CN115521473A - Foliated ZIF material adsorbent for rapidly removing phosphate and preparation method thereof - Google Patents
Foliated ZIF material adsorbent for rapidly removing phosphate and preparation method thereof Download PDFInfo
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- CN115521473A CN115521473A CN202211209664.XA CN202211209664A CN115521473A CN 115521473 A CN115521473 A CN 115521473A CN 202211209664 A CN202211209664 A CN 202211209664A CN 115521473 A CN115521473 A CN 115521473A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
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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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/105—Phosphorus compounds
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Abstract
The invention discloses a foliated ZIF material adsorbent for quickly removing phosphate and a preparation method thereof, belonging to the technical field of sewage treatment. The method specifically comprises the following steps: (1) Zinc nitrate hexahydrate (Zn (NO) 3 ) 2 6H 2O) in ultrapure water to obtain a precursor Zn 2+ A solution; (2) Dissolving 2-methylimidazole in ultrapure water to obtain a precursor 2-methylimidazole solution; (3) Dropwise adding the solution obtained in the step (1) into the solution obtained in the step (2), continuously reacting for a plurality of hours under the stirring action of a magnetic stirrer, washing with absolute ethyl alcohol, and then washingCentrifuging and drying the precipitate to obtain the foliated ZIF material adsorbent. The preparation method of the foliated ZIF material is simple, the prepared adsorbent has good adsorption capacity and excellent selectivity on phosphate, the problems of poor anti-interference performance and low adsorption capacity of the existing phosphate adsorbent in actual water bodies can be solved, and the preparation method has wide practical application prospects.
Description
Technical Field
The invention discloses a foliated ZIF material adsorbent for quickly removing phosphate and a preparation method thereof, belonging to the technical field of sewage treatment.
Background
Phosphorus (P) is a mineral nutrient element, has important functional effects on human metabolism, plant growth, and the like, and is widely used in industry, agriculture, and life. However, when excessive phosphorus enters the water body through mining, industrial and agricultural activities, sewage discharge and other ways, water quality deterioration and death of a large number of organisms (such as fish) are caused, and finally, the ecological environment is harmed.
At present, sewage treatment plants mainly remove phosphorus by biological and chemical methods, but the total phosphorus in effluent after the phosphorus removal by the biological method is still over 0.5mg/L and cannot reach the discharge standard, and chemical phosphorus removal can generate a large amount of sludge, so that an efficient and green phosphate removal method needs to be found.
Adsorption methods have been used in large scale for phosphate removal due to their recyclability, high flexibility, and high efficiency. However, in actual water treatment, when other anions (SO) exist in the solution 4 2- 、CO 3 2- Etc.), the adsorbent cannot perform specific adsorption on the phosphate in the water, and the actual adsorption capacity of the adsorbent on the phosphate is reduced.
Zeolite imidazolate framework materials (ZIFs) are a class of metal organic materials with high porosity and special chemical stability, and are drawing attention in the fields of gas separation, catalysis, adsorption of heavy metals and organic pollutants and the like. However, the reported 3D ZIF-8 material has too large three-dimensional size and hydrophobic property, so that the adsorption speed of the material on phosphate is slow, and the material is difficult to be applied to actual sewage dephosphorization.
Disclosure of Invention
The invention aims to solve the technical problem of providing a foliated ZIF material adsorbent for quickly removing phosphate, wherein the adsorption rate of the adsorbent to phosphate in water is far higher than that of a reported three-dimensional ZIF material, and the problem that the conventional phosphate adsorbent is difficult to be practically applied due to low adsorption rate can be solved.
The invention provides a foliated ZIF material adsorbent for quickly removing phosphate and a preparation method thereof, and the preparation method comprises the following steps: (1) Zinc nitrate hexahydrate (Zn (NO) 3 ) 2 ·6H 2 O) is dissolved in water to obtain a precursor Zn 2+ A solution; (2) Dissolving 2-methylimidazole in water to obtain a precursor 2-methylimidazole solution; (3) Dropwise adding the solution obtained in the step (1) into the solution obtained in the step (2), stirring for reaction, cleaning after the reaction is finished, centrifuging, and drying the precipitate to obtain the foliated ZIF material adsorbent.
In one embodiment of the present invention, the fast speed means that the time required for treating the phosphate wastewater to achieve a phosphate removal rate of 90% is less than 10 minutes.
In one embodiment of the present invention, the mass ratio of the zinc nitrate hexahydrate to the water is 3 to 5.
In one embodiment of the present invention, the mass ratio of the 2-methylimidazole to water is 1 to 3.
In one embodiment of the present invention, the precursor Zn 2+ The volume ratio of the solution to the precursor 2-methylimidazole solution is 1:1.
In one embodiment of the present invention, the stirring reaction time in step (3) is 3 to 5 hours. In one embodiment of the present invention, the stirring in step (3) comprises magnetic stirring.
In one embodiment of the invention, the rate of centrifugation is 6000 to 10000rpm.
In one embodiment of the present invention, the time for the centrifugation is 5 to 10min.
The invention provides a foliated ZIF material adsorbent for quickly removing phosphate, which is prepared by the method.
The second purpose of the invention is to apply the foliated ZIF material adsorbent for rapidly removing phosphate to the field of sewage treatment.
Has the advantages that:
the preparation method of the inventionThe prepared foliated ZIF material adsorbent has rich adsorption active sites, excellent adsorption performance and higher adsorption capacity (75.18 +/-2.65 mg g) -1 ) And faster adsorption kinetic rate (0.0376 g mg -1 min -1 )。
In the presence of four kinds of anti-interference ions (Cl) - ,NO 3 - ,CO 3 2- And SO 4 2- ) Under the coexistence condition, the selective removal rate of the prepared ultrathin leaf-shaped ZIF material adsorbent on phosphate is as high as 98.8 +/-0.4 percent, and the adsorbent has stronger anti-interference performance; the removal rate of the foliated ZIF material adsorbent to 90 percent phosphate (the total phosphorus concentration in the first-grade A discharge standard of a town sewage treatment plant is 0.5mg L) -1 ) The required time is only about 10 minutes; compared with a plurality of reported adsorbents, the preparation method is simple, the needed raw materials are low in price and good in regeneration performance, and the method has a wide practical application prospect.
Drawings
FIG. 1 is an SEM image of a lobed ZIF material.
FIG. 2 is an XRD pattern of the foliated ZIF material.
FIG. 3 is a phosphate adsorption isotherm for foliated and three-dimensional ZIF materials.
FIG. 4 is a graph of P concentration versus time for both foliated and three-dimensional ZIF materials.
FIG. 5 is a graph of the effect of different coexisting anions on phosphate adsorption by a foliate ZIF material.
Detailed Description
The invention is further illustrated by the following specific examples, which do not limit the scope of the invention.
Zn (NO) used in examples of the present invention 3 ) 2 ·6H 2 O,Na 2 CO 3 ,Na 2 SO 4 ,NaNO 3 ,NaCl,(NH 4 ) 6 Mo 7 O 24 ·4H 2 O, 2-methylimidazole and other medicaments are purchased from national chemical reagent, inc. and are analytically pure. All solutions used in the experiment were prepared with deionized water (SYS-I laboratory ultra pure water machine).
Example 1:
(1) 3.25g of zinc nitrate hexahydrate (Zn (NO) 3 ) 2 ·6H 2 O) is dissolved in 100mL of ultrapure water to obtain a precursor Zn solution;
(2) Dissolving 1.475g of 2-methylimidazole in 100mL of ultrapure water to obtain a precursor 2-methylimidazole solution;
(3) Dropwise adding the solution obtained in the step (1) into the solution obtained in the step (2), continuously reacting for 4h under the stirring action of a magnetic stirrer, washing with absolute ethyl alcohol, centrifuging (8000 rpm, 6 min), and drying the precipitate at 60 ℃ to obtain the foliated ZIF material adsorbent (SEM is shown in figure 1, and XRD is shown in figure 2).
Example 2:
0.67g of zinc nitrate hexahydrate (Zn (NO) 3 ) 2 ·6H 2 O) and 0.167g of 2-methylimidazole in 80mL of methanol, continuously reacting for several hours under the action of a magnetic stirrer, washing with methanol, centrifuging, and drying precipitates in a vacuum drying oven to obtain the three-dimensional ZIF material adsorbent, wherein an XRD (X-ray diffraction) spectrum is shown in figure 2.
Wherein, the magnetic stirring time is 24h, the centrifugation speed and the centrifugation time are 8000rpm and 6min respectively, and the drying temperature is 25 ℃.
Example 3:
the initial concentration of the preparation is 200mg L -1 The phosphate solutions of (1) were added to the adsorbents prepared in examples 1 and 2, respectively, in an amount of 0.2g L -1 The mixture was stirred at a speed of 170rpm for 100min at a temperature of 25 ℃.
The results obtained are shown in FIG. 3: the phosphate adsorption capacity of the foliated and three-dimensional ZIF material adsorbents is 75.18 +/-2.65 mg g -1 And 54.82. + -. 4.28mg g -1 。
Example 4:
the following adsorption experiment was carried out using the leaf-shaped ZIF material adsorbent prepared in example 1
A phosphate solution having an initial concentration of 5mg L-1 was prepared, the adsorbent prepared in example 1 was added in an amount of 0.2g L-1, and the mixture was stirred at a temperature of 25 ℃ and a rotation speed of 170rpm for 100min.
The obtained results are shown in the figure4, and (2) is as follows: the removal rate of phosphate of the foliated ZIF material adsorbent reaches 90 percent (the total phosphorus concentration in the first-class A discharge standard of a municipal wastewater treatment plant is 0.5mg L) -1 ) The required time is only about 10 minutes, which is far less than 80 minutes of the three-dimensional ZIF material; the pseudo-second order kinetic model fitting result further shows that the adsorption rate of the foliated ZIF material adsorbent to phosphate is 0.0376g mg -1 min -1 Also much higher than three-dimensional ZIF material (0.0050 g mg -1 min -1 )。
Example 5:
the following adsorption experiment was performed using the foliated ZIF material adsorbent prepared in example 1.
The initial concentration is set to be 1mg L -1 1, 10, 100mg L of the phosphate solution of (1) -1 Cl of - ，NO 3 - ，CO 3 2- ，SO 4 2- And mixtures thereof, to the adsorbent prepared in example 1 in an amount of 0.2g L -1 The mixture was stirred at a speed of 170rpm for 100min at a temperature of 25 ℃.
The results are shown in FIG. 5: when the concentration of single interfering ion is 1, 10, 100mg L -1 In the process, the removal rate of phosphate in the solution is almost 100 percent; when the concentration of mixed ions is up to 100mg L -1 In this case, the adsorbent can still effectively remove 98.8 + -0.4% of phosphate.
Claims (10)
1. A foliated ZIF material adsorbent for rapidly removing phosphate and a preparation method thereof are characterized by comprising the following steps: (1) Dissolving zinc nitrate hexahydrate in water to obtain a precursor Zn 2+ A solution; (2) Dissolving 2-methylimidazole in water to obtain a precursor 2-methylimidazole solution; (3) The precursor Zn in the step (1) is added 2+ Dropwise adding the solution into the precursor 2-methylimidazole solution obtained in the step (2), stirring for reaction, cleaning after the reaction is finished, centrifuging, and drying the precipitate to obtain the foliated ZIF material adsorbent.
2. The method according to claim 1, wherein the mass ratio of the zinc nitrate hexahydrate to the water is 3 to 5.
3. The method according to claim 1, wherein the mass ratio of the 2-methylimidazole to the water is 1 to 3.
4. The method according to claim 1, wherein the precursor Zn 2+ The volume ratio of the solution to the precursor 2-methylimidazole solution is 1:1.
5. The method of claim 1, wherein the reaction time in step (3) is 3 to 5 hours.
6. The method of claim 1, wherein said stirring of step (3) comprises magnetic stirring.
7. The method of claim 1, wherein the centrifugation is performed at a rate of 6000 to 10000rpm.
8. The method of claim 1, wherein the centrifugation time is 5 to 10min.
9. An adsorbent of a rapid phosphate removal foliated ZIF material prepared by the method of any of claims 1 to 8.
10. The use of the foliated ZIF material adsorbent for rapid phosphate removal according to claim 9 in the field of wastewater treatment.
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| CN202211209664.XA CN115521473A (en) | 2022-09-30 | 2022-09-30 | Foliated ZIF material adsorbent for rapidly removing phosphate and preparation method thereof |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20210016245A1 (en) * | 2018-03-14 | 2021-01-21 | Deepak Pahwa | METHOD FOR IN-SITU SYNTHESIS OF METAL ORGANIC FRAMEWORKS (MOFs), COVALENT ORGANIC FRAMEWORKS (COFs) AND ZEOLITE IMIDAZOLATE FRAMEWORKS (ZIFs), AND APPLICATIONS THEREOF |
| CN113717398A (en) * | 2021-09-28 | 2021-11-30 | 南京工程学院 | Zeolite-like imidazole ester framework material and preparation method and application thereof |
-
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- 2022-09-30 CN CN202211209664.XA patent/CN115521473A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20210016245A1 (en) * | 2018-03-14 | 2021-01-21 | Deepak Pahwa | METHOD FOR IN-SITU SYNTHESIS OF METAL ORGANIC FRAMEWORKS (MOFs), COVALENT ORGANIC FRAMEWORKS (COFs) AND ZEOLITE IMIDAZOLATE FRAMEWORKS (ZIFs), AND APPLICATIONS THEREOF |
| CN113717398A (en) * | 2021-09-28 | 2021-11-30 | 南京工程学院 | Zeolite-like imidazole ester framework material and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| CHOU HUANG等: "\"Two-dimensional hydrophilic ZIF-L as a highly-selective adsorbent for rapid phosphate removal from wastewater\"", 《SCIENCE OF THE TOTAL ENVIRONMENT》 * |
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