seal for 1 h to obtain a pretreated feed liquid. The composite complexing agent includes tetrabutylammonium bromide and sodium diethyldithiocarbamate, and the mass ratio of tetrabutylammonium bromide to sodium diethyldithiocarbamate is 1:3. The mass ratio of the composite complexing agent to the ganoderma spore powder is 1:8, and the feed liquid ratio of the composite complexing agent to anhydrous ethanol is 1:10 g / ml.

[0039] (2) Mix the composite surfactant and ethanol solution, then add the mixed solution into the supercritical CO2 fluid phase to obtain a supercritical CO2 solubilizing fluid. The composite surfactant includes sodium bis(2-ethylhexyl) sulfosuccinate and Span 80, and the mass ratio of sodium bis(2-ethylhexyl) sulfosuccinate to Span 80 is 3.5:1. The mass fraction of the ethanol solution is 90%; and the mass ratio of the ethanol solution, anhydrous ethanol and composite surfactant is 1:1:0.1.

[0040] (3) using supercritical CO2 solubilizing fluid to extract heavy metal complexes in the pretreated feed liquid, after extraction is completed, the material in the extractor is taken out, and after drying, it is ready for use. The pressure of supercritical CO2 extraction is 25 MPa, the temperature is 55°C, and the time is 2.5 h.

[0041] Comparative example 2

[0042] A heavy metal removal process for ganoderma spore powder, specifically comprising the following steps:

[0043] (1) Put the complex ligand, Ganoderma lucidum spore powder after rinsing and drying, and anhydrous ethanol into an extractor, mix well and seal, and assist with microwave treatment during the sealing process to obtain a pretreated liquid. The complex ligand includes tetrabutylammonium bromide and sodium diethyldithiocarbamate, and the mass ratio of tetrabutylammonium bromide to sodium diethyldithiocarbamate is 1:3. The mass ratio of the complex ligand to Ganoderma lucidum spore powder is 1:8, and the liquid-solid ratio of the complex ligand to anhydrous ethanol is 1:10 g / ml. The sealing time is 1 h; the microwave power is 220 W, and the microwave time is 70 s.

[0044] (2) Use supercritical CO2 fluid to extract heavy metal complexes in the pretreated liquid, and after the extraction is completed, the material in the extractor is taken out and dried to obtain Ganoderma lucidum spore powder. The pressure of supercritical CO2 extraction is 25 MPa, the temperature is 55°C, and the time is 2.5 h.

[0045] Comparative Example 3

[0046] A Ganoderma lucidum spore powder heavy metal removal process, specifically comprising the following steps:

[0047] (1) Put the complex ligand, Ganoderma lucidum spore powder after rinsing and drying, 90% ethanol solution, and surfactant into an extractor, mix well and seal, and assist with microwave treatment during the sealing process to obtain a pretreated liquid. The complex ligand includes tetrabutylammonium bromide and sodium diethyldithiocarbamate, and the mass ratio of tetrabutylammonium bromide to sodium diethyldithiocarbamate is 1:3. The mass ratio of the complex ligand to Ganoderma lucidum spore powder is 1:8, and the liquid-solid ratio of the complex ligand to ethanol solution is 1:10 g / ml. The sealing time is 1 h; the microwave power is 220 W, and the microwave time is 70 s. The complex surfactant includes sodium bis(2-ethylhexyl) sulfosuccinate and Span 80, and the mass ratio of sodium bis(2-ethylhexyl) sulfosuccinate to Span 80 is 3.5:1. The mass ratio of ethanol solution to complex surfactant is 1:0.1.

[0048] (2) Use supercritical CO2 fluid to extract heavy metal complexes in the pretreated liquid, and after the extraction is completed, the material in the extractor is taken out and dried to obtain Ganoderma lucidum spore powder. The pressure of supercritical CO2 extraction is 25 MPa, the temperature is 55°C, and the time is 2.5 h.

[0049] Heavy metal content detection

[0050] 1. Take 5 g of sample, add 200 ml of nitric acid solution, soak, and digest on an electric heating plate. After cooling, transfer to a 250 ml cuvette, add deionized water to constant volume, and prepare a test solution. Use inductively coupled plasma mass spectrometry to detect the heavy metal content in the test solution. The specific results are shown in the following table.

[0051] Table 1 initial heavy metal content

[0052]

[0053] 2, the same batch of ganoderma lucidum spore powder 7 parts, according to the removal process in examples 1-4 and comparative examples 1-3, then according to the method in 1 to determine the heavy metal content of the treated ganoderma lucidum spore powder. The specific test results are shown in the following table.

[0054]

[0055] Table 2 final heavy metal content

[0056] Group Cadmium (mg / kg) Copper (mg / kg) Lead (mg / kg) Example 1 0.18 10.85 1.78 Example 2 0.17 10.13 1.76 Example 3 0.19 11.14 1.88 Example 4 0.13 7.12 1.33 Comparative Example 1 0.23 11.94 2.05 Comparative Example 2 0.24 12.73 2.24 Comparative Example 3 0.21 11.28 1.91

[0057] Table 3 heavy metal removal rate

[0058]

[0059]

[0060] From the above table, it can be seen that the heavy metal content removal rate of ganoderma lucidum spore powder in example 4 is the highest, which shows that when the microwave power is controlled to be 220W, the microwave time is 70s, the mass ratio of sodium bis (2-ethylhexyl) sulfosuccinate and span 80, bis (2-ethylhexyl) sulfosuccinate (AOT) and span 80 is 3.5:1, the removal effect of heavy metals in ganoderma lucidum spore powder is the best;

[0061] Comparative example 2 has the worst removal effect on heavy metals, which shows that the addition of composite surfactant can promote the extraction of heavy metals;

[0062] The heavy metal removal rate in comparative example 3 is slightly worse than that in example, which shows that first extracting the composite surfactant and ethanol solution with supercritical CO2 fluid, and then extracting the heavy metals with supercritical CO2 solubilizing fluid, can improve the extraction effect of heavy metals.

[0063] The examples of the present application disclose the preferred examples, but are not limited thereto, and those skilled in the art can easily understand the spirit of the present application according to the above examples, and make different inferences and changes, as long as they do not deviate from the spirit of the present application, they are within the protection scope of the present application.

Claims

1. A process for removing heavy metals from ganoderma spores powder, characterized in that, The removal process specifically comprises the following steps: (1) Put the composite complexing agent, Ganoderma lucidum spore powder and anhydrous ethanol into an extractor, mix and seal, and assist with microwave treatment during the sealing process to obtain a pretreated liquid; (2) Mix the composite surfactant and ethanol solution, then add the mixture into a supercritical CO2 fluid phase to obtain a supercritical CO2 solubilized fluid; (3) Use the supercritical CO2 solubilized fluid to extract the heavy metal complex in the pretreated liquid, and after the extraction is completed, take out the material in the extractor and dry it to obtain the product; In step (2), the composite surfactant comprises sodium bis(2-ethylhexyl) sulfosuccinate and Span 80, and the mass ratio of sodium bis(2-ethylhexyl) sulfosuccinate to Span 80 is 3.5:

1.

2. A Ganoderma lucidum spore powder heavy metal removal process as claimed in claim 1, characterized by, In step (1), the composite complexing agent comprises tetrabutylammonium bromide and sodium diethyldithiocarbamate, and the mass ratio of tetrabutylammonium bromide to sodium diethyldithiocarbamate is 1:

3.

3. A Ganoderma lucidum spore powder heavy metal removal process as claimed in claim 1, characterized by, In step (1), the mass ratio of the composite complexing agent to Ganoderma lucidum spore powder is 1:8, and the liquid ratio of the composite complexing agent to anhydrous ethanol is 1:10 g / ml.

4. The Ganoderma lucidum spore powder heavy metal removal process of claim 1, wherein, In step (1), the sealing time is 1 h; the microwave power is 200-250 W, and the microwave time is 60-80 s.

5. A Ganoderma lucidum spore powder heavy metal removal process as claimed in claim 4, characterized by, The microwave power is 220 W, and the microwave time is 70 s.

6. A Ganoderma lucidum spore powder heavy metal removal process as claimed in claim 1, characterized by, The mass fraction of the ethanol solution is 90%, and the mass ratio of the ethanol solution, anhydrous ethanol and composite surfactant is 1:1:0.

1.

7. A Ganoderma lucidum spore powder heavy metal removal process as claimed in claim 1, characterized by, In step (3), the pressure of the supercritical CO2 extraction is 25 MPa, the temperature is 55°C, and the time is 2.5 h.

8. A Ganoderma lucidum spore powder heavy metal removal process as claimed in claim 1, characterized by, The Ganoderma lucidum spore powder is rinsed with clean water in advance before supercritical CO2 extraction, and then dried.

Images