CN112915970A - Method for adsorbing and treating antibiotics in water body by using three-dimensional metal organic framework/aerogel composite material - Google Patents
Method for adsorbing and treating antibiotics in water body by using three-dimensional metal organic framework/aerogel composite material Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/024—Compounds of Zn, Cd, Hg
- B01J20/0244—Compounds of Zn
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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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
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Abstract
The invention discloses a method for adsorbing and treating antibiotics in a water body by using a three-dimensional metal organic framework/aerogel composite material, which comprises the following steps: mixing the three-dimensional metal organic framework/aerogel composite material with the antibiotic wastewater for contact adsorption to complete adsorption and removal of the antibiotic wastewater; the three-dimensional metal organic framework/aerogel composite material comprises ZIF-L and gelatin aerogel, wherein the ZIF-L is loaded on a gelatin aerogel substrate. The three-dimensional metal organic framework/aerogel composite material can realize the efficient adsorption removal of the antibiotic wastewater under static and dynamic conditions, the method has the advantages of simple treatment process, convenient operation, relatively low treatment cost, good adsorption removal effect, high efficiency and good material reusability, and has higher application potential and commercial prospect in practical application as a treatment method which can be generally used and can efficiently adsorb and remove the antibiotic.
Description
Technical Field
The invention belongs to the field of antibiotic wastewater treatment, relates to a method for adsorbing and treating antibiotics in a water body, and particularly relates to a method for adsorbing and treating antibiotics in a water body by using a three-dimensional metal organic framework/aerogel composite material.
Background
Antibiotics are widely used in the treatment and prevention of diseases in humans and animals. However, large-scale production of antibiotics and lack of regulatory requirements for use of antibiotics lead to abuse of antibiotics in daily life and production, and a large amount of antibiotics enter the water environment, induce the generation of resistance genes and promote the propagation of the resistance genes in strains, thereby bringing about various environmental problems and health risks. The high concentration and long-term residue of antibiotics interfere with the stability of an ecological system, and organisms exposed to the antibiotics in the water body for a long time, growth and reproduction and the like are affected. In addition, antibiotics in the water body can be gradually enriched in aquatic organisms and react on human beings through food chains, nets and the like, so that various health problems are caused. Therefore, the method is particularly important for removing the antibiotics in the water body. However, because antibiotics have high stability and are not easily degraded and metabolized by organisms, the sewage treatment technology based on the traditional process of sludge microorganism anaerobic and aerobic oxygen can not effectively remove the antibiotics in the sewage. Therefore, how to remove antibiotics in water bodies in a green and efficient manner also becomes one of the current research hotspots.
Compared with antibiotic treatment technologies such as advanced oxidation, photocatalytic degradation, biodegradation, membrane separation and the like, the adsorption method has the advantages of low cost, simplicity and convenience in operation, small pollution and the like, and shows higher application value and application prospect. The Metal Organic Frameworks (MOFs) are porous materials formed by coordination and assembly of metal ions or ion clusters and organic ligands, and are widely applied to the field of adsorption due to the characteristics of huge specific surface area, high porosity, adjustable pore structure, easiness in functionalization and the like. However, powdered MOFs suffer from the disadvantages of spontaneous agglomeration and stacking, material loss, poor recycling performance and the like during use, and greatly limit further application thereof in the field of water treatment. In recent years, the composite materials of the MOFs and the carrier are widely concerned, however, the preparation processes of many MOFs composite materials are relatively complex, the carrier loading performance is poor, the loading material is easy to fall off, and the performance of the obtained MOFs composite materials is obviously weakened. Therefore, how to select a proper carrier, further improve the performance of the MOFs material such as stability and recoverability, obtain the MOFs composite material with good adsorption performance and high cycle regeneration performance and obtain a preparation method of the MOFs composite material with the advantages of convenience in operation, simplicity in synthesis, environmental friendliness and the like has a very important significance for improving the application of the MOFs material in antibiotic wastewater treatment.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects of the prior art and provide a method for adsorbing and treating antibiotics in water by using a three-dimensional metal organic framework/aerogel composite material, wherein the method has the advantages of simple treatment process and adsorption equipment, convenience in operation, low treatment cost, large adsorption capacity, high adsorption speed and good recycling performance.
In order to solve the technical problems, the invention adopts the following technical scheme:
a method for adsorbing and treating antibiotics in a water body by using a three-dimensional metal organic framework/aerogel composite material is characterized by comprising the following steps: mixing the three-dimensional metal organic framework/aerogel composite material with the antibiotic wastewater for contact adsorption to complete adsorption treatment on the antibiotic wastewater; the three-dimensional metal organic framework/aerogel composite material comprises a ZIF-L and a gelatin aerogel substrate, wherein the ZIF-L is loaded on the gelatin aerogel substrate.
In the method, the method for preparing the three-dimensional metal organic framework/aerogel composite material is further improved, and comprises the following steps:
s1, respectively dispersing zinc nitrate hexahydrate and dimethylimidazole in solvent water, mixing, stirring and drying to obtain a metal organic framework material ZIF-L;
s2, mixing the ZIF-L of the metal organic framework material in the step S1 with a gelatin water solution, adding sodium dodecyl sulfate, stirring and mixing uniformly, and stirring for foaming to obtain a foamed mixed material of the ZIF-L and gelatin;
s3, freezing the mixed material of the ZIF-L and the gelatin in the step S2 at-18 ℃ to obtain a frozen mixed material, and freeze-drying to obtain a ZIF-L/gelatin aerogel composite material;
s4, calcining the ZIF-L/gelatin aerogel composite material obtained in the step S3 under the protection of nitrogen to obtain the three-dimensional metal organic framework/aerogel composite material
In a further improvement of the above preparation method, in step S1, the molar ratio of zinc nitrate hexahydrate to dimethylimidazole is 1: 8.
in the preparation method, the mass ratio of the ZIF-L to the gelatin is 0.4:1 in step S2.
In the above preparation method, further improvement is that, in step S2, the volume-to-mass ratio of the solvent water to the gelatin is 20mL:1g of the total weight of the composition.
In a further improvement of the above preparation method, in step S2, the adding amount ratio of the sodium dodecyl sulfate is 0.1mol/mL.
In the above preparation method, further improvement is provided, in step S2, the rotation speed of stirring and foaming is 1000r/min to 1500 r/min; the stirring and foaming time is 10-15 min.
In a further improvement of the above preparation method, in step S3, the freezing time is 12 hours.
In a further improvement of the above preparation method, in step S3, the freeze-drying time is 36-48 h.
In a further improvement of the preparation method, in step S4, the calcination temperature is 100 ℃ to 300 ℃, the temperature rise rate in the calcination process is 5 ℃/min, the calcination temperature is maintained for 2 hours at the final temperature (100/200/300 ℃), and the temperature is naturally reduced to normal temperature after the calcination is finished. The method also comprises the following steps after the calcination reaction is completed: and washing and drying the product obtained after the calcination. Ultrapure water is adopted for washing; the washing times are 3-5 times; the drying treatment is carried out under the condition of freeze drying; the drying time is 36-48 h.
In the method, the mass-volume ratio of the three-dimensional metal organic framework/aerogel composite material to the antibiotic wastewater is 3.5 g: 1L; the antibiotic in the antibiotic wastewater is tetracycline hydrochloride; the concentration of the antibiotics in the antibiotic wastewater is 20 mg/L-100 mg/L; the pH value of the antibiotic wastewater is 3-11.
In the method, the rotation speed of the oscillating adsorption is further improved to be 150 r/min-200 r/min; the oscillation adsorption time is 2h-3 h.
Compared with the prior art, the invention has the advantages that:
(1) in the invention, the ZIF-L is loaded on the gelatin aerogel substrate, and the ZIF-L is uniformly distributed on the surface of the aerogel substrate, so that the agglomeration and stacking effects of the powder ZIF-L are greatly reduced, more adsorption active sites are exposed, and the adsorption performance is improved. Meanwhile, the ZIF-L is loaded on the aerogel, so that the problem of material loss in the using and recycling processes is reduced, and the recycling performance of the material is improved. In addition, the porous structure of the composite material is beneficial to reducing the transmission resistance in the adsorption process, provides faster adsorption kinetics for adsorption reaction, and improves the adsorption performance of the material. Compared with the prior art, the three-dimensional metal organic framework/aerogel composite material has the advantages of porous structure, high adsorption performance, good recoverability and the like, can realize high-efficiency and rapid adsorption of antibiotics, and has potential practical application prospects.
(2) According to the invention, the preparation process of the three-dimensional metal organic framework/aerogel composite material is researched and optimized, the surface active agent sodium dodecyl sulfate is introduced to reduce the surface tension of the gelatin solution, a large number of micro bubbles are generated in the mixed solution of the ZIF-L and the gelatin through high-speed stirring, and the foamed ZIF-L/gelatin aerogel composite material is prepared.
(3) According to the invention, a chemical cross-linking agent is not required to be used, the water resistance of the composite material is enhanced by optimizing the calcination temperature and increasing the cross-linking degree of the gelatin, and the porous structure of the composite material is further improved. The porous structure of the composite material is more beneficial to the performance of the efficacy of adsorbing active sites, so that stronger adsorption capacity is generated, and the three-dimensional metal organic framework/aerogel composite material with better adsorption effect is obtained. Particularly, when the calcining temperature is 200 ℃, the carbon material has high water resistance, a better porous structure and high-efficiency adsorption removal capacity.
(4) The invention provides a method for adsorbing and treating antibiotics in a water body by using a three-dimensional metal organic framework/aerogel composite material, which is characterized in that the three-dimensional metal organic framework/aerogel composite material is mixed with antibiotic wastewater for contact adsorption, so that the antibiotics in the wastewater can be efficiently adsorbed; the preparation process of the three-dimensional metal organic framework/aerogel composite material has the advantages of convenience in operation, simplicity in synthesis, low cost and the like, and is suitable for large-scale preparation. The method has the advantages of simple treatment process and adsorption equipment, low cost, large material adsorption capacity, high adsorption speed and high repeated utilization rate, can be widely adopted, can efficiently remove the antibiotics in the water body, and has high application value and commercial value.
Drawings
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention.
FIG. 1 shows ZIF-L/FGA of a three-dimensional metal organic framework/aerogel composite material prepared in example 1 of the present invention100、ZIF-L/FGA200、ZIF-L/FGA300、ZIF-L/GA200And a scanning electron micrograph of ZIF-L, wherein (a) ZIF-L, (b, d, e, f, h) is ZIF-L/FGA200(c) is ZIF-L/GA200And (g) is ZIF-L/FGA100(i) is ZIF-L/FGA300。
FIG. 2 shows ZIF-L/FGA of the three-dimensional metal organic framework/aerogel composite material prepared in example 1 of the present invention200X-ray diffraction patterns of gelatin aerogels FGA and ZIF-L.
FIG. 3 shows ZIF-L/FGA of the three-dimensional metal organic framework/aerogel composite material prepared in example 1 of the present invention200And a nitrogen absorption and desorption curve chart of the gelatin aerogel FGA, wherein the mosaic graph is a micropore diameter distribution diagram.
FIG. 4 is a ZIF-L/FGA three-dimensional metal organic framework/aerogel composite, foamed and unfoamed, made in example 1 of the present invention200、ZIF-L/GA200The effect of adsorption removal of tetracycline hydrochloride solution is shown, wherein the mosaic is a rate constant plot.
FIG. 5 shows ZIF-L/FGA of three-dimensional metal organic framework/aerogel composite material in example 2 of the present invention200The effect of adsorbing and removing tetracycline hydrochloride under different pH conditions is shown in the figure.
FIG. 6 shows ZIF-L/FGA of three-dimensional metal organic framework/aerogel composite material in example 3 of the present invention200The adsorption effect of the tetracycline hydrochloride solution with different concentrations is shown.
FIG. 7 shows ZIF-L/FGA of three-dimensional metal organic framework/aerogel composite material in example 4 of the present invention200The effect of the cyclic regeneration adsorption for removing the tetracycline hydrochloride solution is shown.
Detailed Description
The invention is further described below with reference to the drawings and specific preferred embodiments of the description, without thereby limiting the scope of protection of the invention.
The starting materials and equipment used in the following examples are commercially available. In the following examples, unless otherwise specified, the data obtained are the average of three or more repeated experiments.
Example 1
A method for adsorbing and treating antibiotics in a water body by using a three-dimensional metal organic framework/aerogel composite material, in particular to a method for adsorbing tetracycline hydrochloride in the water body by using the three-dimensional metal organic framework/aerogel composite material, which comprises the following steps:
and adding 1 part of the three-dimensional metal organic framework/aerogel composite material into 100mL of tetracycline hydrochloride solution with the concentration of 30mg/L, uniformly mixing and dispersing, oscillating at the rotating speed of 150r/min, and adsorbing for 3 hours to finish the adsorption treatment of the tetracycline hydrochloride.
After the completion of the shaking adsorption, 4mL of the sample was taken and centrifuged. And (3) measuring absorbance of the supernatant obtained by centrifugation by using an ultraviolet-visible spectrophotometer, and determining the concentration of the residual antibiotics after adsorption, so as to obtain the adsorption effect of the three-dimensional metal organic framework/aerogel composite material prepared by foaming and non-foaming on tetracycline hydrochloride, wherein the result is shown in figure 4.
In this example, the three-dimensional metal organic framework/aerogel composite material (ZIF-L/FGA) was used200) Comprises ZIF-L and a gelatin aerogel substrate, wherein the ZIF-L is loaded on the gelatin aerogel substrate. Three-dimensional metal organic framework/aerogel composite material (ZIF-L/FGA)200) The calcination temperature of (2) was 200 ℃.
In this example, the three-dimensional metal organic framework/aerogel composite material (ZIF-L/FGA) was used200) The preparation method specifically comprises the steps of taking zinc nitrate hexahydrate and dimethylimidazole as raw materials, stirring to synthesize a metal organic framework material ZIF-L, mixing the ZIF-L, gelatin and sodium dodecyl sulfate, freeze-drying, and calcining at low temperature to obtain the three-dimensional metal organic framework/aerogel composite material, and comprises the following steps:
(1) respectively dispersing zinc nitrate hexahydrate and dimethylimidazole in solvent water according to the molar ratio of 1:8, mixing, stirring at the rotating speed of 100r/min for 4 hours to obtain a ZIF-L solution of a metal organic framework material, and drying to obtain the ZIF-L.
(2) Mixing the ZIF-L obtained in the step (1) with a gelatin water solution, and adding sodium dodecyl sulfate, wherein the mass ratio of the ZIF-L to the gelatin is 0.4:1, the volume mass of solvent water and gelatin is 20mL:1g, adding 0.1mol/mL of sodium dodecyl sulfate, stirring for 2h at the rotation speed of 200r/min, uniformly mixing, and stirring at a high speed of 1000r/min-1500r/min for 15min to obtain the mixed material of ZIF-L and gelatin.
(3) Freezing the mixed material of the ZIF-L and the gelatin in the step (2) at-18 ℃ for 12h to obtain a frozen mixed material, and freeze-drying for 48h to obtain the ZIF-L/gelatin aerogel composite material
(4) And (4) under the protection of nitrogen, calcining the ZIF-L/gelatin aerogel composite material obtained in the step (3) at a low temperature, wherein the heating rate is 5 ℃/min, and the temperature is kept for 2h when the temperature reaches 200 ℃. Soaking and washing the calcined product after natural cooling by using ultrapure water, freezing and then freeze-drying for 36 hours to obtain the three-dimensional metal organic frameworkAerogel composite material named ZIF-L/FGA200。
In this example, the three-dimensional metal organic framework/aerogel composite material (ZIF-L/FGA) was used100) The preparation method of (A), and a three-dimensional metal organic framework/aerogel composite material (ZIF-L/FGA)200) The preparation method of (a) is basically the same, and the differences are only that: the final calcination temperature of the composite was 100 ℃.
In this example, the three-dimensional metal organic framework/aerogel composite material (ZIF-L/FGA) was used300) The preparation method of (A), and a three-dimensional metal organic framework/aerogel composite material (ZIF-L/FGA)200) The preparation method of (a) is basically the same, and the differences are only that: the final calcination temperature of the composite was 300 ℃.
In this example, a three-dimensional metal organic framework/aerogel composite (ZIF-L/GA) was prepared for comparison without introducing sodium lauryl sulfate for foaming200) The preparation method of (A), and a three-dimensional metal organic framework/aerogel composite material (ZIF-L/FGA)200) The preparation method of (a) is substantially the same, except that: and when the ZIF-L is mixed with the gelatin aqueous solution, no sodium dodecyl sulfate is added, and no foaming process exists.
In this example, a comparative gelatin aerogel material (FGA) containing no ZIF-L was prepared200) The preparation method of (A), and a three-dimensional metal organic framework/aerogel composite material (ZIF-L/FGA)200) The preparation method of (a) is substantially the same, except that: ZIF-L was not added when the gelatin solution was mixed.
In this example, a method of preparing an uncalcined gelatin aerogel material (FGA) was compared with a gelatin aerogel material (FGA)200) The preparation method of (a) is substantially the same, except that: the gelatin aerogel material was not calcined.
FIG. 1 is a scanning electron microscope image of a ZIF-L and three-dimensional metal organic framework/aerogel composite material prepared in example 1 of the present invention, wherein (a) is ZIF-L, the morphology structure of which is two-dimensional foliate, and (b) is ZIF-L/FGA200And (b) is ZIF-L/GA200And the contrast of the two shows that after the sodium dodecyl sulfate is introduced for foaming, the pore diameter of the composite material is reduced, the pore density is greatly increased, and the adsorption and transmission are more facilitated. FIG. (d-f) shows ZIF-L/FGA200Further amplifying the picture, the ZIF-L is uniformly dispersed and loaded on the surface of the gelatin aerogel substrate. The graph (g-i) shows that calcination at different temperatures gives a composite material, the temperature rise is helpful for the construction of the pore structure, but the high temperature (300 ℃) causes the pore structure to collapse and shrink, and the pore walls to curl.
FIG. 2 shows a three-dimensional metal organic framework/aerogel composite (ZIF-L/FGA) prepared in example 1 of the present invention200) Gelatin aerogel substrate (FGA), and ZIF-L. As shown in FIG. 2, FGA shows a flat single peak, and ZIF-L has a sharp multiple peak, indicating that the crystallinity of the sample is better. ZIF-L/FGA200Similar to the main peak of ZIF-L, indicating that ZIF-L was successfully loaded on the substrate.
FIG. 3 shows a three-dimensional metal organic framework/aerogel composite (ZIF-L/FGA) prepared in example 1 of the present invention200) And a nitrogen adsorption and desorption curve chart of a gelatin aerogel substrate (FGA), and as can be seen from figure 3, the FGA is an adsorption and desorption curve type II isotherm which is reflected by mesopores and macropores, ZIF-L/FGA200The adsorption and desorption curve is IV-type isotherm which is micropore, mesopore and macropore, and the micropore is introduced after the ZIF-L is loaded, so that the ZIF-L/FGA is obtained200Has a porous structure.
FIG. 4 is a graph showing the comparison of tetracycline hydrochloride adsorption effect of the three-dimensional metal organic framework/aerogel composite material prepared by foaming and non-foaming in example 1, wherein the introduction of sodium dodecyl sulfate foaming, ZIF-L/FGA200Has a more efficient adsorption removal capacity based on a calculated rate constant, ZIF-L/FGA200The rate constant of the method is far higher than that of ZIF-L/GA200Demonstration of ZIF-L/FGA200The adsorption capacity is higher, more micro bubbles are introduced due to foaming, the pore density and the specific surface area of the composite material are increased, the pollutant transmission resistance in the adsorption process is reduced, and the adsorption performance of the material is improved. Therefore, the introduction of micro bubbles by virtue of the foaming of the sodium dodecyl sulfate is beneficial to improving the pore structure performance of the material, and further improving the adsorption performance of the material.
Example 2
A method for adsorbing and treating antibiotics in a water body by using a three-dimensional metal organic framework/aerogel composite material, in particular to a method for adsorbing tetracycline hydrochloride in the water body by using the three-dimensional metal organic framework/aerogel composite material, which comprises the following steps:
9 parts of the three-dimensional metal organic framework/aerogel composite material (ZIF-L/FGA) of example 1 were taken200) Respectively adding the tetracycline hydrochloride solution into tetracycline hydrochloride solutions with pH values of 3, 4, 5, 6, 7, 8, 9, 10 and 11, wherein the tetracycline hydrochloride solutions have the volume of 100mL and the concentration of 30mg/L, and oscillating and adsorbing for 2h under the condition of the rotation speed of 150r/min to finish the tetracycline hydrochloride adsorption treatment.
After the end of the shaking adsorption, 4mL of sample was taken and centrifuged. Taking supernatant obtained by centrifugation, measuring absorbance by an ultraviolet visible spectrophotometer, and determining the concentration of tetracycline hydrochloride after adsorption to obtain the three-dimensional metal organic framework/aerogel composite material (ZIF-L/FGA)200) The adsorption effect on tetracycline hydrochloride solutions of different pH values is shown in FIG. 5.
FIG. 5 shows the three-dimensional metal organic framework/aerogel composite (ZIF-L/FGA) of example 2 of the present invention200) The adsorption removal effect of the tetracycline hydrochloride under different pH conditions is shown in the figure. FIG. 5 shows that pH affects ZIF-L/FGA200The adsorption performance is ZIF-L/FGA, the pH value is between 4 and 10200The absorption of tetracycline hydrochloride has high removal efficiency of about 95 percent. And when the pH is close to extreme conditions (pH 3, 11), ZIF-L/FGA200The adsorption capacity is significantly reduced. In particular, ZIF-L/FGA at pH 3200The adsorption removal efficiency dropped to 73.3%. Based on the Zeta potential distribution, ZIF-L/FGA200The zero potential point of (B) is close to pH 2, which indicates that the pH is in the range of 3-11, ZIF-L/FGA200The surface is negatively charged. Different pH conditions affect the dissociation of tetracycline hydrochloride molecules, so that the tetracycline hydrochloride molecules have different electrical properties, namely different electrical properties of the tetracycline hydrochloride molecules and ZIF-L/FGA200Electrostatic attraction or repulsion between the two components, resulting in ZIF-L/FGA200Change in adsorption effect. The experimental result shows that the pH is between 4 and 10, and the three-dimensional metal organic framework/aerogel composite material (ZIF-L/FGA)200) Has higher adsorption removal capacity, and proves that ZIF-L/FGA200Has wide pH adaptationThe application capability is high, and the practical application value is high.
Example 3
A method for adsorbing and treating antibiotics in a water body by using a three-dimensional metal organic framework/aerogel composite material, in particular to a method for adsorbing tetracycline hydrochloride in the water body by using the three-dimensional metal organic framework/aerogel composite material, which comprises the following steps:
5 parts of the three-dimensional metal organic framework/aerogel composite material (ZIF-L/FGA) of example 1 were taken200) Respectively adding the tetracycline hydrochloride solution into tetracycline hydrochloride solutions with the concentrations of 20mg/L, 30mg/L, 50mg/L, 70mg/L and 100mg/L, wherein the volume of the tetracycline hydrochloride solution is 1000mL, and oscillating and adsorbing for 3h under the condition that the rotating speed is 150r/min to finish the adsorption treatment of the tetracycline hydrochloride.
After the end of the shaking adsorption, 4mL of sample was taken and centrifuged. Taking supernatant obtained by centrifugation, measuring absorbance by an ultraviolet visible spectrophotometer, and determining the concentration of tetracycline hydrochloride after adsorption to obtain the three-dimensional metal organic framework/aerogel composite material (ZIF-L/FGA)200) The adsorption effect on tetracycline hydrochloride solutions of different concentrations is shown in fig. 6.
FIG. 6 shows a three-dimensional metal organic framework/aerogel composite (ZIF-L/FGA) according to example 3 of the present invention200) The adsorption effect of the tetracycline hydrochloride solution with different concentrations is shown. As can be seen from FIG. 6, the tetracycline hydrochloride solution concentrations were 20mg/L, 30mg/L, 50mg/L, 70mg/L, and 100mg/L, respectively, and the three-dimensional metal-organic framework/aerogel composite material (ZIF-L/FGA)200) The adsorption amounts of (A) were 18.39, 28.61, 47.49, 66.59, and 93.93mg/g, respectively. ZIF-L/FGA for low concentration tetracycline hydrochloride solution (less than 50mg/L)200Can realize quick and effective adsorption, and can reach adsorption balance within 1 h. While for high concentrations, adsorption equilibrium and high adsorption removal can be achieved within 3 h. Thus, the three-dimensional metal organic framework/aerogel composite material (ZIF-L/FGA) of the invention200) Has better adsorption removal effect on tetracycline hydrochloride solutions with different concentrations. As the concentration of the tetracycline hydrochloride solution increases, the corresponding adsorption capacity of the material increases, which also indicates that the ZIF-L/FGA200Has higher adsorption capacityCan effectively adsorb and remove tetracycline hydrochloride.
Example 4
A method for adsorbing and treating antibiotics in a water body by using a three-dimensional metal organic framework/aerogel composite material, in particular to a method for adsorbing tetracycline hydrochloride in the water body by using the three-dimensional metal organic framework/aerogel composite material, which comprises the following steps:
1 part of the three-dimensional metal organic framework/aerogel composite material (ZIF-L/FGA) of example 1 was taken200) And adding the tetracycline hydrochloride solution into the tetracycline hydrochloride solution, wherein the volume of the tetracycline hydrochloride solution is 100mL, the concentration is 20mg/L, and oscillating and adsorbing for 3h under the condition that the rotating speed is 150r/min to finish the adsorption treatment of the tetracycline hydrochloride.
After the end of the shaking adsorption, 4mL of sample was taken and centrifuged. And (4) taking the supernatant obtained by centrifugation, measuring the absorbance by an ultraviolet-visible spectrophotometer, and determining the concentration of the tetracycline hydrochloride after adsorption. The ZIF-L/FGA after use200The column was soaked in ethanol solution for 12h for desorption, followed by washing with ultrapure water for the next cycle as described above. Thereby obtaining the three-dimensional metal organic framework/aerogel composite material (ZIF-L/FGA)200) The effect of cyclic regeneration of the tetracycline hydrochloride solution adsorption is shown in fig. 7.
FIG. 7 shows the three-dimensional metal organic framework/aerogel composite material (ZIF-L/FGA) in example 4 of the present invention200) The effect of the cyclic regeneration adsorption for removing the tetracycline hydrochloride solution is shown. As can be seen from FIG. 7, after 9 adsorption-desorption cycle experiments, ZIF-L/FGA200The high adsorption removal performance is still maintained, and the ninth removal efficiency can still reach 87.4 percent. ZIF-L/FGA200The performance is reduced from 95 percent to 87 percent, the overall performance is reduced by less than 10 percent, and the ZIF-L/FGA is shown200Has excellent cyclic regeneration performance. The dispersion load strategy of the ZIF-L on the aerogel substrate reduces powder agglomeration and stacking, makes full use of material performance, avoids material loss in the using and recycling process, and enhances the recycling performance of the material.
Therefore, the invention utilizes the three-dimensional metal organic framework/aerogel composite material (ZIF-L/FGA)200) Adsorption treated waterMethod for in vivo antibiotics by incorporating three-dimensional metal organic framework/aerogel composite (ZIF-L/FGA)200) The tetracycline hydrochloride wastewater is mixed for contact adsorption, so that the antibiotics in the water body can be efficiently adsorbed and removed. The method has the advantages of simple treatment process, convenient operation, low requirement on adsorption equipment, large adsorption capacity of the material, high adsorption speed, good cyclic utilization rate and environmental friendliness, can be widely adopted, can efficiently remove antibiotics in water, and has high practical application value and commercial prospect.
The above examples are merely preferred embodiments of the present invention, and the scope of the present invention is not limited to the above examples. All technical schemes belonging to the idea of the invention belong to the protection scope of the invention. It should be noted that modifications and embellishments within the scope of the invention may be made by those skilled in the art without departing from the principle of the invention, and such modifications and embellishments should also be considered as within the scope of the invention.
Claims (9)
1. A method for adsorbing and treating antibiotics in a water body by using a three-dimensional metal organic framework/aerogel composite material is characterized by comprising the following steps: mixing the three-dimensional metal organic framework/aerogel composite material with the antibiotic wastewater for contact adsorption to complete adsorption treatment on the antibiotic wastewater; the three-dimensional metal organic framework/aerogel composite material comprises ZIF-L and gelatin aerogel, wherein the ZIF-L is loaded on a gelatin aerogel substrate.
2. The method of claim 1, wherein the method of preparing the three-dimensional metal organic framework/aerogel composite comprises the steps of:
s1, respectively dispersing zinc nitrate hexahydrate and dimethylimidazole in solvent water, mixing, stirring and drying to obtain a metal organic framework material ZIF-L;
s2, mixing the precursor ZIF-L in the step S1 with a gelatin water solution, adding sodium dodecyl sulfate, stirring and mixing uniformly, and stirring and foaming to obtain a foamed mixed material of the ZIF-L and the gelatin;
s3, freezing the mixed material of the ZIF-L and the gelatin in the step S2 at-18 ℃ to obtain a frozen mixed material, and freeze-drying to obtain a ZIF-L/gelatin aerogel composite material;
s4, calcining the ZIF-L/gelatin aerogel composite material obtained in the step S3 under the protection of nitrogen to obtain the three-dimensional metal organic framework/aerogel composite material.
3. The method according to claim 2, wherein in step S1, the molar ratio of zinc nitrate hexahydrate to dimethylimidazole is 1: 8.
4. The method according to claim 2, wherein in step S2, the mass ratio of ZIF-L to gelatin is 0.4:1, the volume mass of the solvent water and gelatin is 20mL:1g, and the amount of sodium lauryl sulfate added is 0.1mol/mL.
5. The method according to claim 2, wherein in step S2, the stirring and foaming speed is 1000r/min to 1500r/min, and the stirring and foaming time is 10 to 15 min.
6. The method of claim 2, wherein the freezing time in step S3 is 12 hours, and the freeze-drying time is 36-48 hours.
7. The preparation method according to claim 2, wherein in step S4, the calcination temperature is 100 ℃ to 300 ℃, the temperature rise rate in the calcination process is 5 ℃/min, the calcination temperature is maintained for 2h at the final temperature (100/200/300 ℃), and the temperature is naturally reduced to normal temperature after the calcination. The method also comprises the following steps after the calcination reaction is completed: and washing and drying the product obtained after the calcination. Ultrapure water is adopted for washing; the washing times are 3-5 times; the drying treatment is carried out under the condition of freeze drying; the drying time is 36-48 h.
8. The method according to any one of claims 1 to 7, wherein the mass-to-volume ratio of the three-dimensional metal-organic framework/aerogel composite material to the antibiotic wastewater is 3.5 g: 1L; the antibiotic in the antibiotic wastewater is tetracycline hydrochloride; the concentration of the antibiotics in the antibiotic wastewater is 20 mg/L-100 mg/L; the pH value of the antibiotic wastewater is 3-11.
9. The method according to any one of claims 1 to 7, wherein the rotation speed of the oscillating adsorption is 150r/min to 200 r/min; the oscillation adsorption time is 2h-3 h.
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