CN111001390A - Composite metal organic adsorption material and preparation method thereof - Google Patents

Composite metal organic adsorption material and preparation method thereof Download PDF

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CN111001390A
CN111001390A CN201911360557.5A CN201911360557A CN111001390A CN 111001390 A CN111001390 A CN 111001390A CN 201911360557 A CN201911360557 A CN 201911360557A CN 111001390 A CN111001390 A CN 111001390A
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adsorption
adsorbent
organic
magnetic stirring
metal salt
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余若冰
吴志聪
张晓焱
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East China University of Science and Technology
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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
    • 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
    • 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
    • C02F2101/36—Organic compounds containing halogen
    • 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
    • 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
    • C02F2101/40—Organic compounds containing sulfur

Abstract

The invention discloses a composite metal organic adsorption material and a preparation method thereof, wherein the preparation method comprises the following steps: s100, respectively drying metal salt and organic ligand, and grinding into fine particles; s200, dissolving metal salt in an organic solvent to obtain a solution A, dissolving an organic ligand in the organic solvent to obtain a solution B, and uniformly mixing A, B solutions; s300, performing magnetic stirring at the temperature of 20-160 ℃, wherein the magnetic stirring speed is 800-3800 r/min, and the reaction time is 12-40 h; s400, drying the product for 6-18 h at 50-95 ℃ after the product is subjected to ultrasonic-assisted dispersion and centrifugal washing for 3-6 times.

Description

Composite metal organic adsorption material and preparation method thereof
Technical Field
The invention relates to a composite metal organic adsorption material and a preparation method thereof, belonging to the field of porous material synthesis and the technical field of water environment treatment.
Background
The antibiotic is one of the most abused drugs in the medical industry and the livestock breeding industry, the antibiotic pollution discharge amount of several provinces in the Yangtze river basin and the coastal region of China is huge, and the antibiotic content in the water body seriously exceeds the standard. Researches find that the long-term retention of antibiotics in water body can affect the growth and reproduction of aquatic animals and plants (such as algae, zooplankton, fish, amphibians and the like), and a large amount of antibiotics are enriched along a food chain to further affect ecological balance. Moreover, even minute amounts of antibiotics in nature cause increased bacterial resistance and even mutation to produce "superbacteria".
The antibiotic wastewater treatment technology mainly comprises a biological treatment method, a physical treatment method and the like, and the treatment principles and effects are different. Although the methods of biodegradation, photocatalytic degradation, advanced oxidation technology and the like can remove antibiotics in water bodies to different degrees, the method has a plurality of defects in the practical application process. The biodegradation process needs strict control of anaerobic conditions, and the treatment period is longer; the photocatalytic degradation technology is generally implemented under the ultraviolet light condition, and simultaneously, the problem that the catalyst is difficult to recover exists; although the effect of removing antibiotics by the advanced oxidation technology is good, the operation and maintenance cost is high, and the generated by-products are more toxic to human bodies than antibiotics; as an adsorption method for removing pollutants in wastewater by utilizing the adsorption characteristic of porous solids, the method has the advantages of simple operation, low raw material consumption, high efficiency, no toxic by-products and the like, can effectively remove various pollutants in the wastewater, and is considered as the most promising technology for treating antibiotic wastewater.
The main materials for adsorbing antibiotics studied in recent years are molecular sieves, carbon nanotubes, adsorption resins, etc., but these adsorption materials have relatively high preparation cost and general adsorption effect, and the adsorbent itself may pollute the environment. Therefore, the development of a novel environment-friendly high-performance adsorbent has important significance for treating antibiotics in wastewater.
The metal organic framework material is a material formed by self-assembly of metal ions and organic ligands, has the advantages of large specific surface area, rich pores, adjustable pore channel structure and the like, and is widely applied to the fields of sensing, catalysis, gas storage, adsorption separation, drug storage, slow release and the like. At present, a plurality of documents report the application of metal organic framework materials in the field of adsorption, but most of the adsorption objects are gas molecules, heavy metal ions and organic dyes, and the reports of the adsorption of antibiotics in wastewater are few. At present, the problem of how to efficiently remove antibiotics in water needs to be solved.
Disclosure of Invention
The invention aims to solve the technical problems of low removal efficiency of antibiotics, poor selective adsorption performance and poor regeneration cycle performance of the adsorbent prepared by the prior art and the like. In order to solve the problems, the invention provides a preparation method of a composite metal organic framework material adsorbent, which comprises the following steps:
s100, respectively drying metal salt and organic ligand, and grinding into fine particles;
s200, dissolving metal salt in an organic solvent to obtain a solution A, dissolving an organic ligand in the organic solvent to obtain a solution B, and uniformly mixing A, B solutions;
s300, performing magnetic stirring at the temperature of 20-160 ℃, wherein the magnetic stirring speed is 800-3800 r/min, and the reaction time is 12-40 h;
s400, drying the product for 6-18 h at 50-95 ℃ after the product is subjected to ultrasonic-assisted dispersion and centrifugal washing for 3-6 times.
Preferably, the metal salt is at least one of cobalt nitrate hexahydrate, nickel nitrate hexahydrate, zinc nitrate hexahydrate, magnesium chloride hexahydrate, aluminum chloride hexahydrate, and ferric chloride hexahydrate; the organic ligand is at least one of terephthalic acid, trimesic acid, 2-methylimidazole, 1, 2-dimethylimidazole, 2-ethyl-4-methylimidazole, ethylene diamine tetraacetic acid and adipic acid.
Preferably, the organic solvent in step S200 is at least one of methanol, ethanol, isopropanol, acetone, N-dimethylformamide and N, N-dimethylacetamide.
Preferably, the metal salt is zinc nitrate hexahydrate, the organic ligand is 2-methylimidazole, and the organic solvent is an N, N-dimethylformamide solvent.
Preferably, the temperature of the magnetic stirring in the step S300 is 20-35 ℃, the magnetic stirring speed is 1200-3000 r/min, and the reaction time is 12-28 h.
Preferably, the temperature of the magnetic stirring in the step S300 is 30 ℃, the magnetic stirring speed is 1800r/min, and the reaction time is 28 h.
Preferably, the mass-to-volume ratio of the metal salt to the organic solvent in step S200 is 1 g: 30 ml-60 ml, the mass volume ratio of the organic ligand to the organic solvent is 1 g: 15 ml-45 ml, and the mass ratio of the metal salt to the organic ligand is 1: 1 to 5.
Preferably, the ultrasonic-assisted dispersion time in step S400 is 40min, the centrifugal washing times are 5 times, the drying temperature is 60 ℃, and the drying time is 12 h.
Preferably, the adsorbing material comprises an adsorbing material prepared by the preparation method of the composite metal-organic adsorbing material.
Preferably, the adsorbent of the adsorbent has a particle size of 67nm to 107nm and an adsorption pore size of 6.13nm to 17.07 nm.
The adsorbent prepared according to the process is applied to adsorption removal of the oxyfluorsaxarene antibiotics in the water body. The invention is applied to the adsorption removal of antibiotics in water and has the beneficial effects that: can quickly adsorb the wastewater for 20min, and can reach 90% of the saturated adsorption capacity.
The invention is applied to the adsorption removal of the oxyfluorfloxacin antibiotics in the water body, and has the beneficial effects that: the ofloxacin pollutant in the wastewater has excellent adsorption removal performance, the adsorption capacity can reach 157mg/g-196mg/g, and the removal rate can reach more than 85%.
The invention is applied to the adsorption removal of antibiotics in water and has the beneficial effects that: the composite material has high-efficiency selective adsorption performance on ofloxacin pollutants in wastewater, and the removal rate of ofloxacin in an Ofloxacin (OFL)/Cefalexin (CEP)/Sulfamethazine (SMZ) multi-component wastewater system can still reach more than 90% of that of a single-component system.
The method is applied to the adsorption removal of the oxyfluorsaxate antibiotics in the water body, has excellent regeneration cycle usability, and can still reach more than 80% of the initial adsorption performance after being recycled for 4-6 times.
Compared with the prior art, the invention has the following advantages and effects:
(1) the novel adsorbent prepared by the invention has excellent adsorption performance on the ofloxacin antibiotics, has simple preparation process and low production cost, and is suitable for industrial mass production;
(2) the adsorption capacity and the adsorption rate of the novel adsorbent prepared by the invention to the ofloxacin antibiotics are superior to those of the traditional adsorbent, the equilibrium adsorption capacity can reach 196mg/g, and the equilibrium adsorption capacity can be approached after 20min of adsorption;
(3) the novel adsorbent prepared by the invention has high-efficiency selective adsorption performance on ofloxacin antibiotics in wastewater, and the removal rate of ofloxacin in a multi-component wastewater system of Ofloxacin (OFL)/Cefalexin (CEP)/Sulfadimidine (SMZ) can still reach more than 90% of that of a single-component system;
(4) the novel adsorbent prepared by the invention has excellent regeneration cycle performance, can be repeatedly used, is easy to strip after adsorption, and does not need to add an additional surfactant;
(5) the novel adsorbent prepared by the invention is green and safe in synthesis and application processes, does not produce secondary pollution, and has wide application prospect.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention.
In the drawings:
FIG. 1 is a flow chart of a preparation method of a composite metal-organic adsorption material;
FIG. 2 is FTIR characterization spectra of example 2 before and after adsorption of ofloxacin;
FIG. 3 is an XRD diffraction pattern before and after adsorption of ofloxacin and an XRD diffraction pattern of ofloxacin in example 2;
FIG. 4 is an SEM photograph of the adsorbent of example 2 before adsorbing ofloxacin;
FIG. 5 is an SEM photograph of the adsorbent of example 2 after adsorbing ofloxacin.
Detailed Description
The present invention will be described in further detail with reference to examples, but the scope of the present invention is not limited to the examples.
As shown in fig. 1, a method for preparing a composite metal-organic adsorption material includes the following steps:
s100, respectively drying metal salt and organic ligand, and grinding into fine particles;
s200, dissolving metal salt in an organic solvent to obtain a solution A, dissolving an organic ligand in the organic solvent to obtain a solution B, and uniformly mixing A, B solutions;
s300, performing magnetic stirring at the temperature of 20-160 ℃, wherein the magnetic stirring speed is 800-3800 r/min, and the reaction time is 12-40 h;
s400, drying the product for 6-18 h at 50-95 ℃ after the product is subjected to ultrasonic-assisted dispersion and centrifugal washing for 3-6 times.
Compared with the prior art, the invention has the following advantages and effects:
(1) the novel adsorbent prepared by the invention has excellent adsorption performance on the ofloxacin antibiotics, has simple preparation process and low production cost, and is suitable for industrial mass production;
(2) the adsorption capacity and the adsorption rate of the novel adsorbent prepared by the invention to the ofloxacin antibiotics are superior to those of the traditional adsorbent, the equilibrium adsorption capacity can reach 196mg/g, and the equilibrium adsorption capacity can be approached after 20min of adsorption;
(3) the novel adsorbent prepared by the invention has high-efficiency selective adsorption performance on ofloxacin antibiotics in wastewater, and the removal rate of ofloxacin in a multi-component wastewater system of Ofloxacin (OFL)/Cefalexin (CEP)/Sulfadimidine (SMZ) can still reach more than 90% of that of a single-component system;
(4) the novel adsorbent prepared by the invention has excellent regeneration cycle performance, can be repeatedly used, is easy to strip after adsorption, and does not need to add an additional surfactant.
As shown in fig. 1, a method for preparing a composite metal-organic adsorption material includes the following steps:
s100, respectively drying metal salt and organic ligand, and grinding into fine particles; wherein the metal salt is at least one of cobalt nitrate hexahydrate, nickel nitrate hexahydrate, zinc nitrate hexahydrate, magnesium chloride hexahydrate, aluminum chloride hexahydrate and ferric chloride hexahydrate; further preferably, the metal salt is zinc nitrate hexahydrate; the organic ligand is at least one of terephthalic acid, trimesic acid, 2-methylimidazole, 1, 2-dimethylimidazole, 2-ethyl-4-methylimidazole, ethylene diamine tetraacetic acid and adipic acid; further preferably, the organic ligand is 2-methylimidazole. Wherein the mass-to-volume ratio of the metal salt to the organic solvent in the step S100 is 1 g: 30 ml-60 ml, the mass volume ratio of the organic ligand to the organic solvent is 1 g: 15 ml-45 ml, and the mass ratio of the metal salt to the organic ligand is 1: 1 to 5.
S200, dissolving metal salt in an organic solvent to obtain a solution A, dissolving an organic ligand in the organic solvent to obtain a solution B, and uniformly mixing A, B solutions; the organic solvent is selected from methanol, ethanol, isopropanol, acetone, N-dimethylformamide and N, N-dimethylacetamide. Further preferred as the organic ligand is N, N-dimethylformamide solvent.
S300, performing magnetic stirring at the temperature of 20-160 ℃, wherein the magnetic stirring speed is 800-3800 r/min, and the reaction time is 12-40 h; preferably, the temperature of the magnetic stirring in the step S200 is 30 ℃, the magnetic stirring speed is 1800r/min, and the reaction time is 28 h.
S400, drying the product for 6-18 h at 50-95 ℃ after the product is subjected to ultrasonic-assisted dispersion and centrifugal washing for 3-6 times. Preferably, the ultrasonic-assisted dispersion time in step S300 is 40min, the centrifugal washing times are 5 times, the drying temperature is 60 ℃, and the drying time is 12 h.
The particle size of the adsorbent of the obtained composite metal organic adsorption material is 67 nm-107 nm, and the adsorption pore size is 6.13 nm-17.07 nm.
The specific embodiment is as follows:
example 1
Liquid phase stirring method for preparing adsorbent
The preparation method of the high-efficiency oxyfluorsaxarene antibiotic adsorbent material comprises the following steps:
s100, respectively drying zinc nitrate hexahydrate and 2-methylimidazole at 65 ℃ for 2 hours, and grinding into fine particles with the particle size of 0.1 mm;
s200, weighing 1.5g of zinc nitrate hexahydrate, and dissolving the zinc nitrate hexahydrate in 70ml of N, N-dimethylformamide solvent to obtain a solution A. 3.5g of 2-methylimidazole was weighed out and dissolved in 85ml of N, N-dimethylformamide solvent to obtain a solution B. Evenly mixing the A, B solution, and carrying out magnetic stirring at the temperature of 20 ℃, wherein the magnetic stirring speed is 2200r/min, and the reaction time is 20 h;
s300, dispersing the product for 40min with the aid of ultrasonic waves, centrifugally washing for 5 times, and drying at 60 ℃ for 12h to obtain the ofloxacin adsorbent which is marked as Zn1.5/3.5-T20n2200t20。
Example 2
Liquid phase stirring method for preparing adsorbent
The preparation method of the high-efficiency oxyfluorsaxarene antibiotic adsorbent material comprises the following steps:
the difference from example 1 is that magnetic stirring is carried out at 25 ℃ and the adsorbent is noted as Zn1.5/3.5-T25n2200t20。
Example 3
Liquid phase stirring method for preparing adsorbent
The preparation method of the high-efficiency oxyfluorsaxarene antibiotic adsorbent material comprises the following steps:
the difference from example 1 is that magnetic stirring is carried out at 30 ℃ and the adsorbent is noted as Zn1.5/3.5-T30n2200t20。
Example 4
Liquid phase stirring method for preparing adsorbent
The preparation method of the high-efficiency oxyfluorsaxarene antibiotic adsorbent material comprises the following steps:
the difference from example 1 is that the magnetization is carried out at 35 deg.CStirring with force, the adsorbent being noted as Zn1.5/3.5-T35n2200t20。
Test example 1
The adsorbent prepared in the embodiment 1 is applied to an adsorption experiment of the oxafloxacin antibiotics in the wastewater, and the adsorption process is as follows:
100ml of ofloxacin solution having a concentration of 100mg/L, PH value of 7 was prepared, and 20mg of the organometallic framework adsorbent prepared in example 1 was added. And (3) putting the mixed solution into a constant-temperature shaking incubator, wherein the temperature is set to be 25 ℃, and the shaking time is 2 hours. After the oscillation is finished, filtering the mixed solution by using a 0.22-micron filter membrane, analyzing the absorbance (A) of the filtrate at a specific wavelength of 342nm by using a UV-5100 ultraviolet spectrophotometer, converting the absorbance into the residual concentration of ofloxacin in the solution, and calculating to obtain the equilibrium adsorption capacity of the adsorbent prepared in the embodiment under corresponding conditions and the equilibrium adsorption capacity capable of being reached by adsorption for 20 min.
Test example 2
The adsorbent prepared in the embodiment 2 is applied to an adsorption experiment of the oxafloxacin antibiotics in the wastewater, and the adsorption process is as follows:
100ml of ofloxacin solution having a concentration of 100mg/L, PH value of 7 was prepared, and 20mg of the organometallic framework adsorbent prepared in example 2 was added. And (3) putting the mixed solution into a constant-temperature shaking incubator, wherein the temperature is set to be 25 ℃, and the shaking time is 2 hours. After the oscillation is finished, filtering the mixed solution by using a 0.22-micron filter membrane, analyzing the absorbance (A) of the filtrate at a specific wavelength of 342nm by using a UV-5100 ultraviolet spectrophotometer, converting the absorbance into the residual concentration of ofloxacin in the solution, and calculating to obtain the equilibrium adsorption capacity of the adsorbent prepared by the embodiment under corresponding conditions, wherein the equilibrium adsorption capacity can be reached after adsorption for 20 min.
Test example 3
The adsorbent prepared in the embodiment 3 is applied to an adsorption experiment of the oxafloxacin antibiotics in the wastewater, and the adsorption process is as follows:
100ml of ofloxacin solution having a concentration of 100mg/L, PH value of 7 was prepared, and 20mg of the organometallic framework adsorbent prepared in example 3 was added. And (3) putting the mixed solution into a constant-temperature shaking incubator, wherein the temperature is set to be 25 ℃, and the shaking time is 2 hours. After the oscillation is finished, filtering the mixed solution by using a 0.22-micron filter membrane, analyzing the absorbance (A) of the filtrate at a specific wavelength of 342nm by using a UV-5100 ultraviolet spectrophotometer, converting the absorbance into the residual concentration of ofloxacin in the solution, and calculating to obtain the equilibrium adsorption capacity of the adsorbent prepared by the embodiment under corresponding conditions, wherein the equilibrium adsorption capacity can be reached after adsorption for 20 min.
Test example 4
The adsorbent prepared in the embodiment 4 is applied to an adsorption experiment of the oxafloxacin antibiotics in the wastewater, and the adsorption process is as follows:
100ml of ofloxacin solution having a concentration of 100mg/L, PH value of 7 was prepared, and 20mg of the organometallic framework adsorbent prepared in example 4 was added. And (3) putting the mixed solution into a constant-temperature shaking incubator, wherein the temperature is set to be 25 ℃, and the shaking time is 2 hours. After the oscillation is finished, filtering the mixed solution by using a 0.22-micron filter membrane, analyzing the absorbance (A) of the filtrate at a specific wavelength of 342nm by using a UV-5100 ultraviolet spectrophotometer, converting the absorbance into the residual concentration of ofloxacin in the solution, and calculating to obtain the equilibrium adsorption capacity of the adsorbent prepared by the embodiment under corresponding conditions, wherein the equilibrium adsorption capacity can be reached after adsorption for 20 min.
The adsorbents prepared in the experimental examples 1 to 4 are applied to adsorption experimental examples 1 to 4 of the ofloxacin antibiotics in the wastewater, and the adsorption effect is shown in the table 1:
TABLE 1 influence of different reaction temperatures on the equilibrium adsorption
Figure BDA0002337062740000081
The state when the concentration of the adsorbate in the solution and the concentration on the surface of the adsorbent are not changed any more is called adsorption equilibrium, the adsorption value when the adsorption process reaches the adsorption equilibrium is called equilibrium adsorption capacity, and the adsorption effect is usually measured by the size of the equilibrium adsorption capacity.
The rapid adsorption performance of the adsorbent is an important index measured by the industrial use of the adsorbent, and a large amount of adsorbate is adsorbed in a short time, which indicates that the adsorbent has strong adsorption power. The quality of the rapid adsorption performance is generally defined as the adsorption capacity of 20min of adsorption as a percentage of the equilibrium adsorption capacity.
In summary, it can be seen from the results of test examples 1-4 in Table 1 that the adsorbent materials obtained in examples 1, 2, 3 and 4 have a reaction temperature in the range of 20 ℃ to 35 ℃ in which the equilibrium adsorption amount is 163mg/g or more and the fast adsorption performance is 90% or more. Considering that the crystallization rate and the crystallinity of the metal organic framework material are changed at relatively low temperature and relatively high temperature, the specific surface area and the pore diameter are further influenced, the reaction temperature is preferably 30 ℃, the equilibrium adsorption amount and the rapid adsorption performance are respectively 175.7mg/g and 92.9 percent under the condition, and the equilibrium adsorption amount and the rapid adsorption performance are in a positive correlation relationship, and fig. 2 shows FTIR characterization spectra of before and after adsorbing ofloxacin and an ofloxacin in example 2.
Example 5
Liquid phase stirring method for preparing adsorbent
The magnetic stirring speed is 1200r/min, other preparation conditions and adsorption experiments are the same as those of the example 3, and the obtained adsorbent is marked as Zn1.5/3.5-T30n1200t20。
Test example 5
The adsorbent prepared in the embodiment 5 is applied to an adsorption experiment of the oxafloxacin antibiotics in the wastewater, and the adsorption process is as follows:
100ml of ofloxacin solution having a concentration of 100mg/L, PH value of 7 was prepared, and 20mg of the organometallic framework adsorbent prepared in example 5 was added. And (3) putting the mixed solution into a constant-temperature shaking incubator, wherein the temperature is set to be 25 ℃, and the shaking time is 2 hours. After the oscillation is finished, filtering the mixed solution by using a 0.22-micron filter membrane, analyzing the absorbance (A) of the filtrate at a specific wavelength of 342nm by using a UV-5100 ultraviolet spectrophotometer, converting the absorbance into the residual concentration of ofloxacin in the solution, and calculating to obtain the equilibrium adsorption capacity of the adsorbent prepared in the embodiment under corresponding conditions and the equilibrium adsorption capacity capable of being reached by adsorption for 20 min.
The results of the effect of the magnetic stirring rate on the equilibrium adsorption amount and the quick adsorption performance are shown in tables 2 and 3.
Example 6
Liquid phase stirring method for preparing adsorbent
Magnetic stirring speed is 1800r/min, other preparation conditions and adsorption experiment and experimentThe same as in example 3, the resulting adsorbent is noted as Zn1.5/3.5-T30n1800t20。
Test example 6
The adsorbent prepared in the embodiment 6 is applied to an adsorption experiment of the ofloxacin antibiotics in the wastewater, and the adsorption process is the same as that of the experimental example 3:
the results of the effect of the magnetic stirring rate on the equilibrium adsorption amount and the quick adsorption performance in test example 6 are shown in tables 2 and 3.
Example 7
Liquid phase stirring method for preparing adsorbent
The magnetic stirring speed is 3000r/min, other preparation conditions are the same as those of experimental example 3, and the obtained adsorbent is marked as Zn1.5/3.5-T30n3000t20。
Test example 7
The adsorbent material of example 7 was selected for the adsorption experiments, and the results of the magnetic stirring rate on the equilibrium adsorption capacity and the quick adsorption performance are shown in tables 2 and 3, which are otherwise the same as in test example 3.
TABLE 2 influence of different magnetic stirring rates on equilibrium adsorption capacity and quick adsorption performance
Figure BDA0002337062740000101
TABLE 3 influence of different magnetic stirring rates on equilibrium adsorption capacity and quick adsorption performance
Figure BDA0002337062740000102
As can be seen from the data in Table 3, the change in the magnetic stirring rate during the reaction significantly affects the adsorption performance of the adsorbent. The magnetic stirring speed influences the contact probability of the metal center and the organic ligand and further influences the coordination of the metal organic framework material, the magnetic stirring speed is preferably 1800r/min, and the equilibrium adsorption capacity and the rapid adsorption performance under the condition are respectively 180.6mg/g and 94.0%.
Example 8
Liquid phase stirring method for preparing adsorbent
The reaction time was 12h, the other preparation conditions were the same as in example 3, and the resulting adsorbent was noted as Zn1.5/3.5-T30n2200t12
Test example 8
The adsorbent material of example 8 was selected for the adsorption experiments, and the reaction time was the same as in test example 3, and the results of the effect on the equilibrium adsorption amount and the quick adsorption performance are shown in tables 4 and 5.
Example 9
Liquid phase stirring method for preparing adsorbent
The reaction time was 28h, the other preparation conditions and the adsorption experiment were the same as in test example 3, and the obtained adsorbent was noted as Zn1.5/3.5-T30n2200t28。
Test example 9
The adsorbent material of example 9 was selected for the adsorption experiments, and the reaction time was the same as in test example 3, and the results of the effect on the equilibrium adsorption amount and the quick adsorption performance are shown in tables 4 and 5.
TABLE 4 influence of different reaction times on equilibrium adsorption and Rapid adsorption Performance
Figure BDA0002337062740000111
TABLE 5 influence of different reaction times on equilibrium adsorption and Rapid adsorption Performance
Figure BDA0002337062740000112
It is understood from comparative test examples 3, 8 and 9 that the reaction time affects the adsorption performance of the adsorbent produced by the present invention. When the reaction time is 12 hours, the crystal form of the metal organic framework material is incomplete, the hierarchical distribution of the pore structure is not stepped, the distribution of adsorption sites of the metal organic framework material is seriously influenced, and the equilibrium adsorption capacity is only 157.3 mg/g. The reaction time is preferably more than 20h, and when the reaction time is 28h, the equilibrium adsorption quantity and the rapid adsorption performance can reach 184.8mg/g and 93.4%.
Example 10
Liquid phase stirring method for preparing adsorbent
3.0g of zinc nitrate hexahydrate is weighed and dissolved in 140ml of N, N-dimethylformamide solvent to obtain solution A, other preparation conditions and adsorption experiment are the same as those in experimental example 3, and the obtained adsorbent is recorded as Zn3/3.5-T30n2200t20。
Test example 10
Adsorption experiment the adsorbent material of example 10 was selected, and the other examples were the same as in test example 3, and the results of the influence of the ratio of the metal center to the organic ligand on the equilibrium adsorption amount and the quick adsorption performance are shown in tables 6 and 7.
TABLE 6 influence of the ratio of metal center to organic ligand on the equilibrium adsorption capacity and the fast adsorption performance
Figure BDA0002337062740000121
TABLE 7 influence of the ratio of metal center to organic ligand on the equilibrium adsorption capacity and the fast adsorption performance
Figure BDA0002337062740000122
From the data in Table 7, it can be seen that the ratio of metal center to organic ligand is one of the factors affecting the adsorption performance. Saturated coordination can reduce adsorption sites of the adsorbent, the metal center ratio is properly increased, the adsorption performance of the adsorbent can be effectively improved, the metal center/organic ligand ratio is preferably 1.5/3.5, and the equilibrium adsorption amount and the rapid adsorption performance under the condition can reach 175.7mg/g and 92.9%.
Example 11
Preparation of compound adsorbent
(1) Respectively drying nickel nitrate hexahydrate and terephthalic acid at 60 ℃ for 1.5h, and grinding into fine particles with the particle size of 0.1 mm;
(2) 2.8g of nickel nitrate hexahydrate was weighed and dissolved in 90ml of N, N-dimethylformamide solvent to obtain solution A. 5.4g of terephthalic acid was weighed and dissolved in 115ml of N, N-dimethylformamide to obtain a B solution. Evenly mixing the A, B solution, and carrying out magnetic stirring at the temperature of 40 ℃, wherein the magnetic stirring speed is 3000r/min, and the reaction time is 28 h;
(3) and dispersing the product for 40min by ultrasonic assistance, centrifugally washing for 5 times, and drying at 70 ℃ for 12h to obtain the adsorbent A component.
The component A of the adsorbent prepared in the example and the Zn adsorbent prepared in the example 21.5/3.5-T25n2200t20(as component B) at a ratio of 1: 1 mass ratio, and the compound adsorbent is marked as M1 (Ni/Zn).
Multi-component selective adsorption test
A plurality of types of antibiotics exist in the antibiotic wastewater, and when the adsorbent acts on an antibiotic mixed system, synergy or antagonism exists among different types of antibiotics. In order to better study the application of the adsorbent in a complex water environment and the selective adsorption performance of the adsorbent prepared by the invention on the ofloxacin antibiotics, cefalexin antibiotics (cephalosporins) and sulfamethazine (sulfonamides) with large market consumption are selected as interference adsorbates in the embodiment, and real antibiotic wastewater is simulated to carry out multi-component adsorption test.
In this example, M1(Ni/Zn) was applied to an adsorption experiment of an Ofloxacin (OFL)/Cefalexin (CEP)/Sulfadimidine (SMZ) multi-component wastewater system, and the adsorption process is as follows:
200ml of Ofloxacin (OFL)/Cefalexin (CEP)/Sulfamethazine (SMZ) mixed solution with the concentration of 75mg/L, PH and the value of 7 is prepared, and 40mgM1(Ni/Zn) is added. And (3) putting the mixed solution into a constant-temperature shaking incubator, wherein the temperature is set to be 25 ℃, and the shaking time is 2 hours. After the oscillation is finished, filtering the mixed solution by using a 0.22 mu m filter membrane, analyzing the absorbance (A) of the filtrate at specific wavelengths of 342nm, 251nm and 259nm by using a UV-5100 ultraviolet spectrophotometer, and respectively converting the absorbance into the residual concentrations of ofloxacin, cefalexin and sulfadimidine in the solution, thereby obtaining that the equilibrium adsorption amount of ofloxacin, cefalexin and sulfadimidine of the adsorbent prepared by the embodiment is 147.5mg/g, 14.6mg/g and 11.9mg/g under corresponding conditions through calculation.
Example 12
Preparation of compound adsorbent
The adsorbent a component prepared in example 11 and the adsorbent B component prepared in example 2 were mixed in a ratio of 1: and mixing the components in a mass ratio of 1.5 to obtain the compound adsorbent.
Test example 12
Multi-component selective adsorption test
The adsorption experiment and the adsorption experiment process of example 11 are the same, and the results of the effect of different compound adsorbent ratios on the multi-component selective adsorption performance (ofloxacin/cefalexin/sulfamethazine) in example 12 are shown in table 8.
Example 13
Preparation of compound adsorbent
The adsorbent a component prepared in example 11 and the adsorbent B component prepared in example 2 were mixed in a ratio of 1: 2 to obtain the compound adsorbent.
Test example 13
Multi-component selective adsorption test
The adsorption experiment of this example is the same as that of test example 11, and the results of the test examples of the different ratios of the compounded adsorbents in example 13 on the selective adsorption performance of the multiple components (ofloxacin/cefalexin/sulfamethazine) are shown in table 8.
TABLE 8 influence of different built-up adsorbent ratios on the Selective adsorption Properties of multiple Components
Group of Compound adsorbent Compounding ratio Multi-component selective adsorption Performance (mg/g)
Test example 11 M1(Ni/Zn) 1：1 147.5/14.6/11.9
Test example 12 M1(Ni/Zn) 1：1.5 155.7/18.1/13.6
Test example 13 M1(Ni/Zn) 1：2 168.2/23.5/16.5
The test results of the composite materials obtained in comparative examples 11, 12 and 13 show that the Ni/Zn compound adsorbent prepared by the invention has high-efficiency selective adsorption performance on a multi-component antibiotic wastewater system, and in an ofloxacin/cefalexin/sulfamethazine compound system, the selective adsorption ratio of the compound adsorbent can reach 10: 1: more than 1, and has strong guiding significance for industrial practical application. The Ni/Zn ratio of the compound adsorbent is reduced, so that the equilibrium adsorption quantity of ofloxacin can be effectively improved, but the selective adsorption performance of ofloxacin can be slightly reduced, and the preferable ratio is 1: 2, the multi-component selective adsorption performance under these conditions was 155.7/18.1/13.6 (mg/g).
Example 14
Preparation of compound adsorbent
(1) Respectively drying ferric chloride hexahydrate and ethylenediamine tetraacetic acid at 75 ℃ for 2 hours, and grinding into fine particles with the particle size of 0.1 mm;
(2) 2.5g of ferric chloride hexahydrate was weighed and dissolved in 100ml of acetone solvent to obtain solution A. 4.5g of ethylenediaminetetraacetic acid was weighed and dissolved in 80ml of acetone solvent to obtain a solution B. Evenly mixing the A, B solution, and carrying out magnetic stirring at the temperature of 25 ℃, wherein the magnetic stirring speed is 1800r/min, and the reaction time is 12 h;
(3) and dispersing the product for 40min by ultrasonic assistance, centrifugally washing for 5 times, and drying at 70 ℃ for 12h to obtain the adsorbent component C.
The adsorbent C component prepared in this example and the adsorbent B component prepared in example 2 were mixed in a ratio of 1: 1 mass ratio, and the compound adsorbent is marked as M2 (Fe/Zn).
Cyclic adsorption performance test
The cyclic regeneration capacity of the material is an important factor for measuring the practical application of the material, and the excellent cyclic adsorption performance not only greatly reduces the use cost of the adsorbent, but also provides an application premise for realizing large-scale industrial production of the adsorbent powder as a composite material additive. The invention takes the equilibrium adsorption capacity accounting for the initial adsorption percentage after the adsorbent is recycled for 4 times as an index for measuring the cyclic adsorption performance.
Test example 14
M2(Fe/Zn) is applied to a regeneration cycle performance test of the ofloxacin antibiotics in the wastewater, and the test process is as follows:
100ml of ofloxacin solution with a concentration of 100mg/L, PH value of 7 was prepared, and 40mgM2(Fe/Zn) was added. Initial adsorption procedure with reference to example 1, after adsorption was completed, ofloxacin was desorbed by washing 5 times with acetone solvent, dried at 65 ℃ for 1 hour to remove the remaining solvent, and then re-adsorption experiments were performed. Experimental results show that the adsorbent prepared by the embodiment has excellent regeneration cycle performance, and the adsorption performance can still reach 85.1% of that of primary adsorption after the adsorbent is recycled for 4 times.
Example 15
Preparation of compound adsorbent
The adsorbent C component prepared in example 14 and the adsorbent B component prepared in example 2 were mixed in a ratio of 1: and mixing the components in a mass ratio of 1.5 to obtain the compound adsorbent.
Test example 15
Cyclic adsorption performance test
The cyclic adsorption experiment of the experimental example 15 is the same as the experimental process of the experimental example 14, and the results of the effect of different compound adsorbent ratios on the cyclic adsorption performance in the experimental example 15 are shown in table 9.
Example 16
Preparation of compound adsorbent
The adsorbent C component prepared in example 14 and the adsorbent B component prepared in example 2 were mixed in a ratio of 1: 2 to obtain the compound adsorbent.
Test example 16
Cyclic adsorption performance test
The cyclic adsorption experiment of the experimental example is the same as the experimental process of the experimental example 14, and the results of the effect of different compound adsorbent ratios on the cyclic adsorption performance in the experimental example 16 are shown in table 9.
TABLE 9 influence of different built adsorbents on the adsorption performance of the cycle
Figure BDA0002337062740000161
As can be seen from the data in Table 9, the Fe/Zn compound adsorbent prepared by the invention has excellent cyclic adsorption performance, and the equilibrium adsorption capacity can still reach more than 80% of the initial adsorption after being recycled for 4 times, so that the compound adsorbent can be recycled. This will effectively reduce its commercial use cost and give the material good industrial application prospects. The compound adsorbent Fe/Zn ratio is reduced, so that the cyclic adsorption performance can be effectively improved, and the compound ratio is 1: and when the adsorption time is 1, the cyclic adsorption performance can reach 85.1 percent.
Finally, it should be noted that: the above description is only a few of the preferred embodiments of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. The preparation method of the composite metal-organic adsorption material is characterized by comprising the following steps:
s100, respectively drying metal salt and organic ligand, and grinding into fine particles;
s200, dissolving metal salt in an organic solvent to obtain a solution A, dissolving an organic ligand in the organic solvent to obtain a solution B, and uniformly mixing A, B solutions;
s300, performing magnetic stirring at the temperature of 20-160 ℃, wherein the magnetic stirring speed is 800-3800 r/min, and the reaction time is 12-40 h;
s400, drying the product for 6-18 h at 50-95 ℃ after the product is subjected to ultrasonic-assisted dispersion and centrifugal washing for 3-6 times.
2. The method of claim 1, wherein the metal salt is at least one of cobalt nitrate hexahydrate, nickel nitrate hexahydrate, zinc nitrate hexahydrate, magnesium chloride hexahydrate, aluminum chloride hexahydrate, and ferric chloride hexahydrate; the organic ligand is at least one of terephthalic acid, trimesic acid, 2-methylimidazole, 1, 2-dimethylimidazole, 2-ethyl-4-methylimidazole, ethylene diamine tetraacetic acid and adipic acid.
3. The method according to claim 1, wherein the organic solvent in step S200 is at least one of methanol, ethanol, isopropanol, acetone, N-dimethylformamide, and N, N-dimethylacetamide.
4. The method of claim 1, wherein the metal salt is zinc nitrate hexahydrate, the organic ligand is 2-methylimidazole, and the organic solvent is N, N-dimethylformamide solvent.
5. The method of claim 1, wherein the temperature of the magnetic stirring in the step S300 is 20 ℃ to 35 ℃, the magnetic stirring rate is 1200r/min to 3000r/min, and the reaction time is 12h to 28 h.
6. The method of claim 1, wherein the temperature of the magnetic stirring in step S300 is 30 ℃, the magnetic stirring rate is 1800r/min, and the reaction time is 28 h.
7. The method according to claim 1, wherein the mass-to-volume ratio of the metal salt to the organic solvent in step S200 is 1 g: 30 ml-60 ml, and the mass volume ratio of the organic ligand to the organic solvent is 1 g: 15 ml-45 ml, and the mass ratio of the metal salt to the organic ligand is 1: 1 to 5.
8. The method according to claim 1, wherein the ultrasonic-assisted dispersion time in step S400 is 40min, the number of centrifugal washing times is 5, the drying temperature is 60 ℃, and the drying time is 12 h.
9. A composite metal-organic adsorption material, characterized in that the adsorption material comprises the adsorption material prepared by the method according to any one of claims 1 to 8.
10. A composite metal-organic adsorption material according to claim 9, wherein the adsorbent particle size of the adsorption material is 67nm to 107nm, and the adsorption pore size is 6.13nm to 17.07 nm.
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