CN112044915A - Novel method for completely harmless and efficient recycling of waste antibiotic medicines - Google Patents
Novel method for completely harmless and efficient recycling of waste antibiotic medicines Download PDFInfo
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Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/0075—Disposal of medical waste
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/40—Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B5/00—Operations not covered by a single other subclass or by a single other group in this subclass
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- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention establishes a novel method for completely harmless and recycling antibiotic medicines with high efficiency and low consumption aiming at the current situations of huge total amount of the discarded antibiotic medicines, high energy consumption of the traditional harmless treatment process, low recycling utilization efficiency and the like in China. The method completely degrades antibiotic components in the waste drugs through hydrothermal treatment under specific conditions, converts organic auxiliary material components in the waste drugs into carbon materials with good porous structures and rich surface functional groups, and can be directly used as an adsorbent or further activated to prepare carbon materials with higher adsorption performance for resource utilization. The invention provides a novel antibiotic drug treatment method which is simple in operation flow, low in energy consumption and cost, thorough in harmlessness and efficient in recycling.
Description
Technical Field
The invention relates to a novel method for thoroughly and harmlessly and efficiently recycling waste antibiotic medicines, belonging to a novel solid waste treatment technology in the field of environmental protection and comprehensive resource utilization.
Technical Field
With the rapid development of pharmaceutical medicine, the variety and yield of drugs are increasing, and at the same time, a large amount of overdue waste drugs are brought. The total amount of the discarded medicines is huge every year in China, and the antibiotic medicines account for a large proportion. If the antibiotic waste flows into the environmental water or soil, the environment is polluted, and the serious consequence of enhancing the drug resistance of bacteria is caused. The existing treatment technologies mainly comprise a pharmaceutical factory recycling and reproduction method, a burning method, a landfill method and the like, and the traditional treatment methods have the defects of high energy consumption, long time consumption, incapability of recycling waste antibiotic medicines at a high value and the like during treatment, and can also generate and discharge harmful pollutants in the treatment process, so that the risk of secondary pollution exists. Therefore, the development of a novel treatment technical means for realizing complete harmlessness and recycling of the antibiotic medicines has important significance.
The main components of the oral antibiotic medicine comprise an effective antibiotic component and medicinal auxiliary materials, wherein the medicinal auxiliary materials playing the roles of a diluent, an adhesive and the like in medicine forming account for more than 80 percent, the components of the medicinal auxiliary materials mainly comprise organic substances such as starch, sucrose, dextrin and the like, and the organic substances have important recycling value in waste medicines.
Hydrothermal carbonization is a process in which water or other solutions are mixed with organic substances in a closed reaction vessel at a certain temperature and pressure, and the temperature is raised to generate autogenous pressure in the vessel, so that the organic substances are subjected to hydrolysis, dehydration decarboxylation, aromatization, polycondensation and other reactions in the fluid at high temperature and high pressure to generate hydrothermal carbon. The hydrothermal carbon can be used for synthesizing carbon-based functional materials and can also be used for synthesizing solid fuels. Compared with pyrolysis carbonization, the hydrothermal carbonization method has the advantages of milder reaction conditions, simpler and more convenient operation, lower energy consumption and the like, and the prepared hydrothermal carbon contains rich pore structures and oxygen-containing functional groups and can be used as an adsorption material or a precursor of a porous carbon material.
The invention firstly proposes that the outdated waste antibiotic medicines are treated by a hydrothermal carbonization method, thereby achieving the aim of completely harmless treatment and obtaining the hydrothermal carbon material with application value. The method has the advantages of simple flow and low energy consumption cost, and the medicines can be converted into hydrothermal carbon materials after treatment, so that a quick and low-consumption treatment technical means is provided for the complete harmless treatment of the waste medicines.
Disclosure of Invention
The invention aims to provide a novel method for completely harmlessly treating and efficiently recycling waste antibiotic medicines with high speed and low consumption in order to solve the current situations of high cost, serious pollution and the like in the existing treatment and disposal process of the waste antibiotic medicines. The method has the advantages of simple operation, mild reaction, low energy consumption and application value of the product.
The purpose of the invention is realized by the following technical scheme:
a novel method for completely harmless and efficient recycling of waste antibiotic medicines comprises the following steps:
(1) crushing the waste medicine and then uniformly mixing the crushed waste medicine with the aqueous solution according to a certain proportion;
(2) placing the mixture obtained in the step (1) in a hydrothermal kettle for hydrothermal carbonization treatment;
(3) washing, drying and crushing the medicine obtained in the step (2) after hydrothermal carbonization;
optionally, in the step (1), the waste drugs are selected from waste antibiotic drugs such as overdue azithromycin dispersible tablets, oxytetracycline tablets, roxithromycin dispersible tablets and the like; the solution can be distilled water or hydrothermal liquid obtained after hydrothermal treatment (recycling); the ratio of drug to solution after disruption is preferably 1: (5-15). Too high proportion can lead to insufficient hydrothermal carbonization, while too low proportion can increase energy consumption in the treatment process and improve treatment cost; optionally adding calcium oxide for co-processing, wherein the mass ratio of calcium oxide in the medicine is preferably 0-10%; calcium oxide is added to catalyze and degrade biological-resistant components and catalyze the carbonization of organic matters; while the alkaline reaction atmosphere and Ca provided by the calcium oxide2+The chelating coordination with the surface of the carbide can increase the carbonization product of the organic matter; too high calcium oxide addition can cause the shedding of functional groups on the surface of the carbide due to too strong alkalinity of a reaction system, thereby influencing the adsorption function of the carbide.
Optionally, in the step (2), the hydrothermal carbonization temperature is preferably 120-300 ℃, and the carbonization time is preferably 0.5-12 h. The lower carbonization temperature and the shorter carbonization time can cause insufficient carbonization of the antibiotic medicines, and the excessively high carbonization temperature and the excessively long carbonization time can increase the energy consumption of treatment and increase the cost.
Optionally, in the step (3), the preferred drying temperature range of the hydrothermal charcoal of the hydrothermal carbonized antibiotic medicine is 80-110 ℃, and the granules are crushed to 70-100 meshes.
The invention provides a novel method for completely harmless and efficient recycling of waste antibiotic medicines by the method.
The principle of the invention is as follows:
according to the invention, the liquid is converted into subcritical fluid by the autogenous pressure generated by raising the temperature in the closed space, so that the dehydration and decarboxylation of antibiotic substances in the waste medicines are promoted, the macromolecular organic substances in the medicines can more easily receive energy and then break bonds to form micromolecular organic substances, and the micromolecular organic substances are further converted to finally achieve the purpose of degrading and removing the antibiotics. On the other hand, the hydrothermal treatment converts organic matters in the organic auxiliary components of the medicines into fixed carbon, and introduces a large number of oxygen-containing functional groups and a mesoporous structure to the carbon surface to obtain the hydrothermal carbon with a specific surface morphology for resource utilization.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the method is simple and easy to implement, high in treatment efficiency and low in cost;
(2) according to the invention, the hydrothermal method is creatively utilized to carry out carbonization treatment on the waste antibiotic medicines, and the final solid product does not contain antibiotic components;
(3) the liquid generated in the hydrothermal process can be recycled, so that the water consumption can be saved, and the cost is reduced;
(4) the invention has the advantages of high processing speed, low energy consumption and no harmful pollutants;
(5) the hydrothermal carbon as a solid product is finally obtained by the method, does not contain antibiotic components, and can be used as an adsorbent or a precursor of a carbon material for resource utilization.
Drawings
FIG. 1 is a process flow diagram of the present invention for treating waste antibiotic drugs.
FIG. 2 is a graph showing the effect of adsorption of methylene blue in a solution by the hydrothermal carbon obtained by the present invention.
Detailed Description
The invention completely degrades the antibiotic components in the waste antibiotic medicines by the hydrothermal carbonization technology. The present invention is described in further detail below with reference to specific processing steps, but embodiments of the present invention include, but are not limited to, the following examples. All alternatives obtained by equivalent substitution or equivalent exchange are within the scope of the invention.
Example 1:
the method for preparing the carbon material by treating the waste antibiotic medicines through hydrothermal carbonization comprises the following steps:
(1) taking overdue azithromycin dispersible tablets as raw materials, mixing 10g of crushed medicine with distilled water according to the proportion of 1:8(m/m), and performing ultrasonic treatment for 30min to fully mix the medicine;
(2) and (3) placing the mixture obtained in the step (1) in a 100mL closed hydrothermal reaction kettle. Carrying out hydrothermal carbonization treatment at 220 ℃ for 10 hours;
(3) and (3) centrifugally separating the solid product after the hydrothermal carbonization at the rotating speed of 5000rpm, washing the solid product for multiple times by using distilled water, and drying the solid product finally obtained in an oven at 105 ℃ for 24 hours. The dried solid sample was ground to 100 mesh.
(4) And (4) quantitatively analyzing the antibiotics in the solid phase and the liquid phase after solid-liquid separation. Solid sample: grinding the raw materials into fine powder, adding acetonitrile to dissolve and quantitatively diluting 1mg of azithromycin in every 1mL, and filtering to obtain filtrate as a test solution; and (4) adding a certain amount of solid product into the diluent for dissolving, and filtering to obtain a filtrate as a test solution. And taking a certain amount of liquid to dilute and fix the volume to obtain a test solution. And (3) determining the content of the antibiotics in the solid-liquid two phases by using a high performance liquid chromatography: octadecylsilane chemically bonded silica is used as a filling agent; the mobile phase A is phosphate buffer (0.05 mol/L dipotassium hydrogen phosphate solution is taken, the pH value is adjusted to 8.2 by 20 percent phosphoric acid solution) -acetonitrile (45:55), the mobile phase B is methanol, and the column temperature is 30 ℃; precisely measuring 50 μ L of reference solution and sample solution, respectively injecting into liquid chromatograph, and calculating by peak area according to external standard method.
Example 2:
(1) taking waste azithromycin dispersible tablets as raw materials, mixing 8g of crushed medicine with the hydrothermal liquid in the embodiment 1 according to the proportion of 1:10(m/m), and carrying out ultrasonic treatment for 30min to fully mix the medicine;
(2) and (3) placing the mixture obtained in the step (1) in a 100mL closed hydrothermal reaction kettle. Carrying out hydrothermal carbonization at 200 ℃ for 12 hours;
(3) and (3) centrifugally separating the solid product after the hydrothermal carbonization at the rotating speed of 5000rpm, washing the solid product for multiple times by using distilled water, and drying the solid product finally obtained in an oven at 105 ℃ for 24 hours. The dried solid sample was ground to 100 mesh.
(4) The method for detecting azithromycin in the raw material and the product is the same as the method (4) in the example 1.
Example 3:
(1) taking overdue waste roxithromycin dispersible tablets as raw materials, mixing 10g of crushed medicine with distilled water according to a ratio of 1:15(m/v), and performing ultrasonic treatment for 30min to fully mix the medicine;
(2) and (3) placing the mixture obtained in the step (1) in a 200mL closed hydrothermal reaction kettle. Carrying out hydrothermal carbonization at 240 ℃ for 8 hours;
(3) and (3) centrifugally separating the solid product after the hydrothermal carbonization at the rotating speed of 5000rpm, washing the solid product for multiple times by using distilled water, and drying the solid product finally obtained in an oven at 105 ℃ for 24 hours. The dried solid sample was ground to 100 mesh.
(4) Solid sample: grinding the raw materials into fine powder, adding mobile phase for dissolving and diluting to prepare a solution containing roxithromycin of about 1.0mg in every 1mL, and filtering to obtain a filtrate as a test solution; adding a certain amount of solid product into a mobile phase for dissolving, and filtering to obtain a filtrate as a test solution; liquid sample: taking a quantitative liquid product, adding a mobile phase to a constant volume to obtain a test solution. The roxithromycin standard substance is added with the mobile phase to prepare a solution containing 1.0mg of roxithromycin in every 1mL, and the solution is shaken up to be used as a control solution. Chromatographic conditions are as follows: octadecylsilane chemically bonded silica is used as a filling agent; 0.067mol/L ammonium dihydrogen phosphate solution (pH value is adjusted to 6.5 by triethylamine) -acetonitrile (65:35) is used as a mobile phase; the detection wavelength is 210 mm. Precisely measuring 20 μ L of control solution and sample solution according to the above chromatographic conditions, injecting into a liquid chromatograph, recording chromatogram, and calculating peak area according to external standard method.
Example 4:
(1) taking overdue roxithromycin dispersible tablets as raw materials, mixing 10g of crushed medicine with distilled water according to the proportion of 1:15(m/m), adding 0.5g of calcium oxide solid, and performing ultrasonic treatment for 30min to fully mix the materials;
(2) and (3) placing the mixture obtained in the step (1) in a 200mL closed hydrothermal reaction kettle. Carrying out hydrothermal carbonization at 240 ℃ for 8 hours;
(3) and (3) centrifugally separating the solid product after the hydrothermal carbonization at the rotating speed of 5000rpm, washing the solid product for multiple times by using distilled water, and drying the solid product finally obtained in an oven at 105 ℃ for 24 hours. The dried solid sample was ground to 100 mesh.
(4) The method for detecting roxithromycin in the raw materials and the products is the same as the method (4) in the example 3.
Table 1 lists the elemental content and yield data for the hydrothermal carbon material prepared by the present invention. The waste antibiotic hydrothermal carbon material prepared by the method has high C, H, O content, the high hydrogen and oxygen content is beneficial to generating more micropores, mesopores and pore diameter channels when the porous carbon is prepared by subsequent activation, and the high carbon content is beneficial to generating a stable graphitized structure when the high-temperature activation is carried out. The results show that the hydrothermal carbon material is a good precursor of the carbon material to further prepare the porous carbon material with stable structure and rich pore diameter.
Table 2 shows the concentration detection results of the antibiotics in the raw material medicines and the solid-phase and liquid-phase products obtained by the method. No target antibiotic is detected in the solid-phase product and the liquid-phase product treated by the method, which shows that the method can completely treat the waste antibiotic medicine in a harmless way.
TABLE 1 elemental content and yield data for waste antibiotic hydrothermal carbon materials prepared according to the present invention
TABLE 2 detection values of antibiotic concentrations in raw materials and products of the present invention
To further verify the effect of the present invention, the hydrothermal carbon material prepared in example 1 was used as an adsorbent, and an adsorption experiment of the organic chloride pigment methylene blue was performed, wherein the specific adsorption experiment operations are as follows:
1L of methylene blue solution with the concentration of 30mg/L is added into a big beaker, 1g of waste antibiotic medicine hydrothermal charcoal prepared by the invention is added, and the mixture is stirred by a magnetic stirrer at the room temperature and the speed of 200 rpm. 2ml of the solution was taken at intervals, after solid-liquid centrifugal separation, the concentration was measured by spectrophotometry, and the amount of adsorption was calculated to obtain a curve of the amount of adsorption changing with time, as shown in FIG. 2. The hydrothermal carbon material prepared by the method can quickly adsorb methylene blue solution, the final adsorption capacity is 25.5mg/g, and the removal effect is more than 80%. And then, the hydrothermal carbon material can be used as a precursor for further activation to prepare an activated carbon material with richer pore structure and more excellent adsorption property.
Claims (5)
1. A novel method for completely harmless and efficient recycling of waste antibiotic medicines is characterized by comprising the following steps:
(1) crushing the waste medicine and then uniformly mixing the crushed waste medicine with the aqueous solution according to a certain proportion;
(2) placing the mixture obtained in the step (1) in a hydrothermal kettle and then carrying out hydrothermal carbonization treatment;
(3) and (3) washing, drying and crushing the medicine obtained in the step (2) after the hydrothermal carbonization.
2. The method as claimed in claim 1, wherein in the step (1), the waste drugs are selected from waste antibiotic drugs such as expired azithromycin dispersible tablets, oxytetracycline tablets, roxithromycin dispersible tablets, etc.; the selection of the solution comprises distilled water or hydrothermal liquid obtained after hydrothermal treatment; the mass ratio of the crushed medicine to the solution is preferably 1: (5-15); optionally, calcium oxide solid is added for synergistic treatment, and the mass ratio of calcium oxide in the sample is preferably 0-10%.
3. The method as set forth in claim 1, wherein in the step (2), the hydrothermal carbonization temperature is 120 ℃ to 300 ℃ and the hydrothermal treatment time is 0.5 to 12 hours.
4. The method as claimed in claim 1, wherein in step (3), the drying temperature of the hydrothermal charcoal which is a solid product obtained by hydrothermally treating the antibiotic drugs is 80-110 ℃, and the charcoal material particles are pulverized to 70-100 mesh.
5. A hydrothermal carbon material prepared by a hydrothermal method by taking waste antibiotic medicines as raw materials, which is prepared according to the method of claims 1-4: the material does not contain the original antibiotic component, has the characteristics of good pore structure, oxygen-containing functional groups on the surface and the like, and can be directly used as an adsorption material or used for preparing a carbon material with higher adsorption performance through further activation.
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