CN112915981A - Nano sponge adsorbent for specifically adsorbing tetracycline antibiotics and preparation method thereof - Google Patents
Nano sponge adsorbent for specifically adsorbing tetracycline antibiotics and preparation method thereof Download PDFInfo
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- CN112915981A CN112915981A CN202110114672.5A CN202110114672A CN112915981A CN 112915981 A CN112915981 A CN 112915981A CN 202110114672 A CN202110114672 A CN 202110114672A CN 112915981 A CN112915981 A CN 112915981A
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/261—Synthetic macromolecular compounds obtained by reactions only involving carbon to carbon unsaturated bonds
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28042—Shaped bodies; Monolithic structures
- B01J20/28045—Honeycomb or cellular structures; Solid foams or sponges
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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Abstract
The invention relates to the field of wastewater purification adsorbents, and particularly discloses a nano sponge adsorbent for specifically adsorbing tetracycline antibiotics and a preparation method thereof, wherein the nano sponge adsorbent comprises the following components in parts by weight: aqueous polyvinyl alcohol solution: 10-50 parts of ethyl cellulose: 12-18 parts of organic solvent: 32-38 parts of melamine: 20 parts of acetone and 5 parts of acetone. The preparation method comprises the steps of dissolving ethyl cellulose, mixing, magnetically stirring, filtering, pretreating melamine and finally mixing; the technical effect is that the pore size of the nano sponge adsorbent is matched with the molecular size of the tetracycline antibiotics, and the nano sponge adsorbent has the advantage of high adsorption to the tetracycline antibiotics.
Description
Technical Field
The invention relates to the field of wastewater purification adsorbents, and particularly relates to an adsorbent for tetracycline antibiotics and a preparation method thereof.
Background
Antibiotics have been widely used in human life since the clinical application of oxytetracycline in 1940; for years, antibiotics are frequently used in large quantities, so that more and more antibiotics are left in water, and the water is increasingly polluted. Tetracycline antibiotics are widely used antibiotics at present, and are mostly used in the process of livestock and poultry breeding or pet breeding, along with the discharge of excrement and urine of livestock and poultry, the tetracycline antibiotics enter surface water and underground water through runoff or leaching, and pose certain threat to the environment.
In the prior art, the sewage containing high-concentration tetracycline antibiotics is treated according to common sewage, and universal active carbon or other adsorbents are selected, so that the pore size of the adsorbent is generally single and common to ensure the universality of the application, the adsorption effect of the adsorbent in the sewage treatment containing single pollutants with high concentration is not ideal, and in the sewage treatment containing high-concentration tetracycline antibiotics, the removal rate of the tetracycline antibiotics is too low, the tetracycline antibiotics are remained and discharged into the environment in a treatment mode to pollute the environment.
Disclosure of Invention
Aiming at the problem of poor specificity of the adsorbent in the prior art, the first object of the invention is to provide a nano sponge adsorbent for specifically adsorbing tetracycline antibiotics, wherein the nano sponge adsorbent has the advantages that the pore size is matched with that of the tetracycline antibiotics, and the adsorption of the tetracycline antibiotics is high.
The second purpose of the invention is to provide a preparation method of the nano sponge adsorbent for specifically adsorbing tetracycline antibiotics, and the preparation method has the advantages of simple steps and high feasibility.
In order to achieve the first object, the invention provides the following technical scheme:
a nano sponge adsorbent for specifically adsorbing tetracycline antibiotics is prepared from the following raw materials in parts by weight:
aqueous polyvinyl alcohol solution: 10-50 parts;
ethyl cellulose: 12-18 parts;
organic solvent: 32-38 parts;
melamine: 20 parts of (1);
and 5 parts of acetone.
By adopting the technical scheme, the ethyl cellulose is dissolved in the dichloromethane and then uniformly dispersed in the aqueous solution of the polyvinyl alcohol to prepare the nano adsorbent dispersion liquid containing the pore structure, and then the original characteristics of the melamine are kept by mixing the adsorbent dispersion liquid and the melamine, and meanwhile, the pore diameter structure of the melamine is changed, so that the pore diameter size of the melamine is matched with the molecular size of the tetracycline antibiotic, and the adsorption rate of the melamine to the tetracycline antibiotic is improved.
Further setting: the polyvinyl alcohol aqueous solution comprises 10-50 parts of polyvinyl alcohol and the balance of deionized water.
By adopting the technical scheme, the polyvinyl alcohol is uniformly dispersed in the deionized water, so that the dispersibility among particles is enhanced.
Further setting: the organic solvent is dichloromethane or a solvent A, and the solvent A is a mixed solvent of toluene and ethanol.
By adopting the technical scheme, the ethyl cellulose can be better dissolved, and the subsequent mixing effect of the ethyl cellulose and the polyvinyl alcohol is better.
Further setting: the polyvinyl alcohol is pharmaceutical grade polyvinyl alcohol with molecular weight of 25-30 ten thousand.
By adopting the technical scheme, the prepared nano sponge has larger specific surface area and better adsorbability.
Further setting: the ethyl cellulose is a commercial pharmaceutical grade product.
By adopting the technical scheme, the adsorbent is ensured to be harmless to human bodies.
In order to achieve the second object, the invention provides the following technical scheme:
a nano sponge adsorbent for specifically adsorbing tetracycline antibiotics is prepared by the following steps:
s1: dissolving ethyl cellulose: the components and the organic solvent are added according to the following weight portions: 32-38 parts; ethyl cellulose: 12-18 parts; adding deionized water into an organic solvent, stirring and mixing, then adding ethyl cellulose, and carrying out ultrasonic oscillation on the solution for 2 hours to obtain a uniformly dispersed ethyl cellulose solution;
s2: mixing: the following components are added in parts by weight: 10-50 parts; aqueous polyvinyl alcohol solution: 10-50 parts; carrying out ultrasonic oscillation on the solution for 1h to obtain a uniformly dispersed mixed solution;
s3: magnetic stirring: placing the mixed solution on a magnetic stirrer, and magnetically stirring;
s4: and (3) filtering: filtering the mixed solution after magnetic stirring through a filter screen membrane to remove undissolved compound residues to obtain a supernatant of the nano adsorbent;
s5: melamine pretreatment: cutting melamine into sponge small blocks, adding acetone and deionized water until the sponge small blocks are immersed, and ultrasonically cleaning;
s6: soaking the small sponge blocks in the supernatant of the nano adsorbent for 12 hours;
s7: absorbing the supernatant of the nano adsorbent on the surface of the sponge by using filter paper, and then placing the nano adsorbent on a filter screen; and transferring the filter screen into an oven for heating and drying to obtain the nano sponge adsorbent.
According to the technical scheme, the nano adsorbent prepared by mixing the polyvinyl alcohol and the ethyl cellulose is combined with the melamine, the holes of the melamine are further divided, the specific surface area of the adsorbent is increased, and meanwhile, the pore diameter of the final nano sponge adsorbent is adapted to the tetracycline antibiotic by adjusting the material ratio, so that the adsorption effect on the tetracycline antibiotic is enhanced.
Further setting: the pretreatment step of the polyvinyl alcohol in the step 1 comprises the following steps: adding polyvinyl alcohol into cold water at the temperature of 18-22 ℃ while stirring for full swelling and dispersion, then heating to 95 ℃ for accelerated dissolution, and preserving heat for 2-2.5 hours until the solution does not contain micro particles any more, and filtering impurities to obtain a uniformly dispersed polyvinyl alcohol aqueous solution.
By adopting the technical scheme, the polyvinyl alcohol is uniformly dispersed in the deionized water solution, so that the dispersibility of the polyvinyl alcohol particles is enhanced.
Further setting: the aperture of the polyvinyl alcohol filtering screen is 200 meshes.
By adopting the technical scheme, polyvinyl alcohol which is not fully dissolved can be filtered, and the dispersion effect of the polyvinyl alcohol is ensured.
In conclusion, the invention has the following beneficial effects: dissolving ethyl cellulose in dichloromethane, uniformly dispersing the ethyl cellulose in a polyvinyl alcohol aqueous solution to prepare a nano adsorbent dispersion liquid containing a pore structure, and mixing the nano adsorbent dispersion liquid with melamine to cut the pores of the melamine while keeping the original characteristics of the melamine, so that the pore diameter structure of the melamine is changed, the pore diameter size of the melamine is matched with the molecular size of tetracycline antibiotics, and the adsorption rate of the melamine antibiotics is improved.
Detailed Description
The present invention will be described in further detail below.
Examples 1 to 12, a nanosponsive adsorbent for specific adsorption of tetracycline antibiotics, whose components and their corresponding masses are shown in table 1, was prepared by the following steps:
s1: dissolving ethyl cellulose: slowly adding deionized water into an organic solvent in a reactor, stirring and mixing, then adding ethyl cellulose, and carrying out ultrasonic oscillation on the solution for 2 hours to obtain a uniformly dispersed ethyl cellulose solution;
s2: mixing: adding an ethyl cellulose solution and a polyvinyl alcohol aqueous solution into a reactor, and carrying out ultrasonic oscillation on the solution for 1h to obtain a uniformly dispersed mixed solution;
s3: magnetic stirring: placing the mixed solution on a magnetic stirrer, and magnetically stirring;
s4: and (3) filtering: filtering the mixed solution after magnetic stirring through a filter screen membrane to remove undissolved compound residues to obtain a supernatant of the nano adsorbent;
s5: melamine pretreatment: cutting melamine into sponge small blocks, adding acetone and deionized water to clean the sponge small blocks, and ultrasonically cleaning;
s6: soaking the small sponge blocks in the supernatant of the nano adsorbent for 12 hours;
s7: and (3) absorbing the supernatant of the nano adsorbent on the surface of the sponge by using filter paper, and then placing the nano adsorbent on an iron wire net. And transferring the wire mesh into an oven for heating and drying to obtain the nano sponge adsorbent.
In the preparation process:
the preparation method of the polyvinyl alcohol aqueous solution in the step S1 comprises the following steps: adding polyvinyl alcohol into cold water at the temperature of 18-22 ℃ while stirring for full swelling and dispersion, then heating to 95 ℃ for accelerated dissolution, and preserving heat for 2-2.5 hours until the solution does not contain micro particles any more, and filtering impurities to obtain a uniformly dispersed polyvinyl alcohol aqueous solution. The filtering impurities are screened with 200 mesh.
The polyvinyl alcohol and the ethyl cellulose are both pharmaceutical-grade products, so that the human body is not injured in the preparation process; the polyvinyl alcohol is a product with ultrahigh polymerization degree, so that the prepared nano sponge has larger specific surface area and better adsorbability.
The rotation speed of the magnetic stirring in the step S3 is 800 rpm;
the drying temperature in step S7 was 90 ℃ and the time was 6 hours.
Table 1 preparation example of nano sponge adsorbent
In Table 1, the mixing ratio of the toluene and ethanol mixed reagent is 1: 4 of methanol and ethanol;
the preparation principle of the nano adsorbent is that polyvinyl alcohol is uniformly dispersed in aqueous solution, and then under the action of ethyl cellulose, particles are crosslinked to form a porous structure; the relative proportion of the polyvinyl alcohol aqueous solution and the ethyl cellulose is changed, the bonding degree of polyvinyl alcohol particles can be adjusted, the pore size of the final pore is further changed, and the pore size is adjusted to be in a range similar to the particle size of the tetracycline antibiotic, so that the absorption of the agent to the tetracycline antibiotic is quicker;
the melamine is a porous material, but the aperture of the melamine is too large compared with that of tetracycline antibiotics, so that the melamine is combined with the prepared nano adsorbent, the particle size of the nano adsorbent is smaller, the nano adsorbent can be dispersed in the melamine, the specific surface area of the melamine is increased, the pores of the melamine are subdivided, the aperture size of the melamine is adapted to that of the tetracycline antibiotics, and the adsorption effect of the melamine on the tetracycline antibiotics is increased; meanwhile, the nano sponge adsorbent is obtained by combining the melamine and the nano adsorbent, the problem that the nano adsorbent is difficult to collect due to small particles is effectively solved, and the nano adsorbent is collected, so that the follow-up recovery is facilitated.
Performance detection test:
the nano sponge adsorbent prepared in the above embodiment is subjected to adsorption performance tests, and the adsorption performance tests include isothermal adsorption tests and adsorption kinetics tests.
Isothermal adsorption test:
0.01g of nanosponge adsorbent was added to 20mL of tetracycline solution with an initial concentration ranging from 40mg/L to 800mg/L, and each of 2 parallel samples was set with a blank control vial without nanosponge adsorbent and an activated carbon control (i.e., 0.01g of activated carbon was weighed into tetracycline solution of the same concentration), and the sample vials were shaken at 25. + -. 0.5 ℃ on an orbital shaker at 150rpm for 24 hours to equilibrate. Fitting the data obtained by the test according to an isothermal adsorption formula, wherein the concrete formula is as follows:
(1) langmuir isothermal
(2) Freundlich isothermal model
Qe＝KFCe 1/n
In the formula: qe is the adsorption capacity in adsorption equilibrium, mg/g;
q is maximum saturated adsorption capacity, mg/g;
KLlangmuir adsorption constant, L/mg;
Ceis the equilibrium concentration of adsorbate in the water solution, mg/L;
the saturated adsorption quantity of the nano sponge adsorbent to the tetracycline antibiotics can be obtained through an isothermal adsorption test.
And (3) testing adsorption kinetics:
0.01g of nano sponge adsorbent is added into a 22mL sample bottle, 20mL of tetracycline solution with the concentration of 800ppm is added, one group of 2 parallel samples are added, and each group is provided with a blank control bottle and an activated carbon control group. And simultaneously placing the three groups of samples into a constant temperature oscillator (25 ℃, 150r/min) for oscillation, taking out the samples respectively when the samples are oscillated for 5min, 10min, 15min, 30min, 1h, 2h, 4h, 6h and 24h, and measuring the absorbance of the penicillin in the samples. Fitting the data obtained by the test according to a kinetic formula, wherein the specific formula is as follows:
(1) a quasi-first order kinetic model:
(2) a quasi-second order kinetic model:
in the formula:
qtrefers to the adsorption capacity at the time of adsorption t, mg/g;
qethe adsorption amount is mg/g when the adsorption reaches an equilibrium state;
k1is a quasi-first-order kinetic adsorption rate constant of 1/min;
k2a quasi-second-order kinetic adsorption rate constant, g/mg/min;
t is the adsorption time, min.
Through adsorption kinetics test, the adsorption equilibrium time of the nano sponge adsorbent to the tetracycline antibiotics can be obtained, and the shorter the adsorption equilibrium time is, the faster the adsorption rate is.
The test results are given in table 2 below:
TABLE 2 Performance test results for Nano sponge adsorbents and comparative adsorbents
The data in the table show that the prepared nano sponge adsorbent has a larger saturated adsorption capacity and a shorter adsorption equilibrium time than an activated carbon adsorbent frequently used in the daily technology, which indicates that the nano sponge adsorbent prepared by the preparation method provided in example 1 or example 2 can adsorb and remove more tetracycline in a shorter time and has a better adsorption effect.
The analysis of the two structures shows that the aperture of the activated carbon adsorbent is suitable for most pollutants, the aperture is generally macroporous or mesoporous, and the particle size matching degree with the tetracycline antibiotics is poor, so the adsorption effect is poor; the pore size of the obtained nano sponge adsorbent is matched with the tetracycline antibiotic by adjusting the component proportion of the polyvinyl alcohol aqueous solution and the ethyl cellulose, so that the adsorption effect of the nano sponge adsorbent on the tetracycline antibiotic is improved; the melamine sponge has an undesirable adsorption effect on tetracycline hydrochloride due to the overlarge pore diameter.
Compared with the nano adsorbent without melamine and the nano sponge adsorbent with melamine sponge, the nano sponge adsorbent with melamine sponge has better adsorption effect because the nano adsorbent with smaller particles subdivides the melamine sponge, and a pore structure is formed between the nano adsorbent and the melamine sponge, so that the density of pores is improved, and the adsorption effect is increased.
Meanwhile, the addition of the melamine greatly reduces the difficulty of the subsequent recovery treatment of the adsorbent, and is more beneficial to the practical industrial use.
In the two organic solvents, dichloroethane has a better dissolving effect on ethyl cellulose, and the finally prepared nano sponge adsorbent has a better adsorption effect on tetracycline antibiotics.
The above-mentioned embodiments are merely illustrative and not restrictive, and those skilled in the art can make modifications to the embodiments without inventive contribution as required after reading the present specification, but only protected by the patent laws within the scope of the claims.
Claims (10)
1. A nanometer sponge adsorbent for specifically adsorbing tetracycline antibiotics is characterized in that:
the nano sponge adsorbent comprises the following raw materials in parts by weight:
aqueous polyvinyl alcohol solution: 10-50 parts;
ethyl cellulose: 12-18 parts;
organic solvent: 32-38 parts;
melamine: 20 parts of (1);
and 5 parts of acetone.
2. The nanosponge adsorbent for specific adsorption of tetracycline antibiotics of claim 1, characterized in that: the polyvinyl alcohol aqueous solution comprises 10-50 parts of polyvinyl alcohol and the balance of deionized water.
3. The nanosponge adsorbent for specific adsorption of tetracycline antibiotics of claim 1, characterized in that: the organic solvent is dichloromethane or a solvent A, and the solvent A is a mixed solvent of toluene and ethanol.
4. The nanosponge adsorbent for specific adsorption of tetracycline antibiotics of claim 1, characterized in that: the polyvinyl alcohol is pharmaceutical grade polyvinyl alcohol with molecular weight of 25-30 ten thousand.
5. The nanosponge adsorbent for specific adsorption of tetracycline antibiotics of claim 1, characterized in that: the ethyl cellulose is a commercial pharmaceutical grade product.
6. A nano sponge adsorbent for specifically adsorbing tetracycline antibiotics is prepared by the following steps:
s1 dissolving ethyl cellulose: adding deionized water into an organic solvent, stirring and mixing, then adding ethyl cellulose, and carrying out ultrasonic oscillation on the solution for 2 hours to obtain a uniformly dispersed ethyl cellulose solution;
s2, mixing: adding an ethyl cellulose solution and a polyvinyl alcohol aqueous solution, and carrying out ultrasonic oscillation on the solution for 1 hour to obtain a uniformly dispersed mixed solution;
s3, magnetic stirring: placing the mixed solution on a magnetic stirrer, and magnetically stirring;
s4, filtering, namely filtering the mixed solution after magnetic stirring through a filter screen film to remove undissolved compound residues to obtain a supernatant of the nano adsorbent;
s5: melamine pretreatment: cutting melamine into sponge small blocks, adding acetone and deionized water until the sponge small blocks are immersed, and ultrasonically cleaning;
s6: soaking the small sponge blocks in the supernatant of the nano adsorbent for 12 hours;
s7: absorbing the supernatant of the nano adsorbent on the surface of the sponge by using filter paper, and then placing the nano adsorbent on a filter screen; and transferring the filter screen into an oven for heating and drying to obtain the nano sponge adsorbent.
7. The method for preparing the nanosponge adsorbent for the specific adsorption of tetracycline antibiotics of claim 6, characterized in that: the preparation method of the polyvinyl alcohol aqueous solution in the step S1 comprises the following steps: adding polyvinyl alcohol into cold water at the temperature of 18-22 ℃ while stirring for full swelling and dispersion, then heating to 95 ℃ for accelerated dissolution, and preserving heat for 2-2.5 hours until the solution does not contain micro particles any more, and filtering impurities to obtain a uniformly dispersed polyvinyl alcohol aqueous solution.
8. The method for preparing the nanosponge adsorbent for the specific adsorption of tetracycline antibiotics of claim 6, characterized in that: the rotation speed of the magnetic stirring in the step S3 is 800rpm-1200 rpm.
9. The method for preparing the nanosponge adsorbent for the specific adsorption of tetracycline antibiotics of claim 6, characterized in that: the drying temperature in step S7 is 90 ℃ and the time is 6 h.
10. The method for preparing the nanosponge adsorbent for the specific adsorption of tetracycline antibiotics of claim 5, characterized in that: the aperture of the polyvinyl alcohol filtering screen is 200 meshes.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114225916A (en) * | 2021-11-05 | 2022-03-25 | 南京大学 | Method for adsorbing antibiotics in sewage by using sulfonated alkali lignin-based polyvinyl formal sponge |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114225916A (en) * | 2021-11-05 | 2022-03-25 | 南京大学 | Method for adsorbing antibiotics in sewage by using sulfonated alkali lignin-based polyvinyl formal sponge |
| CN114225916B (en) * | 2021-11-05 | 2022-07-29 | 南京大学 | Method for adsorbing antibiotics in sewage by using sulfonated alkali lignin-based polyvinyl formal sponge |
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Application publication date: 20210608 |