CN113070037A - Preparation method of composite material for rapidly detecting chromium metal and composite material - Google Patents
Preparation method of composite material for rapidly detecting chromium metal and composite material Download PDFInfo
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- CN113070037A CN113070037A CN202110371400.3A CN202110371400A CN113070037A CN 113070037 A CN113070037 A CN 113070037A CN 202110371400 A CN202110371400 A CN 202110371400A CN 113070037 A CN113070037 A CN 113070037A
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- 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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- 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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- 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
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
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Abstract
The invention provides a preparation method of a composite material for rapidly detecting metal chromium and the composite material. The material has good adsorption performance on heavy metal chromium ions in wastewater, and the adsorption of sponge on chromium ions can be improved by more than 70% due to the adoption of the material with both macropores and micropores; the raw materials are cheap and easy to obtain, and expensive raw materials are not used, so that the production cost of the material is low; the material preparation process has mild conditions, simple process flow, safety and feasibility, and is suitable for industrial batch production.
Description
Technical Field
The invention belongs to the technical field of preparation of a hierarchical pore composite adsorption material, and particularly relates to a preparation method of a composite material for rapidly detecting metal chromium and the composite material.
Background
Now, heavy metals generally refer to metals having a specific gravity greater than 5 (metals having a density greater than 4.5 grams per cubic centimeter), and are commonly gold, silver, copper, chromium, iron, lead, and the like. Unlike the pollution caused by other organic compounds, the heavy metal pollution can reduce or eliminate the harmfulness of some organic compounds by the self-purification action of the natural world. Heavy metals are difficult to degrade in the environment and have enrichment in the environment or in organisms. Because the working procedures of mining, smelting, processing and the like of heavy metals are not strictly post-treated by a small number of enterprises or research institutions, a lot of heavy metals such as lead, chromium, mercury, cadmium, cobalt and the like enter natural environments such as atmosphere, water, soil and the like, and the environment is hardly abraded. However, heavy metals have strong toxicity, even trace amounts of them have significant toxicity, and they cannot be degraded by most microorganisms, and once they enter the organism, they are easily accumulated in the organism or possibly in only one organ, and the accumulated heavy metal ions are easily reacted with proteins in the organism to denature them, thereby damaging the organism. Nowadays, heavy metal pollution has become a major environmental problem focused on the world, which has attracted extensive attention of people in all communities, and the prevention and treatment of heavy metal pollution become a research hotspot and a target of international environmental protection workers. Therefore, the development of the treatment of the heavy metal wastewater has important significance for the production life and the social development of human beings.
At present, the methods for treating heavy metal wastewater mainly comprise the following types: 1. chemical precipitation method, adding some chemical reagents and metal ions to generate insoluble metal salt precipitate; 2. the ferrite method, adding some oxide crystals composed of iron ions and oxygen ions to react with metal ions to generate indissolvable ferrite precipitates; 3. an ion exchange method, which utilizes ion exchange resin to carry out ion exchange with heavy metal ions; 4. the membrane separation method is that under high pressure, feed liquid flows through an ultrafiltration membrane at a certain flow rate to be filtered; 5. a flotation method: utilizing the difference of surface physical and chemical properties, using a specific chemical reagent to combine with heavy metal ions to generate suspended particles, and after air is blown in, attaching air bubbles to the particles or precipitates to realize the separation from the wastewater; 6. an electrochemical method for treating metal ions by an electrochemical reaction; 7. an adsorption method: the porous solid material has a high specific surface or has active groups capable of coordinating with heavy metal ions to adsorb the metal ions. Among various methods, the adsorption method has a good development prospect due to the advantages of simple operation, high efficiency, low cost and the like.
Common adsorbing materials for treating heavy metal wastewater are roughly natural adsorbing materials, synthetic adsorbing materials and biological adsorbing materials. The natural adsorption material has defects in the aspects of structure and the like, and a good adsorption effect is difficult to achieve. The synthetic adsorption material is mainly prepared by a physical and chemical method according to different performance requirements. The adsorbent has a performance foundation superior to that of a natural adsorbent material, and can meet different adsorption requirements and adsorption conditions. At present, carbonaceous adsorption materials, synthetic resin materials, synthetic porous materials, synthetic nanomaterials, and the like are commonly used. However, the existing materials have the defects of more or less complicated preparation process, difficult realization of large-scale production, higher production cost, low adsorption efficiency and the like.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a preparation method of a composite material with high adsorbability to metal chromium and the composite material, and aims to solve the problems of complex preparation process, difficult realization of large-scale production, high production cost and low adsorption efficiency in the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme:
the preparation method of the composite material for rapidly detecting the chromium metal is characterized by comprising the following steps of:
A. modifying the sponge by using an organosilane coupling agent in an alkaline solution so that the microporous MOFs grow on the macroporous sponge;
B. and (2) growing the microporous MOFs on the inner surface and the outer surface of the sponge by adopting a solvothermal reaction method to prepare the hierarchical porous sponge @ MOFs composite material.
Preferably, the alkaline solution is potassium hydroxide or sodium bicarbonate or an anionic resin.
Preferably, the macroporous sponge is foamed polyurethane or polyvinyl alcohol or polyether or melamine.
Preferably, the organosilane coupling agent is KH-540 or KH-550 or KH-560.
Preferably, the MOFs are MOF-5 and MOF-5-NH2、UIO-66、UIO-66-NH2Any one of ZIF-8 and ZIF-67.
Preferably, the solvent is one or more of water, ethanol, methanol and DMF.
In addition, the invention also provides a composite material which is characterized by being prepared by any one of the preparation methods.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a preparation method of a composite material for rapidly detecting metal chromium and the composite material. The material has good adsorption performance on heavy metal chromium ions in wastewater, and the adsorption of sponge on chromium ions can be improved by more than 70% due to the adoption of the material with both macropores and micropores; the raw materials are cheap and easy to obtain, and expensive raw materials are not used, so that the production cost of the material is low; the material preparation process has mild conditions, simple process flow, safety and feasibility, and is suitable for industrial batch production.
Drawings
FIG. 1 is a block flow diagram of a manufacturing process of the present invention;
FIG. 2 is an SEM image of the outer surface (left) and inner surface (right) of the sponge material of the present invention;
FIG. 3 is an SEM image of the outer surface of the multi-level pore sponge @ MOFs material in the invention;
FIG. 4 is an SEM image of the inner surface of the multi-level pore sponge @ MOFs material in the present invention;
FIG. 5 is a standard curve diagram of the multilevel pore sponge @ MOFs material of the present invention for heavy metal chromium ions.
Detailed Description
In order to make the objects, technical solutions and effects of the present invention clearer and clearer, the present invention is further described in detail below with reference to the accompanying drawings and examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
As shown in fig. 1-5, the preparation method of the composite material for rapidly detecting chromium metal provided by the invention comprises the following steps:
A. modifying the sponge by using an organosilane coupling agent in an alkaline solution so that the microporous MOFs grow on the macroporous sponge;
B. and (2) growing the microporous MOFs on the inner surface and the outer surface of the sponge by adopting a solvothermal reaction method to prepare the hierarchical porous sponge @ MOFs composite material.
The method comprises the following steps of fully washing a sponge material with a certain shape and size in absolute methanol, carrying out ultrasonic oscillation for a certain time, continuously soaking in a methanol solution for 2 hours, fully soaking, and then putting into an oven for drying. Weighing a certain amount of organosilane coupling agent, dissolving in an alkaline aqueous solution, and then putting the cleaned sponge into the solution to be soaked for 24 hours. After soaking, taking out the sponge material, washing the sponge material with deionized water for 3 times, and drying to obtain modified macroporous sponge; weighing a certain amount of dicarboxylic acid compound or imidazole compound to dissolve in a solvent, then putting the modified sponge into the solution to soak for a certain time, taking out the modified sponge, then adding the modified sponge into an aqueous solution in which metal ions are dissolved, then adding the modified sponge into a reaction kettle, and reacting for 24 hours in an oven at 120 ℃. And after the reaction is finished, cooling to room temperature, washing the solid with anhydrous methanol, and drying to obtain the hierarchical porous sponge @ MOFs composite material.
In some embodiments, the alkaline solution is potassium hydroxide or sodium bicarbonate or an anionic resin.
Further, the macroporous sponge is foamed polyurethane or polyvinyl alcohol or polyether or melamine.
Further, the organosilane coupling agent is KH-540, KH-550 or KH-560, for example, a sponge material with a certain shape and size is placed in absolute methanol to be fully soaked for 10min, subjected to ultrasonic treatment for 15min, soaked for 2h, and then placed in an oven to be dried. 1g of organosilane coupling agent KH-550 is weighed and dissolved in 30ml of 0.5M sodium hydroxide solution, and then the cleaned polyurethane sponge material is put into the solution and soaked for 24 hours. After soaking, taking out the sponge material, washing the sponge material with deionized water for 3 times, and putting the sponge material into an oven for drying to prepare the modified polyurethane sponge.
Further, the MOFs are MOF-5 and MOF-5-NH2、UIO-66、UIO-66-NH2Any one of ZIF-8 and ZIF-67. For example, 0.045g of 2-aminoterephthalic acid is weighed and dissolved in 10ml of anhydrous methanol, the modified polyurethane sponge is put into the solution and soaked for 1h, then the solution is taken out and added into 5ml of deionized water containing 0.048g of zirconium tetrachloride, the solution and the sponge material are added into a 25ml reaction kettle together, and the reaction is carried out in an oven at 120 ℃ for 24 h. And after the reaction, cooling to room temperature, taking out the composite material, washing for 3 times by using anhydrous methanol, and drying to obtain the hierarchical porous polyurethane sponge @ MOFs composite material.
Further, the solvent is one or a mixture of water, ethanol, methanol and DMF.
And in addition, judging the adsorption capacity of the multi-level pore sponge @ MOFs material on heavy metal chromium ions according to the national standard, taking 6 50ml volumetric flasks, sequentially adding 0, 0.50, 1.00, 2.00, 4.00 and 8.00ml of chromium standard use solution, adding 0.5ml of sulfuric acid and 0.5ml of phosphoric acid, and shaking uniformly. Then 2ml of developer solution is added, diluted to the marked line by water and shaken up. And standing the solution for 5-10min, and respectively measuring the absorbance of the chromium ion solution with various concentrations at 540nm by using a 1cm cuvette and taking deionized water as a reference. And drawing a standard curve according to the relation between the concentration and the absorbance. Soaking a certain amount of the multi-level pore sponge @ MOFs material in a chromium solution for a certain time, then adding 4ml of reaction liquid into a 50ml volumetric flask, adding 0.5ml of sulfuric acid and 0.5ml of phosphoric acid, and shaking up. Then 2ml of color developing agent solution is added, diluted to the marked line by deionized water and shaken up. Standing for 5-10min, and measuring the absorbance of the chromium ion solution with various concentrations at 540nm with a 1cm cuvette and deionized water as reference. And (3) calculating the concentration of the chromium solution according to a standard curve formula, and calculating the adsorption rate compared with the solution before soaking the multi-level pore sponge @ MOFs material. The MOFs-improved polyurethane sponge material can obtain a good adsorption effect within 24 hours, the adsorption rate reaches 81%, and the adsorption rate is improved by about 70% compared with that of a blank sponge.
In addition, the invention also provides a composite material which is characterized by being prepared by any one of the preparation methods.
In summary, the working principle of the invention is as follows:
the invention provides a preparation method of a composite material for rapidly detecting metal chromium and the composite material. The material has good adsorption performance on heavy metal chromium ions in wastewater, and the adsorption of sponge on chromium ions can be improved by more than 70% due to the adoption of the material with both macropores and micropores; the raw materials are cheap and easy to obtain, and expensive raw materials are not used, so that the production cost of the material is low; the material preparation process has mild conditions, simple process flow, safety and feasibility, and is suitable for industrial batch production.
It should be understood that equivalents and modifications of the technical solution and inventive concept thereof may occur to those skilled in the art, and all such modifications and alterations should fall within the scope of the appended claims.
Claims (7)
1. The preparation method of the composite material for rapidly detecting the chromium metal is characterized by comprising the following steps of:
A. modifying the sponge by using an organosilane coupling agent in an alkaline solution so that the microporous MOFs grow on the macroporous sponge;
B. and (2) growing the microporous MOFs on the inner surface and the outer surface of the sponge by adopting a solvothermal reaction method to prepare the hierarchical porous sponge @ MOFs composite material.
2. The method for preparing the composite material for rapidly detecting metallic chromium according to claim 1, wherein the alkaline solution is potassium hydroxide or sodium bicarbonate or an anionic resin.
3. The method for preparing the composite material for rapidly detecting metallic chromium according to claim 1, wherein the macroporous sponge is foamed polyurethane, polyvinyl alcohol, polyether or melamine.
4. The method for preparing the composite material for rapidly detecting metallic chromium according to claim 1, wherein the organosilane coupling agent is KH-540, KH-550 or KH-560.
5. The method for preparing the composite material for rapidly detecting metal chromium according to claim 1, wherein the MOFs are MOF-5 and MOF-5-NH2、UIO-66、UIO-66-NH2Any one of ZIF-8 and ZIF-67.
6. The method for preparing the composite material for rapidly detecting metallic chromium according to claim 1, wherein the solvent is a mixture of one or more of water, ethanol, methanol and DMF.
7. A composite material produced by the production method according to any one of claims 1 to 6.
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| CN202110371400.3A CN113070037A (en) | 2021-04-07 | 2021-04-07 | Preparation method of composite material for rapidly detecting chromium metal and composite material |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114471731A (en) * | 2022-03-02 | 2022-05-13 | 淮阴师范学院 | Preparation method, product and application of Cu (I) catalyst |
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2021
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114471731A (en) * | 2022-03-02 | 2022-05-13 | 淮阴师范学院 | Preparation method, product and application of Cu (I) catalyst |
| CN114471731B (en) * | 2022-03-02 | 2022-10-04 | 淮阴师范学院 | Preparation method, product and application of Cu (I) catalyst |
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