CN105268410B - A kind of preparation method and application method of antibiotic adsorbed film - Google Patents

Abstract

The invention discloses a kind of preparation method of antibiotic adsorbed film, belong to organic/inorganic composite film preparing technical field.The preparation method is：Soluble chitosan is dissolved in the glacial acetic acid aqueous solution by step 1, is designated as solution A；Lanthanum nitrate is dissolved in water by step 2, wiring solution-forming, is designated as solution B；Step 3 takes a certain amount of solution A and solution B to mix, and adds glycerine and stirs, is designated as solution C；Solution C is placed in culture dish by step 4, sprawls uniformly, culture dish is put into drying box and dried, dry composite film is made；Step 5 separates dry composite film with culture dish, and antibiotic adsorbed film is made.The invention also discloses the application method of above-mentioned antibiotic adsorbed film, application method is that antibiotic adsorbed film is put into the waste water of antibiotic and stirred.Antibiotic adsorbed film cost is cheap made of the present invention, prepares simple, degradation rate height, easy to use, the processing for the antibiotics waste water that is particularly suitable for use in.

Description

A kind of preparation method and application method of antibiotic adsorption film

technical field

The invention specifically relates to a method for preparing and using an antibiotic adsorption film, and belongs to the technical field of organic-inorganic composite film preparation.

Background technique

Antibiotics are a large class of antimicrobial drugs, which are chemical substances produced by organisms in the metabolic process; after antibiotics are used, most of them are usually excreted with feces in the form of drugs, and the content of antibiotics in the influent and effluent water of sewage treatment plants is very high, resulting in Contaminated by antibiotics, the concentration of antibiotics in large-scale farm animal feces is also high. The use and discharge of antibiotics in farms is one of the important sources of antibiotics in the surface environment. Although antibiotics are released into soil, water and air and will be redistributed, antibiotics are easily adsorbed and accumulated in soil and water environments, causing damage to them. Therefore, the elimination of antibiotic residues in the water environment has important research significance for ensuring the safety of water resources and human survival.

Based on the serious harm caused by antibiotics to humans, the current physical methods for dealing with antibiotics mainly include adsorption, coagulation, and membrane separation methods. Membrane separation technology mainly uses the selective separation function of the membrane to separate antibiotic molecules from water molecules. Membrane separation technology has the advantages of high efficiency, energy saving, simple operation, and strong applicability.

Chitosan is called deacetylated chitosan polyglucosamine, which widely exists in nature, such as in the shells of crustaceans such as shrimps and crabs or in the cell walls of lower plants. It is an organic resource that exists widely on the earth. The viscosity of chitosan Large, good film-forming property, strong adsorption, good effect on the treatment of pharmaceutical wastewater. Rare earth elements have extremely strong chemical activity. Rare earth lanthanum has a high content in rare earth ores and has a wide range of uses. It is widely used in the study of adsorbent modification in water treatment. At present, there are many technologies about chitosan as a flocculant for pharmaceutical wastewater, but there are generally problems such as poor flocculation effect, low adsorption efficiency, and complicated operation. The present invention mainly uses chitosan-rare earth composite membrane to replace the flocculant, and the antibiotic in the wastewater is fully contacted and adsorbed by the membrane and the wastewater. After the membrane is taken out, the antibiotic has been adsorbed and degraded, avoiding the complicated process of separating the wastewater from the flocculant. .

Contents of the invention

Therefore, the object of the present invention is to provide a kind of low cost, simple preparation, high degradation rate, easy to use the preparation method of antibiotic adsorption membrane, described preparation method comprises the following steps:

Step 1 dissolves soluble chitosan in the aqueous solution of glacial acetic acid, which is denoted as solution A;

Step 2 dissolves lanthanum nitrate in water to form a solution, which is referred to as solution B;

Step 3 Take a certain amount of solution A and solution B and mix, add glycerin and stir, and record it as solution C;

Step 4: Put solution C in a petri dish, spread it evenly, put the petri dish in a drying oven to dry, and make a dry composite film;

Step 5: separating the dried composite film from the culture dish to make an antibiotic adsorption film.

Further, the step 1 is specifically dissolving the soluble chitosan in a prepared 2% aqueous solution of glacial acetic acid, stirring magnetically until the chitosan powder is completely dissolved, which is referred to as solution A.

Further, the third step is specifically to mix a certain amount of solution A and solution B, wherein the ratio of the mass mA of solution A to the mass mB of solution B is 10:1≤mA:mB≤10:3, adding glycerin, magnetic Stir for 24 hours, record as solution C, put solution C in an ultrasonic cleaner, and shake for 30 minutes.

Further, the step four is specifically to place solution C in a petri dish, wherein the volume V of solution C is 3.5mL≤V≤5mL, use a 6cm glass petri dish for the petri dish, spread it evenly, put the petri dish into the electric heating drum In an air drying oven, dry at 60°C for 12 hours to make a dry composite film.

Further, the fifth step is specifically to separate the dry composite membrane from the culture dish by soaking in 2% NaOH solution to separate the dry composite membrane from the culture dish to form an antibiotic adsorption membrane.

The present invention also provides a method for using the antibiotic adsorption membrane. The usage method is to put the antibiotic adsorption membrane prepared by the above method into antibiotic waste water and stir.

Further, in the use method, the antibiotic adsorption membrane is first washed with distilled water to neutrality, dried at room temperature, and then put into antibiotic waste water and magnetically stirred.

Chitosan itself has antibacterial effect, which is better than general antibacterial agents and non-toxic, and rare earth ions have also been found to have pharmacological effects such as anticancer and bactericidal. Chitosan plays the role of adsorption bridging and netting in water treatment, and rare earth ions play the role of adsorption neutralization and compression of the electric double layer. The cooperation of the two can exert a better adsorption effect.

The beneficial effect of the present invention is that: in the preparation method and the use method of the antibiotic adsorption film of the present invention, chitosan has a wide range of sources, is cheap and economical. Rare earth lanthanum is abundant in rare earth ores and has a large output. Lanthanum nitrate with composite membrane has low purity requirements and is easy to prepare. The mixture of the two can well treat pharmaceutical wastewater, and the degradation rate is high. The invention is mainly aimed at the treatment of residual antibiotics in pharmaceutical wastewater. After the wastewater is treated, only the membrane needs to be taken out without separation from the flocculant, the operation is simple, and the environmental protection requirement can be met. The invention is especially suitable for the treatment of antibiotic pharmaceutical waste water.

Description of drawings

Fig. 1 is a comparison chart of test results before and after wastewater treatment of the fluorescence spectrometer in Embodiment 1 of the present invention.

detailed description

The specific embodiment of the present invention is described below in conjunction with accompanying drawing:

The soluble chitosan used in the following specific embodiments, also known as water-soluble chitosan, refers to chitosan that can dissolve in water.

Specific implementation mode 1

1. Accurately measure 20ml of glacial acetic acid into a 1000ml volumetric flask, add distilled water to constant volume, and prepare an acetic acid solution with a volume fraction of 2% for later use.

2. Take 0.5g of chitosan powder and place it in a 100ml beaker, add 20ml of 2% acetic acid solution, stir with magnetic force until the chitosan is completely dissolved and the solution is transparent, and then make solution A.

3. Take 0.05g of lanthanum nitrate and place it in a 100ml beaker, add 20ml of distilled water to completely dissolve the lanthanum nitrate, and make solution B.

4. Mix solutions A and B in another 100ml beaker, add 0.8g glycerin, and stir magnetically for 24h. At this time, the mass ratio of chitosan and lanthanum nitrate is 10:1, the mass concentration of glycerin is 2%, the solution volume is 40ml, and the volume of added glycerin is ignored, which is recorded as solution C.

5. Place C in an ultrasonic cleaner and oscillate ultrasonically for 30 minutes to remove air bubbles.

6. Accurately measure 3.5ml of solution C in a glass petri dish with a diameter of 6mm, and spread evenly.

7. Place the culture dish covered with the film in an electric blast drying oven, and keep it dry at 60°C for 12 hours to finally prepare a dry composite film.

8. Prepare 1000ml of NaOH solution with a mass concentration of 2%, add 20ml to the petri dish, soak until the membrane is separated from the petri dish.

9. Rinse the membrane with distilled water until the washed water is neutral, and dry it at room temperature for use. At this time, the film is uniform, with good hardness and flexibility.

10. Put the prepared composite membrane into 80mg/L, 25ml levofloxacin solution, stir with a magnetic stirrer at room temperature for 30min, take out the membrane, and test the fluorescence intensity of the solution.

It is used to treat the simulated antibiotic levofloxacin wastewater. The fluorescence intensity of the drug solution before and after degradation is tested by a F4500 fluorescence spectrometer. The maximum fluorescence excitation wavelength and emission wavelength are 370nm and 500nm, respectively. After performing the fluorescence intensity test, follow the Calculate the degradation rate, wherein, I ₀ is the fluorescence intensity of the pharmaceutical wastewater before treatment, and I is the fluorescence intensity of the pharmaceutical wastewater after membrane treatment, and the calculated degradation rate is 65.23%.

Specific implementation mode 2

1. Accurately measure 20ml of glacial acetic acid into a 1000ml volumetric flask, add distilled water to constant volume, and prepare an acetic acid solution with a volume fraction of 2% for later use.

2. Take 0.5g of chitosan powder and place it in a 100ml beaker, add 20ml of 2% acetic acid solution, stir with magnetic force until the chitosan is completely dissolved and the solution is transparent, and then make solution A.

3. Take 0.10g of lanthanum nitrate and place it in a 100ml beaker, add 20ml of distilled water to completely dissolve the lanthanum nitrate, and make solution B.

4. Mix solutions A and B in another 100ml beaker, add 1.6g glycerin, and stir magnetically for 20 hours. At this time, the mass ratio of chitosan and lanthanum nitrate is 10:1, the mass concentration of glycerin is 4%, the solution volume is 40ml, and the volume of added glycerin is ignored, which is recorded as solution C.

5. Place C in an ultrasonic cleaner and oscillate ultrasonically for 20 minutes to remove air bubbles.

6. Accurately measure solution C, 4.0ml, in a glass petri dish with a diameter of 6mm, and spread evenly.

7. Place the culture dish covered with the film in an electric blast drying oven, and keep it at 70°C for 10 hours to dry, and finally a dry composite film is obtained.

8. Prepare 1000ml of NaOH solution with a mass concentration of 2%, add 20ml to the petri dish, soak until the membrane is separated from the petri dish.

9. Rinse the membrane with distilled water until the washed water is neutral, and dry it at room temperature for use. At this time, the film is uniform, with good hardness and flexibility.

10. Put the prepared composite membrane into 80mg/L, 30ml levofloxacin solution, stir with a magnetic stirrer at room temperature for 25min, take out the membrane, and test the fluorescence intensity of the solution. The drug degradation rate was 70.34%.

Specific implementation mode 3

1. Accurately measure 20ml of glacial acetic acid into a 1000ml volumetric flask, add distilled water to constant volume, and prepare an acetic acid solution with a volume fraction of 2% for later use.

2. Take 0.5g of chitosan powder and place it in a 100ml beaker, add 20ml of 2% acetic acid solution, stir with magnetic force until the chitosan is completely dissolved and the solution is transparent, and then make solution A.

3. Take 0.15g of lanthanum nitrate and place it in a 100ml beaker, add 20ml of distilled water to completely dissolve the lanthanum nitrate, and make solution B.

4. Mix solutions A and B in another 100ml beaker, add 2.0g glycerin, and stir magnetically for 18h. At this time, the mass ratio of chitosan and lanthanum nitrate is 10:3, the mass concentration of glycerin is 5%, the solution volume is 40ml, and the volume of added glycerin is ignored, which is recorded as solution C.

5. Place C in an ultrasonic cleaner and oscillate ultrasonically for 40 minutes to remove air bubbles.

6. Accurately measure solution C, 4.5ml in a glass petri dish with a diameter of 6mm, and spread evenly.

7. Place the culture dish covered with film in an electric blast drying oven, keep it dry at 80°C for 8 hours, and finally obtain a dry composite film.

8. Prepare 1000ml of NaOH solution with a mass concentration of 2%, add 20ml to the petri dish, soak until the membrane is separated from the petri dish.

9. Rinse the membrane with distilled water until the washed water is neutral, and dry it at room temperature for use. At this time, the film is uniform, with good hardness and flexibility.

10. Put the prepared composite membrane into 80mg/L, 20ml levofloxacin solution, stir with a magnetic stirrer at room temperature for 15min, take out the membrane, and test the fluorescence intensity of the solution. The drug degradation rate is 72.86%.

Specific implementation mode 4

1. Accurately measure 20ml of glacial acetic acid into a 1000ml volumetric flask, add distilled water to constant volume, and prepare an acetic acid solution with a volume fraction of 2% for later use.

2. Take 0.5g of chitosan powder and place it in a 100ml beaker, add 20ml of 2% acetic acid solution, stir with magnetic force until the chitosan is completely dissolved and the solution is transparent, and then make solution A.

3. Take 0.20g of lanthanum nitrate and place it in a 100ml beaker, add 20ml of distilled water to completely dissolve the lanthanum nitrate, and make solution B.

4. Mix solutions A and B in another 100ml beaker, add 3.2g glycerin, and stir magnetically for 22h. At this moment, the mass ratio of chitosan and lanthanum nitrate is 10:3, the mass concentration of glycerin is 8%, the solution volume is 40ml, and the volume of added glycerin is ignored, which is recorded as solution C.

5. Place C in an ultrasonic cleaner and oscillate ultrasonically for 50 minutes to remove air bubbles.

6. Accurately measure 5.0ml of solution C in a glass petri dish with a diameter of 6mm, and spread evenly.

7. Place the culture dish covered with the film in an electric blast drying oven, and keep it at 90°C for 6 hours to dry, and finally a dry composite film is obtained.

8. Prepare 1000ml of NaOH solution with a mass concentration of 2%, add 20ml to the petri dish, soak until the membrane is separated from the petri dish.

9. Rinse the membrane with distilled water until the washed water is neutral, and dry it at room temperature for use. At this time, the film is uniform, with good hardness and flexibility.

10. Put the prepared composite membrane into 80mg/L, 15ml levofloxacin solution, stir with a magnetic stirrer at room temperature for 20min, take out the membrane, and test the fluorescence intensity of the solution. The drug degradation rate is 68.54%.

The above specific implementation methods are experiments carried out in laboratories, and those skilled in the art can also extend the above preparation methods and usage methods to production practice.

The above description is a preferred embodiment of the present invention, it should be pointed out that for those of ordinary skill in the art, without departing from the principle of the present invention, some improvements and modifications can also be made, and these improvements and modifications can also be made. It should be regarded as the protection scope of the present invention.

Claims (3)

1. a kind of preparation method of antibiotic adsorbed film, it is characterised in that the preparation method comprises the following steps：

Soluble chitosan is dissolved in the glacial acetic acid aqueous solution by step 1, is designated as solution A；

Lanthanum nitrate is dissolved in water by step 2, wiring solution-forming, is designated as solution B；

Step 3 takes a certain amount of solution A and solution B to mix, and adds glycerine and stirs, is designated as solution C；

Solution C is placed in culture dish by step 4, sprawls uniformly, culture dish is put into drying box and dried, dry composite is made Film；

Step 5 separates dry composite film with culture dish, and antibiotic adsorbed film is made；

The step 1 is specially to be dissolved in soluble chitosan in configured the 2% glacial acetic acid aqueous solution, and magnetic agitation is extremely Chitosan powder is completely dissolved, and is designated as solution A；

The step 3 is specially to take a certain amount of solution A and solution B to mix, the quality mB of wherein solution A quality mA and solution B The ratio between be 10：1≤mA：mB≤10：3, glycerine is added, magnetic agitation 24 hours is designated as solution C, solution C is placed in into ultrasonic cleaning In device, 30min is vibrated；

The step 4 is specially that solution C is placed in culture dish, and the wherein volume V of solution C is 3.5mL≤V≤5mL, culture Ware uses 6cm glass culture dish, sprawls uniformly, culture dish is put into electric drying oven with forced convection, 60 DEG C of dryings 12 hours, is made Dry composite film；

The step 5 is specially to separate dry composite film with culture dish, and separation method is to be soaked with 2% NaOH solution, is made Dry composite film and culture dish separate, and antibiotic adsorbed film is made.

2. a kind of application method of antibiotic adsorbed film, it is characterised in that the application method is by claim 1 methods described In the waste water of manufactured antibiotic adsorbed film input antibiotic and stir.

3. the application method of antibiotic adsorbed film as claimed in claim 2, it is characterised in that use antibiosis in the application method Plain adsorbed film with distilled water flushing to neutrality, is dried at room temperature first, then is put into the waste water of antibiotic and magnetic agitation.