CN112774635B - Preparation method and application of activated alumina-loaded Fe-MOF green composite granules - Google Patents
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Abstract
The invention discloses a preparation method and application of active alumina-loaded Fe-MOF green composite granules, which comprises the following steps: dissolving soluble ferric salt in water, stirring to obtain a ferric salt water solution, then adding activated alumina, and fully stirring and mixing to obtain a mixed solution of alumina and ferric salt; adding the organic ligand into alkali liquor, and stirring to dissolve the organic ligand to obtain an organic ligand solution; adding the organic ligand solution into the mixed solution, carrying out mild stirring, and separating after reaction to obtain an initial product of the activated alumina-loaded Fe-MOF green composite granules; and (3) washing the primary product, and heating and activating to obtain the activated alumina-loaded Fe-MOF green composite granules. The method has the advantages of simple and efficient process, easy operation, low requirement on equipment conditions, extremely low energy consumption, zero use of organic solvent in the whole process, and excellent removal performance of the active alumina-loaded Fe-MOF composite granules on the antibiotic pollutants detected in the current water body.
Description
Technical Field
The invention belongs to the field of material science and water pollution control and treatment, and particularly relates to a preparation method and application of active alumina-loaded Fe-MOF green composite granules.
Background
Antibiotics are closely related to people's daily life. The existing research shows that the traditional process of the existing sewage treatment plant can not effectively remove antibiotics in water to a certain extent, a large amount of antibiotic residues can still be detected in some municipal tail water, and the municipal tail water can enter different receiving water bodies through discharging, so that the phenomenon of antibiotic pollution to different degrees exists in natural water bodies. Antibiotic pollutants remained in the water environment can cause harm to human health through the enrichment effect of a food chain, and can also have great influence on the biodiversity in the water body. Therefore, research on the removal of wastewater containing antibiotics is receiving more and more attention. Adsorption methods have been favored in the fields of water pollution treatment and the like because of their advantages of being convenient to operate, economical, efficient, simple, feasible and the like.
Metal-Organic Frameworks (MOFs) exhibit great application prospects in many fields, such as energy storage, catalysis, sensing, drug release, adsorption, and the like, due to their advantages of ultra-high specific surface area, low crystal density, pore size, and functional adjustability. At present, thousands of MOFs materials are reported, but most of the MOFs materials are powdery and difficult to be practically applied; in addition to powdered MOFs materials, research has been devoted to the development of bulk MOFs, which still present certain difficulties in scale-up. The existing material forming method mainly comprises extrusion forming, crosslinking curing, substrate fixing and the like, and a proper substrate is selected to realize the high-efficiency loading of the MOFs material by considering the factors of the thermal stability, the chemical stability and the like of the MOFs, so that the problem that the current powdery MOFs are difficult to apply is expected to be solved.
Fe-MOF is a metal organic framework material taking an iron source as a metal node, and is paid much attention to due to good hydrothermal stability; meanwhile, the iron source is cheap and easy to obtain, and the regular pore channel structure is enriched, particularly the mesoporous structure which most MOFs do not have is obtained, so that the iron source is made to stand out in the field of adsorption separation. According to the invention, granular activated alumina is selected as a base material, on one hand, the surface functional group of the granular activated alumina can provide a large number of nucleation sites for the immobilized growth of Fe-MOF, and on the other hand, the high specific surface area of the granular activated alumina also provides favorable conditions for the efficient loading of Fe-MOF.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention mainly aims to provide a preparation method of active alumina-loaded Fe-MOF green composite granules
The invention also aims to provide application of the activated alumina-loaded Fe-MOF green composite granules in water pollution treatment, in particular application in removing tetracycline antibiotic pollutants in water.
The first purpose of the invention is realized by the following scheme:
a preparation method of active alumina-loaded Fe-MOF green composite granules mainly comprises the following steps:
s1, dissolving soluble ferric salt in water, stirring to obtain a ferric salt aqueous solution, adding activated alumina, and fully stirring and mixing to obtain a mixed solution of the activated alumina and the ferric salt;
s2, adding the organic ligand into the alkali liquor, and stirring to dissolve the organic ligand to obtain an organic ligand solution;
s3, adding the organic ligand solution obtained in the step S2 into the mixed solution obtained in the step S1, carrying out mild stirring, and carrying out centrifugal separation after reaction to obtain an initial product of the activated alumina-loaded Fe-MOF green composite granules;
and S4, washing the primary product of the activated alumina-loaded Fe-MOF green composite granules obtained in the step S3, and heating and activating to obtain the activated alumina-loaded Fe-MOF green composite granules.
Further, the soluble ferric salt in the step S1 is ferrous chloride hydrate; the concentration of the soluble ferric salt is 10-30 g/L.
Further, the activated alumina in the step S1 is spherical particles with the diameter interval of 0.2 mm-5 mm; the dosage of the activated alumina is 20-80 g/L.
Further, in the step S2, the organic ligand is trimesic acid, and the alkali in the alkali liquor is sodium hydroxide; the concentration of the organic ligand is 30-70 g/L; the concentration of the sodium hydroxide is 10-50 g/L.
Further, the molar ratio of the organic ligand to the iron salt in the step S3 is 1: (1-4).
Furthermore, in the step S3, the stirring speed is 100-350 rpm, the reaction time is 10-24 h, and the reaction condition is normal temperature.
Further, the washing process in the step S4 is washing for 3-5 times by using hot water at 70-90 ℃; the heating and activating process in the step S4 is vacuum drying for 8-12 h at the temperature of 100-150 ℃.
Another object of the present invention is achieved by the following scheme:
the active alumina-loaded Fe-MOF green composite granules prepared by the method are applied to the field of water pollution treatment, and particularly applied to adsorbing tetracycline antibiotic pollutants in water.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) The invention obtains a novel process technology for the large-scale production of the Fe-MOF/alumina composite granules with high energy efficiency and high stability, and breaks through the bottleneck that the powdery MOFs materials are difficult to apply.
(2) According to the invention, the efficient and uniform immobilization of Fe-MOF is realized by means of rich functional groups on the surface of activated alumina through a step method and a self-assembly strategy, and the problems of serious loss of specific surface area and active sites and the like in the traditional forming method (such as bonding, extrusion forming and the like) can be effectively avoided.
(3) The active alumina-loaded Fe-MOF green composite granules prepared by the invention have the advantages of simple and efficient process, easiness in operation, low requirements on equipment conditions, extremely low energy consumption, zero use of organic solvents in the whole process, and environmental friendliness.
Drawings
FIG. 1 is an XRD spectrum of powdered Fe-MOF prepared in example 1, commercial granular activated alumina, and Fe-MOF-supported activated alumina green composite pellets prepared in examples 2 to 4, wherein FIG. 1 (a) is a comparison of powdered Fe-MOF prepared in example 1 with a standard spectrum thereof, and FIG. 1 (b) is a comparison of commercial granular activated alumina with Fe-MOF-supported active alumina green composite pellets prepared in examples 2 to 4;
FIG. 2 is an SEM image of commercially available granular activated alumina and Fe-MOF-supported activated alumina green composite pellets prepared in example 3, wherein FIG. 2 (a) is an SEM image of commercially available granular activated alumina and FIG. 2 (b) is an SEM image of Fe-MOF-supported activated alumina green composite pellets prepared in example 3;
FIG. 3 is a graph comparing the effect of the activated alumina-supported Fe-MOF green composite granules prepared in example 4 on the removal of tetracycline hydrochloride in a water body by powdered Fe-MOF, commercially available granular activated alumina, and a conventional porous granular material.
Detailed Description
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, and it is obvious that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
The reagents used in the examples are commercially available without specific reference.
Example 1
7.5g FeCl 2 ·4H 2 Adding O into a round-bottom flask, adding 330mL of deionized water, and stirring to dissolve; dissolving 3.6g of sodium hydroxide in 90mL of deionized water, performing ultrasonic treatment for 5min to dissolve the sodium hydroxide, adding 4.5g of trimesic acid, and stirring to dissolve the trimesic acid to obtain a clear solution; then adding the obtained trimesic acid solution into the ferric salt solution, stirring and reacting for 15 hours at normal temperature under the condition of 130rpm, and cleaning for 2 times by using hot water at the temperature of 80 ℃ after centrifugal separation; activating for 12h under the condition of vacuum 100 ℃, obtaining a sample and marking the sample as Fe-MOF.
Example 2
7.5g FeCl 2 ·4H 2 Adding O into a round-bottom flask, adding 330mL of deionized water, stirring to dissolve, then adding 10g of alumina with the particle size of 0.2-0.5 mm, and fully stirring to obtain a mixed solution of activated alumina and ferric salt; dissolving 3.6g of sodium hydroxide in 90mL of deionized water, performing ultrasonic treatment for 5min to dissolve the sodium hydroxide, adding 4.5g of trimesic acid, and stirring to dissolve the trimesic acid to obtain a clear solution; then the obtained trimesic acid is treatedAdding the solution into a mixed solution of activated alumina and ferric salt, stirring at normal temperature for reaction for 15h under the condition of 130rpm, performing centrifugal separation, and washing with hot water at 70 ℃ for 4 times; activating for 8h under the condition of vacuum 100 ℃, obtaining a sample and marking the sample as Fe-MOF/activated alumina-1.
Example 3
1.5g FeCl 2 ·4H 2 Adding O into a round-bottom flask, adding 130mL of deionized water, stirring to dissolve, adding 6.8g of activated alumina with the particle size of 1-2 mm, and fully stirring to obtain a mixed solution of the activated alumina and ferric salt; dissolving 0.27g of sodium hydroxide in 15mL of deionized water, performing ultrasonic treatment for 5min to dissolve the sodium hydroxide, adding 0.53g of trimesic acid, and stirring to dissolve the trimesic acid to obtain a clear solution; then adding the obtained trimesic acid solution into a mixed solution of activated alumina and ferric salt, stirring and reacting for 20 hours at normal temperature under the condition of 220rpm, and washing for 3 times by hot water at 90 ℃ after centrifugal separation; activating for 10h under the condition of vacuum 120 ℃, obtaining a sample and marking the sample as Fe-MOF/activated alumina-2.
Example 4:
4.9g of FeCl 2 ·4H 2 Adding O into a round-bottom flask, adding 165mL of deionized water, stirring to dissolve, then adding 12g of activated alumina with the particle size of 3-5 mm, and fully stirring to obtain a mixed solution of the activated alumina and ferric salt; dissolving 1.0g of sodium hydroxide in 20mL of deionized water, performing ultrasonic treatment for 5min to dissolve the sodium hydroxide, adding 1.4g of trimesic acid, and stirring to dissolve the trimesic acid to obtain a clear solution; then adding the obtained trimesic acid solution into a mixed solution of activated alumina and ferric salt, stirring and reacting for 24 hours at normal temperature under the condition of 350rpm, and washing for 3 times by using hot water at the temperature of 80 ℃ after centrifugal separation; activating for 12h under the condition of vacuum 150 ℃, obtaining a sample and marking the sample as Fe-MOF/activated alumina-3.
In summary, the performance of the materials prepared in the above examples 1-4 for characterization analysis and adsorption removal of tetracycline hydrochloride in water is as follows:
(1) XRD characterization results
The activated alumina and the samples prepared in examples 1 to 4 of the present invention were characterized by an Empyrean sharp X-ray diffractometer, produced by parnaciaceae, the netherlands, wherein the operating conditions were: copper target, 40KV,40mA, step size 0.0131 degree, scanning speed 9.664 seconds/step. As shown in FIG. 1 (a), the characteristic diffraction peak of Fe-MOF prepared in example 1 is consistent with the peak position reported in the existing literature, and the diffraction peak is strong and sharp, which indicates that Fe-MOF is successfully prepared in the invention; in addition, as can be seen by comparing with the spectrum of the activated alumina (see fig. 1 (b)), distinct characteristic diffraction peaks of Fe-MOF appear in the spectrum of the activated alumina-supported Fe-MOF green composite granules prepared in examples 2-4, which indicates that Fe-MOF is successfully supported on the activated alumina granules; it is also noted that the intensity of the diffraction peaks of alumina is reduced, probably because the high crystallinity of Fe-MOF dominates over the lower crystallinity of alumina.
(2) SEM characterization analysis
The surface morphology of the activated alumina particles and the green composite pellets prepared in example 3 of the present invention were analyzed and compared using a MERLIN field emission scanning electron microscope (SEM, carl Zeiss, germany). As can be seen from fig. 2 (a) and 2 (b) in fig. 2, the surface of the activated alumina particles was rough and not smooth, and the particle surface of the composite pellets became relatively flat and dense after Fe-MOF loading.
(3) Tetracycline hydrochloride (TCH) adsorption removal performance test
The specific experimental conditions are as follows: TCH initial concentration is 10mg/L, reaction liquid volume is 1L, the adding amount of the powdery Fe-MOF is 0.5g/L, the adding amounts of the activated alumina, the Fe-MOF green composite granules loaded by the activated alumina prepared by the invention and the traditional porous material are 10g/L, sampling is carried out at preset time, and the sampling volume is 4mL. And (3) quantitatively testing the TCH in the collected water sample at the maximum absorption wavelength of 357nm by using an ultraviolet visible spectrophotometer (TU-1810, beijing Punjac analysis), wherein the test result is shown in figure 3.
As can be seen from FIG. 3, the powdery Fe-MOF has excellent TCH removal effect, and complete TCH removal is realized within 2h, but the problems of difficult powder recovery, easy secondary pollution and the like exist; for removing TCH from granular activated alumina, the adsorption phenomenon of the granular activated alumina is fast before slow, but the final removal rate is only about 40%; in addition, the activated alumina-supported Fe-MOF green composite granules prepared by the method can realize complete TCH removal within 3h, and the adsorption time is slightly longer than that of powdery Fe-MOF, which is caused by the properties of the granules, and because the mass transfer process of larger-sized bulk particles is limited by steric hindrance, the phenomenon of mass transfer rate lower than that in a powder state can occur. In addition, compared with the performance of the traditional granular porous materials (columnar activated carbon, coconut shell activated carbon and molecular sieve) on the market, the invention also carries out the performance comparison research, and as can be seen from the figure, the traditional granular porous materials have obviously slower adsorption rate to TCH and poorer treatment effect. The coconut shell activated carbon has certain adsorption performance relatively, and the columnar activated carbon and the molecular sieve have no adsorption effect on the TCH basically. On the whole, the active alumina-loaded Fe-MOF green composite granules prepared by the invention not only solve the problem of difficult application of powdered MOFs, but also have excellent adsorption performance and strong practicability, thereby having great application potential in the field of water treatment.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (7)
1. The preparation method of the active alumina supported Fe-MOF green composite granules is characterized by comprising the following steps of:
s1, dissolving soluble ferric salt in water, stirring to obtain a ferric salt water solution, adding activated alumina, and fully stirring and mixing to obtain a mixed solution of the activated alumina and the ferric salt; the soluble ferric salt is ferrous chloride hydrate; the concentration of the soluble ferric salt is 10-30 g/L; the active alumina is spherical particles with the diameter interval of 0.2 mm-5 mm; the dosage of the activated alumina is 20-80 g/L;
s2, adding an organic ligand into the alkali liquor, and stirring to dissolve the organic ligand to obtain an organic ligand solution, wherein the organic ligand is trimesic acid;
s3, adding the organic ligand solution obtained in the step S2 into the mixed solution obtained in the step S1, carrying out mild stirring, carrying out centrifugal separation after reaction to obtain an initial product of the activated alumina-loaded Fe-MOF green composite granules, wherein the reaction condition is normal temperature;
and S4, washing the primary product of the activated alumina-loaded Fe-MOF green composite granules obtained in the step S3, and heating and activating to obtain the activated alumina-loaded Fe-MOF green composite granules.
2. The method for preparing the activated alumina-supported Fe-MOF green composite granules according to claim 1, wherein the alkali in the alkali liquor in the step S2 is sodium hydroxide; the concentration of the organic ligand is 30-70 g/L; the concentration of the sodium hydroxide is 10-50 g/L.
3. The method for preparing the activated alumina-supported Fe-MOF green composite granules according to claim 1, wherein the molar ratio of the organic ligand to the iron salt in the step S3 is 1: (1-4).
4. The preparation method of the activated alumina-supported Fe-MOF green composite granules according to claim 1, wherein the stirring speed in the step S3 is 100-350 rpm, and the reaction time is 10-24 h.
5. The method for preparing the activated alumina-supported Fe-MOF green composite granules according to claim 1, wherein the washing process in the step S4 is washing 3 to 5 times by using hot water at 70 to 90 ℃; the heating and activating process in the step S4 is vacuum drying for 8-12 h at the temperature of 100-150 ℃.
6. The application of the active alumina-supported Fe-MOF green composite granules obtained by the preparation method according to any one of claims 1 to 5 is characterized in that the active alumina-supported Fe-MOF green composite granules are used for water pollution treatment.
7. The application of the activated alumina-supported Fe-MOF green composite granules obtained by the preparation method according to any one of claims 1 to 5 is characterized in that the activated alumina-supported Fe-MOF green composite granules are used for adsorbing tetracycline antibiotic pollutants in a water body.
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