CN111167420A - Polyurethane foam with heavy metal adsorption function and preparation method thereof - Google Patents
Polyurethane foam with heavy metal adsorption function and preparation method thereof Download PDFInfo
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- CN111167420A CN111167420A CN201811356156.8A CN201811356156A CN111167420A CN 111167420 A CN111167420 A CN 111167420A CN 201811356156 A CN201811356156 A CN 201811356156A CN 111167420 A CN111167420 A CN 111167420A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/262—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
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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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—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 form
- B01J20/28042—Shaped bodies; Monolithic structures
- B01J20/28045—Honeycomb or cellular structures; Solid foams or sponges
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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
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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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
- C02F2101/20—Heavy metals or heavy metal compounds
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- Chemical Kinetics & Catalysis (AREA)
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- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to polyurethane foam with a heavy metal adsorption function and a preparation method thereof. Polyurethane foam is used as a base material, firstly, an imidazole ester metal-organic framework material (ZIF-8) is prepared in a water phase, and then the ZIF-8 is attached to the polyurethane foam through physical adsorption. And secondly, plating a thin polydopamine protective film on the surface of the polyurethane foam to obtain the polyurethane foam with the heavy metal adsorption function. The operation method is simple and quick, the preparation conditions are mild and environment-friendly, the requirements on equipment are low, the cost is low, and the method is suitable for industrial production.
Description
Technical Field
The invention belongs to the field of porous foam materials, and particularly relates to polyurethane foam with a heavy metal adsorption function and a preparation method thereof.
Background
Metal-Organic Frameworks (MOFs), which are Organic-inorganic hybrid crystal materials formed by self-assembly of Metal ions and Organic ligands. By selecting specific organic ligands and metal ions, a wide variety of MOFs materials can be obtained. The MOFs material has very high specific surface area and very high porosity, different crystal configurations, void sizes, pore structures and the like endow the MOFs material with different characteristics, and the MOFs material can form a topological structure, so that the MOFs material has great potential application value in many fields.
Among many MOFs, imidazole ester metal-organic framework materials (Zeolite Imidazolate frameworks), abbreviated as ZIFs, have a zeolite-like structure and show good stability in water and organic solvents. ZIFs are MOFs materials with zeolite-like framework structures generated by self-assembly in water or organic solvents by taking Zn or Co as a metal source and imidazole and derivatives thereof as organic ligands. Because the structure of the ZIFs material is similar to that of zeolite, the stability of the ZIFs material is good, and meanwhile, the function of the ZIFs material is adjustable as a part of the material composition, so that the ZIFs material is widely researched in the fields of gas separation, molecular probes, catalytic oxidation and the like.
Theoretically, ZIFs materials can also be used in ion adsorption. The current research on applying ZIFs materials to water body adsorption is less, and one reason is that no suitable adsorption carrier exists. ZIFs materials are generally present in powder form, and their dispersibility can reduce their utility and reproducibility if applied directly to ion adsorption in the aqueous phase. The polyurethane foam has high porosity, small apparent density, rich pore channel structure and strong toughness, and meets the general requirements of adsorption materials.
The polyurethane foam is used as a substrate, the surface of a framework of the polyurethane foam is covered with a ZIF-8 material, the ZIF-8 material is used as an effective adsorbent, and the polydopamine is used as a protective layer on the outermost layer. The polyurethane foam provides a good carrier for the adsorption process, and meanwhile, the adsorption efficiency of the ZIF-8 to ions can be kept. The modified foam shows excellent adsorption capacity in an adsorption experiment, so that the polyurethane foam with the heavy metal adsorption function is obtained.
Disclosure of Invention
Through research and experiments, the polyurethane foam with the heavy metal adsorption function is obtained by a simple and quick method. Firstly, preparing an imidazolate metal-organic framework material (ZIF-8) in a water phase, and then attaching the ZIF-8 to polyurethane foam through physical adsorption. And secondly, plating a thin polydopamine protective film on the surface of the polyurethane foam. And drying to obtain the polyurethane foam with the heavy metal adsorption function.
The preparation method of the polyurethane foam with the heavy metal adsorption function comprises the following steps:
(1) firstly, 2-methylimidazole is dissolved in water to obtain a 2-methylimidazole solution. And dissolving zinc nitrate hexahydrate in water to obtain a zinc nitrate solution. And dropwise adding the solution of the latter into the solution of the former, stirring for 5-20 min, centrifuging at the rotating speed of 5000-15000 r/min, collecting precipitate, washing the precipitate with water for three times, and drying to obtain ZIF-8 powder.
(2) And (2) dispersing the ZIF-8 powder obtained in the step (1) with water to obtain a ZIF-8 dispersion liquid, putting polyurethane foam of 1x1x1cm3 in the dispersion liquid, fully adsorbing for 12-48 h, and drying to obtain the polyurethane foam adsorbing ZIF-8.
(3) And (3) soaking the polyurethane foam adsorbing the ZIF-8 obtained in the step (2) in a dopamine buffer solution for 4-12 h, washing with water, and finally drying to obtain the polyurethane foam with the heavy metal adsorption function.
The concentration of the 2-methylimidazole solution in the step (1) is 0.1-0.4 g/mL, and the concentration of the zinc nitrate solution is 0.1-0.4 g/mL.
The concentration of the ZIF-8 dispersion liquid in the step (2) is 3-9 mg/mL.
The concentration of the dopamine buffer solution in the step (3) is 0.5-3.5 mg/mL, and the pH value is 7.5-9.5.
According to the invention, the ZIF-8 powder with the particle size of about 200nm is prepared by a hydration method, the method is efficient, rapid and environment-friendly, the ZIF-8 is carried on a polyurethane foam framework by physical adsorption, polydopamine is taken as a protective layer, and the adsorption material with the ZIF-8 carrying amount of up to 20% in mass fraction is obtained, and the adsorption material has excellent heavy metal adsorption performance.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto. Other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principles of the invention are intended to be included within the scope of the invention.
Example 1
Dissolving 4g of 2-methylimidazole in 40mL of water, dissolving 0.4g of zinc nitrate hexahydrate in 4mL of water, slowly dropwise adding the latter into the former, stirring for 5min, centrifuging at the rotating speed of 5000r/min, collecting precipitate, washing the precipitate with water for three times, and drying to obtain ZIF-8 powder.
0.15g of ZIF-8 powder was dispersed in 50mL of ultrapure water, and polyurethane foam of 1X1cm3 was placed therein, sufficiently adsorbed for 12 hours, and dried to obtain ZIF-8-adsorbed polyurethane foam.
And (3) soaking the polyurethane foam adsorbing ZIF-8 obtained in the last step into 0.5mg/mL dopamine buffer solution with the pH value of 7.5 for 4 hours, washing with water, and finally drying to obtain the polyurethane foam with the heavy metal adsorption function.
Example 2
Dissolving 11.35g of 2-methylimidazole in 40mL of water, dissolving 0.585g of zinc nitrate hexahydrate in 4mL of water, slowly and dropwise adding the zinc nitrate hexahydrate into the water, stirring for 10min, centrifuging at the rotating speed of 10000r/min, collecting precipitate, washing the precipitate with water for three times, and drying to obtain ZIF-8 powder.
0.3g of ZIF-8 powder was dispersed in 50mL of ultrapure water, and polyurethane foam of 1X1cm3 was placed therein, sufficiently adsorbed for 24 hours, and dried to obtain ZIF-8-adsorbed polyurethane foam.
And (3) soaking the polyurethane foam adsorbing ZIF-8 obtained in the last step into 2mg/mL dopamine buffer solution with the pH value of 8.5 for 8h, washing with water, and finally drying to obtain the polyurethane foam with the heavy metal adsorption function.
Example 3
Dissolving 16g of 2-methylimidazole in 40mL of water, dissolving 1.6g of zinc nitrate hexahydrate in 4mL of water, slowly and dropwise adding the latter into the former, stirring for 20min, centrifuging at the speed of 15000r/min to collect precipitates, washing the precipitates with water for three times, and drying to obtain ZIF-8 powder.
0.45g of ZIF-8 powder was dispersed in 50mL of ultrapure water, and polyurethane foam of 1X1cm3 was placed therein, sufficiently adsorbed for 48 hours, and dried to obtain ZIF-8-adsorbed polyurethane foam.
And (3) soaking the polyurethane foam adsorbing ZIF-8 obtained in the last step into 3.5mg/mL dopamine buffer solution with the pH value of 9.5 for 12h, washing with water, and finally drying to obtain the polyurethane foam with the heavy metal adsorption function.
Example 4
Dissolving 11.35g of 2-methylimidazole in 40mL of water, dissolving 0.585g of zinc nitrate hexahydrate in 4mL of water, slowly and dropwise adding the zinc nitrate hexahydrate into the water, stirring for 10min, centrifuging at the rotating speed of 10000r/min, collecting precipitate, washing the precipitate with water for three times, and drying to obtain ZIF-8 powder.
0.45g of ZIF-8 powder was dispersed in 50mL of ultrapure water, and polyurethane foam of 1X1cm3 was placed therein, sufficiently adsorbed for 48 hours, and dried to obtain ZIF-8-adsorbed polyurethane foam.
And (3) soaking the polyurethane foam adsorbing ZIF-8 obtained in the last step into 3.5mg/mL dopamine buffer solution with the pH value of 9.5 for 12h, washing with water, and finally drying to obtain the polyurethane foam with the heavy metal adsorption function.
Example 5
Dissolving 11.35g of 2-methylimidazole in 40mL of water, dissolving 0.4g of zinc nitrate hexahydrate in 4mL of water, slowly dropwise adding the latter into the former, stirring for 5min, centrifuging at the rotating speed of 5000r/min to collect precipitates, washing the precipitates with water for three times, and drying to obtain the ZIF-8 powder.
0.15g of ZIF-8 powder was dispersed in 50mL of ultrapure water, and polyurethane foam of 1X1cm3 was placed therein, sufficiently adsorbed for 12 hours, and dried to obtain ZIF-8-adsorbed polyurethane foam.
And (3) soaking the polyurethane foam adsorbing ZIF-8 obtained in the last step into 0.5mg/mL dopamine buffer solution with the pH value of 8.5 for 8h, washing with water, and finally drying to obtain the polyurethane foam with the heavy metal adsorption function.
Example 6
Dissolving 4g of 2-methylimidazole in 40mL of water, dissolving 0.585g of zinc nitrate hexahydrate in 4mL of water, slowly and dropwise adding the zinc nitrate hexahydrate into the water, stirring for 20min, centrifuging at the rotating speed of 10000r/min, collecting precipitate, washing the precipitate with water for three times, and drying to obtain ZIF-8 powder.
0.3g of ZIF-8 powder was dispersed in 50mL of ultrapure water, and polyurethane foam of 1X1cm3 was placed therein, sufficiently adsorbed for 48 hours, and dried to obtain ZIF-8-adsorbed polyurethane foam.
And (3) soaking the polyurethane foam adsorbing ZIF-8 obtained in the last step into 2mg/mL dopamine buffer solution with the pH value of 9.5 for 12h, washing with water, and finally drying to obtain the polyurethane foam with the heavy metal adsorption function.
Claims (5)
1. A polyurethane foam with a heavy metal adsorption function is characterized in that the polyurethane foam with the heavy metal adsorption function is obtained by a simple and rapid method, firstly, an imidazole ester metal-organic framework material (ZIF-8) is prepared in a water phase, then, the ZIF-8 is attached to the polyurethane foam through physical adsorption, and secondly, a thin polydopamine protective film is plated on the surface of the polyurethane foam.
2. The process for producing a polyurethane foam having a heavy metal adsorption function as claimed in claim 1, wherein: dissolving 2-methylimidazole in water to obtain a 2-methylimidazole solution, dissolving zinc nitrate hexahydrate in water to obtain a zinc nitrate solution, dropwise adding the zinc nitrate solution into the zinc nitrate solution, stirring for 5-20 min, centrifuging at the rotating speed of 5000-15000 r/min to collect precipitates, washing the precipitates with water for three times, drying to obtain ZIF-8 powder, dispersing the ZIF-8 powder with water to obtain a ZIF-8 dispersion liquid, placing polyurethane foam in the dispersion liquid, fully adsorbing for 12-48 h, drying to obtain a polyurethane foam for adsorbing ZIF-8, soaking the obtained polyurethane foam for adsorbing ZIF-8 in a dopamine buffer solution for 4-12 h, washing with water, and drying to obtain the polyurethane foam with the heavy metal adsorption function.
3. The 2-methylimidazole solution according to claim 2 having a concentration of 0.1-0.4 g/mL and the zinc nitrate solution having a concentration of 0.1-0.4 g/mL.
4. The ZIF-8 dispersion of claim 2 having a concentration of 3-9 mg/mL.
5. The dopamine-buffering solution according to claim 2, wherein the concentration of the dopamine-buffering solution is 0.5-3.5 mg/mL, and the pH value is 7.5-9.5.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811356156.8A CN111167420A (en) | 2018-11-09 | 2018-11-09 | Polyurethane foam with heavy metal adsorption function and preparation method thereof |
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| CN201811356156.8A CN111167420A (en) | 2018-11-09 | 2018-11-09 | Polyurethane foam with heavy metal adsorption function and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111841514A (en) * | 2020-08-06 | 2020-10-30 | 四川大学 | High-performance underwater super-oleophobic recycled foam and preparation method thereof |
| CN112044414A (en) * | 2020-09-21 | 2020-12-08 | 陕西科技大学 | Three-dimensional porous UIO-66@ PUF composite material and preparation method and application thereof |
| CN112062933A (en) * | 2020-09-21 | 2020-12-11 | 长春富晟汽车饰件有限公司 | Closed-mold polyurethane foaming formula for automotive interior |
| CN115232280A (en) * | 2022-07-26 | 2022-10-25 | 山东蓝天新材料科技有限公司 | Polyurethane foam for water treatment and preparation method thereof |
-
2018
- 2018-11-09 CN CN201811356156.8A patent/CN111167420A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111841514A (en) * | 2020-08-06 | 2020-10-30 | 四川大学 | High-performance underwater super-oleophobic recycled foam and preparation method thereof |
| CN111841514B (en) * | 2020-08-06 | 2022-03-29 | 四川大学 | High-performance underwater super-oleophobic recycled foam and preparation method thereof |
| CN112044414A (en) * | 2020-09-21 | 2020-12-08 | 陕西科技大学 | Three-dimensional porous UIO-66@ PUF composite material and preparation method and application thereof |
| CN112062933A (en) * | 2020-09-21 | 2020-12-11 | 长春富晟汽车饰件有限公司 | Closed-mold polyurethane foaming formula for automotive interior |
| CN115232280A (en) * | 2022-07-26 | 2022-10-25 | 山东蓝天新材料科技有限公司 | Polyurethane foam for water treatment and preparation method thereof |
| CN115232280B (en) * | 2022-07-26 | 2024-02-23 | 山东蓝天新材料科技有限公司 | Polyurethane foam for water treatment and preparation method thereof |
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Application publication date: 20200519 |