CN115041127A - Magnetic cerium-based metal oxide adsorbent and preparation method and application thereof - Google Patents
Magnetic cerium-based metal oxide adsorbent and preparation method and application thereof Download PDFInfo
- Publication number
- CN115041127A CN115041127A CN202210529328.7A CN202210529328A CN115041127A CN 115041127 A CN115041127 A CN 115041127A CN 202210529328 A CN202210529328 A CN 202210529328A CN 115041127 A CN115041127 A CN 115041127A
- Authority
- CN
- China
- Prior art keywords
- cerium
- metal oxide
- based metal
- adsorbent
- magnetic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- 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]
-
- 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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28009—Magnetic properties
-
- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
-
- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/345—Regenerating or reactivating using a particular desorbing compound or mixture
- B01J20/3475—Regenerating or reactivating using a particular desorbing compound or mixture in the liquid phase
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- 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
- C02F1/48—Treatment of water, waste water, or sewage with magnetic or electric fields
- C02F1/488—Treatment of water, waste water, or sewage with magnetic or electric fields for separation of magnetic materials, e.g. magnetic flocculation
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/105—Phosphorus compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/18—PO4-P
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/16—Regeneration of sorbents, filters
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Compounds Of Iron (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention provides a magnetic cerium-based metal oxide adsorbent and a preparation method and application thereof, and relates to the technical field of water treatment materials. The method specifically comprises the following steps: directly dissolving cerium salt, ferric salt and organic acid in a polar solvent to be used as effective components of the adsorbent, taking trimesic acid dissolved in the polar solvent to be used as a ligand, uniformly mixing the ligand with the effective components, standing and drying to obtain a precursor, and pyrolyzing the precursor to obtain the magnetic cerium-based metal oxide adsorbent. The synthesis method is simple and safe, the reaction temperature is low, and the production process is easy to control. In addition, after the magnetic separation and recovery of the adsorbent, the adsorption operation can be carried out again through simple activation, so that the adsorption cost is further reduced, and the adsorption efficiency is improved. After the adsorbent is recycled for multiple times, the adsorption performance of the water body pollutants is not obviously influenced.
Description
Technical Field
The invention belongs to the technical field of water body treatment materials, and particularly relates to a magnetic cerium-based metal oxide adsorbent as well as a preparation method and application thereof.
Background
The existing methods for removing phosphorus in water mainly comprise biotechnology, physical and chemical technology and the like, wherein the adsorption method has the advantages of high efficiency, low cost and recoverability and is widely concerned. The utilization efficiency of effective components in the adsorbent material determines the use cost of the adsorbent, and although various types of high-efficiency nano adsorbents are developed in recent years, the problem of the utilization rate of the effective components is not solved, so that the preparation cost of the adsorbent is overhigh, and the practical application of the adsorbent is greatly influenced.
Cerium-based oxides are highly efficient phosphate adsorbents that can achieve selective adsorption of phosphate by means of surface ligand exchange, precipitation (chem. eng.j.,2020,379: 122431.; environ. sci. technol.,2020,54(1): 50-66.). However, the currently developed cerium-based oxide phosphate adsorbent has the problem of low utilization rate of Ce atoms, which results in high use cost. In order to solve the above problems, researchers developed schemes such as defect site regulation (chem.eng.j.,2020,394:124912.), surface functional group modification (environ.sci.technol.,2020,54(7): 4601-4608) and the like to improve the phosphate adsorption capacity of cerium-based oxide, however, the above methods only adopt a reducing atmosphere to change the number of adsorption sites on the surface of the adsorbent, and do not fundamentally solve the problem of low utilization rate of Ce atoms. Meanwhile, the above-mentioned nano-adsorbent also has a problem in separation after adsorption.
In the prior art, patent application No. 201410220313.8 discloses cerium oxide modified Fe 3 O 4 @SiO 2 The method for removing phosphate in water body by particle adsorption is simple and the cerium oxide is loaded to Fe 3 O 4 @SiO 2 On the particles, only the high-efficiency separation process of the cerium-based oxide is realized, and the atom utilization efficiency of cerium is not improved. The patent with application number 202010986573.1 disclosesThe patent only loads cerium oxide nano particles into porous polyacrylic acid microsphere pore channels, does not regulate and control the element utilization rate of cerium, and cannot reduce the use cost of cerium.
Therefore, the development of a high-performance adsorbent for selective phosphorus removal has the advantages of simple preparation process, low cost, high utilization rate of effective components and capability of realizing rapid separation and recovery, and is a problem to be solved by technical personnel in the field.
Disclosure of Invention
The invention aims to provide a preparation method of a magnetic cerium-based metal oxide adsorbent, which is characterized in that cerium salt, iron salt and organic acid are directly dissolved in a polar solvent to be used as effective components of the adsorbent, trimesic acid dissolved in the polar solvent is used as a ligand, the ligand and the effective components are uniformly mixed and stand to obtain a precursor, and the precursor is pyrolyzed to obtain the magnetic cerium-based metal oxide adsorbent. The synthesis method is simple and safe, the reaction temperature is low, the effective components are directly mixed and dissolved uniformly, the reaction steps and the reaction time can be reduced, and the method has the beneficial effect of quickly and efficiently preparing the adsorbent.
In order to achieve the above object, the present invention provides a method for preparing a magnetic cerium-based metal oxide adsorbent, comprising the following steps:
1) weighing a certain amount of cerium salt, ferric salt and organic acid, and dissolving in a polar solvent to obtain a solution A;
2) dissolving a certain amount of trimesic acid ligand in a polar solvent to obtain a solution B;
3) slowly adding the solution A into the solution B under the condition of continuous stirring, adjusting the pH value of the system, standing, collecting precipitate, washing with a polar solvent, and drying to obtain a precursor;
4) and pyrolyzing the mixture under the protection of inert gas to obtain a precursor, thus obtaining the magnetic cerium-based metal oxide adsorbent.
In a preferred embodiment, the polar solvent in step 1), step 2) and step 3) comprises ethanol and/or water.
In a preferred embodiment, the cerium salt in step 1) is cerium nitrate or a hydrate thereof, the iron salt is ferric nitrate or a hydrate thereof, and the organic acid is citric acid; in the step 1), the mass concentration of the cerium salt in the solution A is 1-25%, the mass concentration of the iron salt in the solution A is 1-25%, and the mass concentration of the organic acid in the solution A is 0.01-10%.
In a preferred embodiment, the mass concentration of the trimesic acid ligand in the solution B in the step 2) is 0.01 to 10%.
In a preferred embodiment, the volume ratio of the solution a to the solution B in the step 3) is 1: (1-10).
In a preferred embodiment, the continuous stirring conditions in step 3) are: the stirring speed is 50-600rpm, and the stirring time is 1-6 h; the slow adding time is 1-2 h; and adjusting the pH of the system to 7-9.
In a preferred embodiment, the pyrolysis conditions in step 4) are: the calcination temperature is 400-.
Another objective of the present invention is to provide the magnetic cerium-based metal oxide adsorbent prepared by any one of the above methods, wherein the magnetic cerium-based metal oxide adsorbent with high cerium utilization rate is prepared by selecting raw materials and optimizing reaction conditions, such that raw material cost can be effectively reduced, adsorption effect can be improved, and excellent selectivity for phosphate ions in water is provided.
The invention also aims to provide the application of the magnetic cerium-based metal oxide adsorbent prepared by any one of the methods in removing water pollutants. And the magnet can be used for recovering the adsorbent after adsorption is finished, and adsorption operation is carried out again after activation, so that the adsorption cost is further reduced, and the adsorption efficiency is improved.
In order to achieve the purpose, the invention provides an application of removing water body pollutants, which specifically comprises the following steps:
the magnetic cerium-based metal oxide adsorbent prepared by any one of the methods is put into a phosphate-containing water body, and is stirred for reaction, so that the removal of water body pollutants can be completed; after the reaction is finished, the magnetic cerium-based metal oxide adsorbent can be separated and recovered from the water body by using a magnet, and then rinsed to be neutral by using alkali liquor and deionized water, so that the magnetic cerium-based metal oxide adsorbent can be recycled.
In a preferred embodiment, the mass ratio of the magnetic cerium-based metal oxide adsorbent to the phosphate is (2-4): 1, the adsorption capacity of the adsorbent to phosphate can reach 240mg of Pg -1 The adsorption capacity of the phosphate based on the cerium element can reach 468mg of pg -1 。
Compared with the prior art, the technical scheme of the invention has the following advantages:
1. the magnetic cerium-based metal oxide phosphorus removal adsorbent provided by the invention promotes the Ce active site in the adsorbent through the electronic shift action between Fe and Ce. The pyrolysis regulation and control function of the organic acid increases the concentration of the hydroxyl functional group on the surface of the Ce-based adsorbent, and improves the hydroxyl capacity of ligand exchange with phosphate. The metal organic framework structure constructed by the trimesic acid further effectively disperses the effective components in the adsorbent, and enhances the adsorption effect of the adsorbent on phosphate. The Fe component in the adsorbent provides a magnetic separation function, so that the recovery cost of the adsorbent is reduced.
2. The magnetic cerium-based metal oxide phosphate adsorbent has the characteristic of high utilization rate of cerium element, can effectively reduce the raw material cost of the adsorbent, and can reach the adsorption capacity of 240mg Pg to phosphate by the adsorbent through condition optimization -1 The adsorption capacity of the phosphate based on cerium is up to 468mg of Pg -1 Is far higher than the similar adsorbents reported at present; meanwhile, the iron component is introduced to regulate and control the cerium adsorption active site, so that the adsorbent has the characteristic of magnetic separation, and the use cost of the adsorbent is effectively reduced. In addition, the adsorbent obtained by the invention has the advantages of excellent pH adaptability and resistance to common coexisting ions in water, and is a high-efficiency phosphate adsorbent with low use cost.
3. The magnetic cerium-based metal oxide phosphate adsorbent prepared by the method has the advantages of simple process steps, low reaction energy consumption, short time and easy control of the production process, and is particularly suitable for large-scale industrial preparation and production.
4. After the magnetic cerium-based metal oxide phosphate adsorbent prepared by the invention is magnetically separated and recovered, the adsorption operation can be carried out again through simple activation, so that the adsorption cost is further reduced, and the adsorption efficiency is improved. The adsorbent has excellent adsorption-desorption cycle stability, wherein the adsorption-desorption-activation is recorded as 1 time of utilization, the adsorption capacity of the same adsorbent is more than 80% of the initial adsorption capacity after 10 times of cycle utilization, and the adsorption capacity of the same adsorbent is more than 55% of the initial adsorption capacity after 40 times of adsorption-desorption-activation cycle utilization.
Drawings
These and/or other aspects and advantages of the present invention will become more apparent and more readily appreciated from the following detailed description of the embodiments of the invention, taken in conjunction with the accompanying drawings of which:
FIG. 1 is an SEM electron micrograph of a magnetic cerium-based metal oxide phosphate adsorbent prepared in example 1 of the present invention;
FIG. 2 is a hysteresis regression line graph of the magnetic cerium-based metal oxide phosphate adsorbent prepared in example 1 of the present invention, wherein a is the state of the adsorbent in a pollutant-containing water body, and b is the magnetic separation effect;
FIG. 3 is a graph showing the adsorption performance of the magnetic cerium-based metal oxide phosphate adsorbent prepared in examples 1-2 of the present invention and the adsorbents prepared in comparative examples 1-4;
FIG. 4 is a graph showing the effect of different pH on the adsorption capacity of the magnetic cerium-based metal oxide phosphate adsorbent prepared in example 1 of the present invention;
FIG. 5 shows the effect of different concentrations of coexisting interfering ions in water on the adsorption capacity of the magnetic cerium-based metal oxide phosphate adsorbent prepared in example 1 of the present invention;
fig. 6 is a graph showing the effect of the number of adsorption-desorption-activation times on the adsorption capacity and desorption capacity of the magnetic cerium-based metal oxide phosphate adsorbent prepared in example 1.
Detailed Description
For a better understanding of the present invention for those skilled in the art, the present invention will be described in further detail with reference to the accompanying drawings and specific embodiments, but it should be understood that the scope of the present invention is not limited to the specific embodiments.
The embodiment of the invention provides a magnetic cerium-based metal oxide adsorbent and a preparation method and application thereof, and solves the problems of poor adsorption performance, low utilization rate of effective components, complex preparation process, long time consumption, high adsorption cost and the like of the adsorbent in the prior art.
In order to solve the above problems, the technical solution in the embodiments of the present invention has the following general idea:
the invention provides a preparation method of a magnetic cerium-based metal oxide adsorbent, which specifically comprises the following steps:
1) weighing a certain amount of cerium salt, ferric salt and organic acid, and dissolving in a polar solvent to obtain a solution A;
2) dissolving a certain amount of trimesic acid ligand in a polar solvent to obtain a solution B;
3) slowly adding the solution A into the solution B under the condition of continuous stirring, adjusting the pH value of the system, standing, collecting precipitate, washing with a polar solvent, and drying to obtain a precursor;
4) and pyrolyzing the mixture under the protection of inert gas to obtain a precursor, thereby obtaining the magnetic cerium-based metal oxide adsorbent.
In a preferred embodiment, the polar solvent in step 1), step 2) and step 3) comprises ethanol and/or water; more preferably, the polar solvent in the step 1) and the step 2) is ethanol and water which are mixed according to the volume ratio of 1 (0.5-1.5); most preferably, the polar solvent in the steps 1) and 2) is ethanol and water mixed according to the volume ratio of 1: 1. The polar solvent can realize efficient dissolution of ferric salt and cerium salt and effective dispersion of trimesic acid, so that the cerium salt, the ferric salt and the ligand can be uniformly mixed by applying the polar solvent, and further the atomic-level dispersion of Fe and Ce in the subsequent ligand reaction can be realized.
In a preferred embodiment, in step 1), the cerium salt is cerium nitrate or a hydrate thereof, the iron salt is ferric nitrate or a hydrate thereof, and the organic acid is citric acid. Citric acid is combined on the surface of the precursor through the action of static electricity and hydrogen bonds in the reaction process of the formation of the precursor, the dispersibility of the precursor is effectively improved by adjusting the Zeta potential of the surface, and meanwhile, a large amount of hydroxyl functional groups can be generated by the decomposition of the citric acid through the subsequent pyrolysis reaction, so that the phosphate adsorption performance can be greatly improved.
In a preferred embodiment, the cerium salt in the solution A in the step 1) has a mass concentration of 1-25%, the iron salt in the solution A has a mass concentration of 1-25%, and the organic acid in the solution A has a mass concentration of 0.01-10%; more preferably, the mass concentration of the cerium salt in the solution A is 1-10%, the mass concentration of the iron salt in the solution A is 1-10%, and the mass concentration of the organic acid in the solution A is 0.02-2%; most preferably, the cerium salt has a mass concentration of 2% in the solution a, the iron salt has a mass concentration of 2% in the solution a, and the organic acid has a mass concentration of 0.1% in the solution a. The cerium component plays a decisive role in the adsorption capacity of the phosphate, the iron component can regulate and control the valence and the dispersity of the cerium component and provide magnetism for the material, and the organic acid can improve the dispersity and the surface hydroxyl functional group content of the adsorbent material. Based on the principle, on the premise of ensuring the magnetism of the material, the adsorption capacity of the material can be effectively improved by increasing the content of the cerium component within a certain range, and meanwhile, the addition amount of the organic acid is reduced as far as possible on the premise of ensuring the dispersibility of the material. Therefore, by setting the mass concentration range, both the adsorption performance and the adsorption efficiency of the material can be achieved.
In a preferred embodiment, the mass concentration of the trimesic acid ligand in the solution B in the step 2) is 0.01 to 10%; more preferably, the mass concentration of the trimesic acid ligand in the solution B is 0.2-5%; most preferably, the mass concentration of the trimesic acid ligand in the solution B is 0.8%. The trimesic acid is used for being matched with cerium salt and ferric salt to form an MOF precursor, and the dosage is within the range, so that the metal organic framework can be effectively constructed.
In a preferred embodiment, the volume ratio of the solution a to the solution B in the step 3) is 1: (1-10), more preferably, the volume ratio of the solution A to the solution B is 1 (1-4), and most preferably, the volume ratio of the solution A to the solution B is 1: 2.3. In order to achieve uniform mixing of cerium and iron salts with the ligand, the volume of the salt solution should be as small as possible compared to the volume of the ligand solution to prevent excessive aggregation during the precursor formation process.
In a preferred embodiment, the continuous stirring conditions in step 3) are: the stirring speed is 50-600rpm, and the stirring time is 1-6 h; the slow adding time is 1-2 h; and adjusting the pH of the system to 7-9. The slow addition is to slow down the reaction speed of cerium salt, iron salt and ligand, prevent the heterogeneous phenomenon caused by the violent reaction of MOF precursor, and adjust the pH value subsequently to regulate the Zeta potential of the reactant, thereby collecting the precursor rapidly. Therefore, there is no particular requirement for the reactant for adjusting the pH of the system as long as the aforementioned object can be achieved, and it is preferable to adjust the pH with aqueous ammonia.
In a preferred embodiment, the polar solvent washing in step 3) is not limited in any way, and can be performed in any way known to those skilled in the art, and the washing is performed to remove impurities on the surface of the precipitate for subsequent operations; preferably, the polar solvent is ethanol and water mixed according to the volume ratio of 1:1, and the precipitate is washed for 2-4 times.
In a preferred embodiment, the drying device and conditions in step 3) are not limited, and any device or conditions may be used as will be appreciated by those skilled in the art, and the drying function is to fully dry the precursor and then perform pyrolysis; preferably, the drying condition is 60-80 deg.C for 1-2h
In a preferred embodiment, the pyrolysis conditions in step 4) are: the calcination temperature is 400-; more preferably, the calcination temperature is 500 ℃, the calcination time is 2h, and the temperature rise rate is 5 ℃/min.
The invention also provides the magnetic cerium-based metal oxide adsorbent prepared by any one of the methods, wherein the magnetic cerium-based metal oxide adsorbent is in a rod shape and is aggregated into a bundle shape.
The invention also provides an application of the magnetic cerium-based metal oxide adsorbent prepared by any one of the methods in removing water pollutants, which specifically comprises the following steps:
the magnetic cerium-based metal oxide adsorbent is put into a phosphate-containing water body, and is stirred for reaction, so that the removal of water body pollutants can be completed; after the reaction is finished, the magnetic cerium-based metal oxide adsorbent can be separated and recovered from the water body by using a magnet, and then rinsed to be neutral by using alkali liquor and deionized water, so that the magnetic cerium-based metal oxide adsorbent can be recycled.
In a preferred embodiment, the mass ratio of the magnetic cerium-based metal oxide adsorbent to the phosphate is (2-4): 1, the adsorption capacity of the adsorbent to phosphate can reach 240mg of Pg -1 (ii) a The adsorption capacity of the phosphate based on cerium element is up to 468mg Pg -1 。
In a preferred embodiment, the stirring reaction speed is 100-200rpm, and the reaction time is 2-4 h.
Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art; all raw materials are commercial products, and are analytically pure unless otherwise specified.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1
Preparing a magnetic iron-cerium-based metal oxide adsorbent:
adding Ce (NO) 3 ) 3 ·6H 2 O(5mmol)、Fe(NO 3 ) 3 ·9H 2 Mixing O (5mmol) and citric acid (1mmol) dissolved in 150mL ethanol/water (volume ratio v/v-1/1) to give solution a; h is to be 3 BTC (15mmol) was dissolved in 350mL of a mixture of ethanol/water (volume ratio v/v-1/1) to form solution B; slowly pouring the solution A into the solution B under continuous stirring (the stirring speed is 100rpm, and the stirring and pouring time is 2 hours); after stirring and mixing, the mixture was neutralized to pH 7 with 28 wt.% aqueous ammonia, and finally the precipitate was collected by centrifugation, washed several times with a mixture of ethanol/water (volume ratio v/v. 1/1), and then dried in a drying oven at 60 ℃ to obtain a precursor. N in tube furnace of the above precursor 2 Calcining at 500 deg.C for 2 hr under atmosphere, and heating at 5 deg.C for min -1 . Naturally cooling to room temperature to obtain a magnetic adsorbent FeFe @ mC (CA) 1 ) The material morphology is shown in fig. 1, and the magnetic test data is shown in fig. 2. As can be seen from FIG. 1, the adsorbent has a uniform rod-like structure, which is helpful for enhancing the mass transfer process between the adsorbent and the substance to be adsorbed, and as can be seen from FIG. 2, the saturation magnetization of the adsorbent reaches 7.1emu g -1 The rapid separation process of the adsorbent can be realized by the permanent magnet.
Example 2
Preparing a magnetic iron-cerium-based metal oxide adsorbent:
adding Ce (NO) 3 ) 3 ·6H 2 O(15mmol)、Fe(NO 3 ) 3 ·9H 2 Mixing O (5mmol) and citric acid (1mmol) dissolved in 150mL ethanol/water (volume ratio v/v-1/1) to give solution a;
the rest steps and the using amount are completely the same as the example 1, and the magnetic adsorbent Fe is obtained 1 Ce 3 @mC(CA 1 )。
Comparative example 1
Preparation of cerium-based metal oxide adsorbent:
adding Ce (NO) 3 ) 3 ·6H 2 Mixing O (5mmol) and citric acid (1mmol) dissolved in 150mL ethanol/water (volume ratio v/v-1/1) to give solution a;
the remaining steps and amounts were exactly the same as in example 1, obtaining the adsorbent Ce @ mC (CA) 1 )。
Comparative example 2
Preparing a magnetic iron-cerium-based metal oxide adsorbent:
adding Ce (NO) 3 ) 3 ·6H 2 O(5mmol)、Fe(NO 3 ) 3 ·9H 2 Mixing O (5mmol) dissolved in 150mL ethanol/water (volume ratio v/v: 1/1) to give solution a;
the remaining steps and amounts were exactly the same as in example 1 to obtain the magnetic adsorbent FeCe @ mC.
Comparative example 3
Preparing an iron-based metal oxide adsorbent:
mixing Fe (NO) 3 ) 3 ·9H 2 Mixing O (5mmol) dissolved in 150mL ethanol/water (volume ratio v/v: 1/1) to give solution a;
the rest steps and the amount are completely the same as the example 1, and the magnetic adsorbent Fe @ mC is obtained.
Comparative example 4
Preparation of cerium-based metal oxide adsorbent:
ce (NO) 3 ) 3 ·6H 2 Mixing O (5mmol) dissolved in 150mL ethanol/water (volume ratio v/v: 1/1) to give solution a;
the remaining steps and amounts were exactly the same as in example 1, yielding adsorbent Ce @ mC.
Effect example 1
The magnetic adsorbent FeFe @ mC (CA) prepared in example 1-2 1 ) And Fe 1 Ce 3 @mC(CA 1 ) Comparative examples 1 to 4, the adsorbents Ce @ mC (CA) prepared in the examples 1 ) FeFe @ mC, Fe @ mC and Ce @ mC, and the effect of removing the water pollutants is verified, and the specific steps are as follows:
to a phosphate concentration of 5mg L -1 Adding the adsorbent into the wastewater (pH 6) in an amount of 0.02g L -1 Controlling the rotation speed of a stirring paddle to be 150rpm, carrying out adsorption reaction for 3h, taking supernate at proper time, filtering the supernate with a 0.45-micron microporous filter membrane, measuring the phosphate concentration of the filtrate by using an ammonium molybdate spectrophotometry (GB11893-89), and drawing an adsorbent adsorption performance curve.
The results are shown in FIG. 3, from which Fe is seen 1 Ce 3 @mC(CA 1 ) Having the highest adsorption capacity, FeFe @ mC (CA) 1 ) Adsorption Capacity and Ce @ mC (CA) 1 ) The three adsorbents are obviously higher than the adsorbent prepared without adding citric acid, and meanwhile, the adsorbent containing Fe and Ce obviously improves the phosphate adsorption capacity of the Ce-based adsorbent.
Effect example 2
The magnetic adsorbent FeFe @ mC (CA) prepared in example 1-2 1 ) And Fe 1 Ce 3 @mC(CA 1 ) Compared with the adsorbent in the prior art, the adsorbent has the advantage of higher adsorption performance. The results are shown in table 1:
TABLE 1
Wherein, the prior art respectively is:
[1]Shan Sujie,Zhang Tao,Wang Wei,et al.Magnetite/hydrated cer ium(III)carbonate for efficient phosphate elimination from aqueous solutions and the mechanistic investigation[J].Chem Eng J,2021,425:128894.
[2]Wu Baile,Lo Irene M.C.Surface Functional Group Engineering of CeO2 Particles for Enhanced Phosphate Adsorption[J].Envi ron Sci Technol,2020,54(7):4601-4608.
[3]Liu Xiaohuan,He Xia,Zhang Jiantao,et al.Cerium oxide nanoparticle functionalized lignin as a nano-biosorbent for efficient phosphate removal[J].RSC Adv,2020,10(3):1249-1260.
[4]Feng Yanfang,Lu Haiying,Liu Yang,et al.Nano-cerium oxide functionalized biochar for phosphate retention:preparation,optimizationand rice paddy application[J].Chemosphere,2017,185:816-825.
[5]Wang Li,Wang Jingyi,He Chi,et al.Development of rare earth element doped magnetic biochars with enhanced phosphate adsorption performance[J].Colloid Surface A,2019,561:236-243.
[6]Yang Wenlan,Shi Xinxing,Dong Hao,et al.Fabrication of a reusable polymer-based cerium hydroxide nanocomposite with high stability for preferable phosphate removal[J].Chem Eng J,2021,405:126649.
as can be seen from table 1, the magnetic adsorbent prepared in the examples of the present application is significantly superior to the prior art in terms of the adsorption capacity of phosphate in wastewater, both based on the adsorption capacity of the adsorbent and based on the adsorption capacity of cerium.
Effect example 3
The magnetic adsorbent FeFe @ mC (CA) prepared in example 1 1 ) The pH adaptability test includes the following steps:
adjusting the phosphate concentration to 5mg L -1 The pH range of the wastewater is 3-11, and a magnetic adsorbent FeFe @ mC (CA) is respectively added 1 ) The adding amount is 0.02g L -1 Controlling the rotating speed of the stirring paddle to be 150rpm, carrying out adsorption reaction for 3h, and adsorbing the adsorbent at the bottom of the reactor for 10min by using a permanent magnet to separate the adsorbent from the wastewater.
The adsorption results under different pH are shown in FIG. 4, and it can be seen from the figure that the adsorption capacity of the prepared adsorbent is 175mg Pg in the pH range of 3-10 in water -1 From the above, it is known that the adsorbent has excellent pH adaptability, and can maintain high adsorption performance in water bodies of different pH values.
Effect example 4
The magnetic adsorbent FeFe @ mC (CA) prepared in example 1 1 ) The method for verifying the anti-interference ions comprises the following specific steps:
adjusting the phosphate concentration to 5mg L -1 The wastewater of (2) contains coexisting ions (0.01M, 0.05M, 0.1M NaCL, Na) of different concentrations 2 SO 4 、Na 2 CO 3 ) Adding a magnetic adsorbent FeFe @ mC (CA) respectively 1 ) The adding amount is 0.02g L -1 Controlling the rotating speed of the stirring paddle to be 150rpm, carrying out adsorption reaction for 3h, and adsorbing the adsorbent at the bottom of the reactor for 10min by using a permanent magnet to separate the adsorbent from the wastewater.
The adsorption results under the influence of different coexisting ions are shown in FIG. 5, from which it can be seen that Cl-and SO having high ionic strengths 4 2- The ion has small influence on the adsorption performance of the adsorbent, and simultaneously CO 3 2- The effect on the adsorption capacity is mainly due to pH and surface precipitation, which can be mitigated by pH adjustment in applications.
Effect example 5
The magnetic adsorbent FeFe @ mC (CA) prepared in example 1 1 ) A stability test validation experiment was performed to determine,the method comprises the following specific steps:
adsorption: adsorbing agent FeFe @ mC (CA) 1 ) The concentration of the added phosphate is 5mg L -1 The amount of the wastewater (pH 6) added was 0.02g L -1 The rotating speed of the stirring paddle is controlled to be 150 rpm.
Desorption: after adsorption reaction for 3h, the permanent magnet is used for adsorbing at the bottom of the reactor for 10min to separate the adsorbent from the wastewater.
And (3) activation: after desorption, the solution is rinsed and regenerated by NaOH solution containing 0.1M, and then is rinsed by deionized water until the effluent is neutral, thus completing the magnetic adsorbent FeFe @ mC (CA) 1 ) And (4) recovering and regenerating.
The regenerated adsorbent can be repeatedly used for adsorbing and removing phosphate in the wastewater. The same magnetic adsorbent FeFe @ mC (CA) was used for 1-time use of the adsorption-desorption-activation 1 ) After 10 times of cyclic utilization, the adsorption capacity is more than 80% of the initial adsorption capacity, and after 40 times of cyclic utilization, the adsorption capacity is more than 55% of the initial adsorption capacity. The number of cycles was compared with the adsorption/desorption capacity of the adsorbent, and the specific results are shown in fig. 6.
The foregoing descriptions of specific exemplary embodiments of the present invention have been presented for purposes of illustration and description. It is not intended to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain certain principles of the invention and its practical application to enable one skilled in the art to make and use various exemplary embodiments of the invention and various alternatives and modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims and their equivalents.
Claims (10)
1. The preparation method of the magnetic cerium-based metal oxide adsorbent is characterized by comprising the following steps of:
1) weighing a certain amount of cerium salt, ferric salt and organic acid, and dissolving in a polar solvent to obtain a solution A;
2) dissolving a certain amount of trimesic acid ligand in a polar solvent to obtain a solution B;
3) slowly adding the solution A into the solution B under the condition of continuous stirring, adjusting the pH value of the system, standing, collecting precipitate, washing with a polar solvent, and drying to obtain a precursor;
4) and pyrolyzing the mixture under the protection of inert gas to obtain a precursor, thus obtaining the magnetic cerium-based metal oxide adsorbent.
2. The method of preparing a magnetic cerium-based metal oxide adsorbent according to claim 1, wherein the polar solvent in step 1), step 2) and step 3) comprises ethanol and/or water.
3. The method for preparing a magnetic cerium-based metal oxide adsorbent according to claim 1, wherein the cerium salt in step 1) is cerium nitrate or a hydrate thereof, the iron salt is ferric nitrate or a hydrate thereof, and the organic acid is citric acid; in the step 1), the mass concentration of the cerium salt in the solution A is 1-25%, the mass concentration of the iron salt in the solution A is 1-25%, and the mass concentration of the organic acid in the solution A is 0.01-10%.
4. The method for preparing a magnetic cerium-based metal oxide adsorbent according to claim 1, wherein the mass concentration of the trimesic acid ligand in the solution B in the step 2) is 0.01 to 10%.
5. The method for preparing a magnetic cerium-based metal oxide adsorbent according to claim 1, wherein the volume ratio of the solution a to the solution B in the step 3) is 1: (1-10).
6. The method for preparing a magnetic cerium-based metal oxide adsorbent according to claim 1, wherein the continuous stirring conditions in step 3) are: the stirring speed is 50-600rpm, and the stirring time is 1-6 h; the slow adding time is 1-2 h; and adjusting the pH of the system to 7-9.
7. The method for preparing a magnetic cerium-based metal oxide adsorbent according to claim 1, wherein the pyrolysis conditions in step 4) are: the calcination temperature is 400-.
8. A magnetic cerium-based metal oxide adsorbent, comprising a cerium oxide powder prepared by the method of any one of claims 1 to 7.
9. The application of removing water body pollutants is characterized in that the magnetic cerium-based metal oxide adsorbent prepared by the preparation method of any one of claims 1 to 7 or the magnetic cerium-based metal oxide adsorbent of claim 8 is put into a phosphate-containing water body and stirred for reaction, so that the water body pollutants can be removed; after the reaction is finished, the magnetic cerium-based metal oxide adsorbent can be separated and recovered from the water body by using a magnet, and then rinsed to be neutral by using alkali liquor and deionized water, so that the magnetic cerium-based metal oxide adsorbent can be recycled.
10. The use of claim 9 for removing contaminants from a body of water, wherein the magnetic cerium-based metal oxide adsorbent is present in a mass ratio to phosphate of (2-4): 1, the adsorption capacity of the adsorbent to phosphate can reach 240mg of Pg -1 The adsorption capacity of the phosphate based on cerium can reach 468mg Pg -1 。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210529328.7A CN115041127B (en) | 2022-05-16 | 2022-05-16 | Magnetic cerium-based metal oxide adsorbent and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210529328.7A CN115041127B (en) | 2022-05-16 | 2022-05-16 | Magnetic cerium-based metal oxide adsorbent and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115041127A true CN115041127A (en) | 2022-09-13 |
| CN115041127B CN115041127B (en) | 2023-06-09 |
Family
ID=83158477
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210529328.7A Active CN115041127B (en) | 2022-05-16 | 2022-05-16 | Magnetic cerium-based metal oxide adsorbent and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115041127B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116832793A (en) * | 2023-06-20 | 2023-10-03 | 昆明理工大学 | Industrial wastewater adsorbent and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109569552A (en) * | 2018-12-13 | 2019-04-05 | 北京林业大学 | A kind of magnetic/non magnetic lanthanum carbonate sodium dephosphorization adsorbent and its synthetic method |
| CN110292912A (en) * | 2019-07-19 | 2019-10-01 | 长安大学 | Tufted cerium base dephosphorization adsorbent derived from a kind of MOF and preparation method thereof |
| CN110694583A (en) * | 2019-10-29 | 2020-01-17 | 哈尔滨工业大学 | Preparation method and application of magnetic recyclable lanthanum oxycarbonate phosphorus removal adsorbent |
| CN111203190A (en) * | 2020-02-23 | 2020-05-29 | 长安大学 | Preparation method of high-unsaturation coordination system trivalent cerium phosphorus removal adsorbent |
| CN113019305A (en) * | 2021-03-03 | 2021-06-25 | 重庆三峡学院 | Preparation and application of porous lanthanum carbonate hydroxide phosphate adsorbent |
-
2022
- 2022-05-16 CN CN202210529328.7A patent/CN115041127B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109569552A (en) * | 2018-12-13 | 2019-04-05 | 北京林业大学 | A kind of magnetic/non magnetic lanthanum carbonate sodium dephosphorization adsorbent and its synthetic method |
| CN110292912A (en) * | 2019-07-19 | 2019-10-01 | 长安大学 | Tufted cerium base dephosphorization adsorbent derived from a kind of MOF and preparation method thereof |
| CN110694583A (en) * | 2019-10-29 | 2020-01-17 | 哈尔滨工业大学 | Preparation method and application of magnetic recyclable lanthanum oxycarbonate phosphorus removal adsorbent |
| CN111203190A (en) * | 2020-02-23 | 2020-05-29 | 长安大学 | Preparation method of high-unsaturation coordination system trivalent cerium phosphorus removal adsorbent |
| CN113019305A (en) * | 2021-03-03 | 2021-06-25 | 重庆三峡学院 | Preparation and application of porous lanthanum carbonate hydroxide phosphate adsorbent |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116832793A (en) * | 2023-06-20 | 2023-10-03 | 昆明理工大学 | Industrial wastewater adsorbent and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115041127B (en) | 2023-06-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | Taming wettability of lithium ion sieve via different TiO2 precursors for effective Li recovery from aqueous lithium resources | |
| Shi et al. | Synthesis and properties of Li1. 6Mn1. 6O4 and its adsorption application | |
| CN109317087B (en) | Doped lithium titanate adsorbent and preparation method thereof | |
| Wei et al. | Efficient removal of uranium (vi) from simulated seawater using amidoximated polyacrylonitrile/FeOOH composites | |
| CN108543514B (en) | A kind of separation method of aluminum salt adsorbent, preparation method and Lithium from Salt Lake Brine | |
| CN113042003B (en) | Zirconium-based metal-organic framework material and preparation method and application thereof | |
| CN108704610B (en) | Magnetic carbon modified magnesium-iron hydrotalcite composite material and preparation method and application thereof | |
| CN110368894B (en) | Efficient fluorine removal agent for removing fluorine ions in wastewater and preparation method thereof | |
| CN112607785B (en) | MnFe 2 O 4 C nano composite microsphere and preparation method thereof | |
| CN109078602B (en) | Magnetic microporous lithium adsorbent and preparation method and application thereof | |
| CN103599749A (en) | Magnetic cobalt loaded ordered mesoporous carbon, its preparation method and application | |
| CN103736445A (en) | Modified montmorillonite and preparation method as well as application thereof in water resource purification | |
| CN110205502A (en) | A kind of method that use adsorbent containing aluminium removes fluorine in lepidolite ore neutrality leachate | |
| CN115041127B (en) | Magnetic cerium-based metal oxide adsorbent and preparation method and application thereof | |
| Wang et al. | Synthesis of zirconium-coated lithium ion sieve with enhanced cycle stability | |
| CN113019331A (en) | Rare earth element doped defect UiO-66 material and preparation method and application thereof | |
| CN110180489B (en) | Sulfur-doped lithium-rich manganese lithium adsorbent and preparation method and application thereof | |
| CN108201876B (en) | Method for deeply adsorbing zinc ions by using NaP molecular sieve | |
| WO2023216729A1 (en) | Method for recovering phosphite ions in wastewater | |
| CN112619591A (en) | Preparation method and application of magnetic composite adsorption material | |
| Xie et al. | A green synthesis strategy toward calcined calcium-aluminum layered double hydroxide with sludge as aluminum source for efficient removal of phosphate from water | |
| CN114457461B (en) | Preparation method and application of magnetic lanthanum-aluminum composite oxide porous nanofiber | |
| CN114367267B (en) | Mesoporous composite material and preparation method and application thereof | |
| CN107935018B (en) | Preparation method of two-dimensional transition metal nano-sheet with structure memory | |
| CN113198414B (en) | Hydrated chromium oxide adsorbent, preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |