CN114522671A - Adsorbing material and preparation method and application thereof - Google Patents

Adsorbing material and preparation method and application thereof Download PDF

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Publication number
CN114522671A
CN114522671A CN202210084546.4A CN202210084546A CN114522671A CN 114522671 A CN114522671 A CN 114522671A CN 202210084546 A CN202210084546 A CN 202210084546A CN 114522671 A CN114522671 A CN 114522671A
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adsorbing
adsorbing material
framework
dye
preparation
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CN114522671B (en
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张晓霞
黄德银
张晓美
韦高玲
田婷婷
刘秀英
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Institute of Eco Environmental and Soil Sciences of Guangdong Academy of Sciens
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Institute of Eco Environmental and Soil Sciences of Guangdong Academy of Sciens
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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
    • B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
    • 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]
    • 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
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/308—Dyes; Colorants; Fluorescent agents
    • 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

Abstract

The invention discloses an adsorbing material and a preparation method and application thereof. An adsorbing material is a composite material of alginate and an organic metal framework; the organometallic framework is NUS-8. The adsorbing material disclosed by the invention can be used for effectively separating dyes in wastewater, is simple in adsorption process, and is easy to separate from a water body after adsorption. The preparation method of the adsorbing material is simple and convenient to operate. The preparation method of the metal organic framework is simple, does not need to carry out reaction at high temperature, carries out reaction at room temperature, and has high safety, energy conservation and environmental protection.

Description

Adsorbing material and preparation method and application thereof
Technical Field
The invention relates to the technical field of material preparation, in particular to an adsorbing material and a preparation method and application thereof.
Background
The dye brings bright and colorful colors to the life of people and generates great economic benefit, and simultaneously generates a great amount of dye wastewater harmful to the environment, and the dye wastewater is discharged into the environmental water area to cause pollution of natural water areas. Certain dyes produce significant color in the receiving water at low concentrations, and thus even small amounts of dye can contaminate large areas of water. With the continuous development of the dye industry, the production wastewater thereof becomes a main water body pollution source. Dyes are mostly composed of harmful chemicals such as benzidine, metals, etc., some dyes have carcinogenic and mutagenic effects, and these waste waters must be treated before being discharged into the water.
Metal Organic Frameworks (MOFs) are crystalline materials with a multidimensional periodic network structure formed by self-assembling oxygen-nitrogen-containing multidentate Organic connectors (mostly aromatic polyacids and polybases) and metal ions, and generally metal ions are used as connection points, and Organic ligand sites are supported to form spatial three-dimensional extension; different metal ions or the same metal ion in different oxidation states react with different types of organic ligands to generate different framework structures. The diversity of Metal Organic Framework (MOF) structures and pore sizes, as well as the high surface area and adsorption affinity, make MOFs have great potential for energy-and environmentally-friendly separation of mixtures.
Disclosure of Invention
The invention aims at providing an adsorbing material, aims at providing a preparation method of the adsorbing material, aims at providing an application of the adsorbing material, and aims at providing a method for adsorbing dye in wastewater.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention provides an adsorbing material, which is an alginate and organic metal framework composite material; the organic metal framework is NUS-8.
Preferably, in the adsorbing material, the diameter of the adsorbing material is 1.5-3 mm; further preferably, the diameter of the adsorbing material is 1.5-2.5 mm; still more preferably, the diameter of the adsorbent material is 1.8-2.0 mm.
Preferably, in the adsorbing material, the mass ratio of the alginate to the organic metal skeleton is (4-2500): 1; further preferably, the mass ratio of the alginate to the organic metal skeleton is (4-100): 1; still more preferably, the mass ratio of the alginate to the organic metal skeleton is (4-49): 1; more preferably, the mass ratio of the alginate to the organic metal skeleton is (4-20): 1.
preferably, in the adsorbing material, the alginate is at least one of sodium alginate and potassium alginate.
Preferably, in the adsorbing material, the preparation method of the organic metal framework is as follows:
1,3, 5-trimesic acid (H)3BTB), metal salt solution and solvent are mixed and reacted at room temperature to obtain the organic metal framework.
Further preferably, in the method for preparing the organometallic framework, the metal salt is at least one of a zirconium source and a hafnium source; still more preferably, the metal salt is ZrCl4、HfCl4At least one of (a); more preferably, the metal salt is ZrCl4。
Further preferably, in the preparation method of the organic metal framework, the molar mass ratio of the 1,3, 5-trimesic acid to the metal salt is 1: (0.8-1.2); still more preferably, the molar mass ratio of the 1,3, 5-trimesic acid to the metal salt is 1: (0.9-1.1).
Further preferably, the method for preparing the organometallic framework comprises a step of preparing the organometallic framework from a solvent including at least one of water, acetic acid, methanol and N, N-Dimethylformamide (DMF); still more preferably, the solvent is a mixture of water, acetic acid and DMF; still more preferably, the volume ratio of DMF, water and acetic acid is 5: (1-2): 1; in some preferred embodiments of the invention, the volume ratio of DMF, water and acetic acid is 5: 1.5: 1.
further preferably, 1,3, 5-trimesic acid (H), a process for preparing such an organometallic framework, is provided3BTB) to solvent molar volume ratio 1 mmol: (2.5-3.5) mL; still further preferred, the first and second polymers, 1,3,the molar volume ratio of the 5-trimesic acid to the solvent is 1 mmol: (2.8-3.2) mL; more preferably, the molar volume ratio of the 1,3, 5-trimesic acid to the solvent is 1 mmol: 3 mL.
Further preferably, in the preparation method of the organic metal framework, 1,3, 5-trimesic acid, metal salt and a solvent are mixed, and the reaction time is 3 to 8 days at room temperature; still more preferably, the 1,3, 5-trimesic acid, metal salt and solvent are mixed and reacted at room temperature for 5 to 7 days.
Further preferably, the preparation method of the organometallic framework further comprises a cleaning step, specifically: soaking the obtained solid product in DMF at room temperature for 2.5-3.5 days, decanting the extract and adding fresh DMF every day; then treating the solid product with anhydrous methanol for another 2.5-3.5 days; this process is carried out to wash off the residual reagent in the crevices; after removal of the methanol by decantation, the solid product was dried under vacuum at 110 ℃ and 130 ℃ for 20-26 hours.
Preferably, the surface of the organometallic skeleton is folded in a stack with cracks.
The second aspect of the invention provides a preparation method of the adsorbing material, which comprises the following steps:
mixing the alginate solution with the organic metal framework, and stirring to obtain a mixed solution; and dropping the mixed solution into the alkaline earth metal salt solution to obtain a solid product serving as the adsorption material.
Preferably, in the preparation method of the adsorbing material, the alginate is at least one of sodium alginate and potassium alginate; in some preferred embodiments of the invention, the alginate is at least one of sodium alginate salts having a high α -L-guluronic acid/β -D-mannuronic acid ratio.
Preferably, the preparation method of the adsorbing material comprises the steps of enabling the concentration of an alginate solution to be 1.0-2.0 wt%; further preferably, the concentration of the alginate solution is 1.2-1.8 wt%; still more preferably, the concentration of the alginate solution is 1.4-1.6 wt%.
Preferably, the preparation method of the adsorbing material is that the alginate solution is stirred into a transparent and viscous solution at 70-90 ℃ before being mixed with the organic metal framework.
Preferably, the preparation method of the adsorbing material has the stirring time of 1-3 h; further preferably, the stirring time is 1.5-2.5 h; still more preferably, the stirring time is 2 hours.
Preferably, the preparation method of the adsorbing material comprises the steps of mixing the alginate solution and the organic metal framework, and stirring at the temperature of 70-90 ℃; further preferably, the stirring temperature is 75-85 ℃; still more preferably, the temperature of stirring is 80 ℃.
Preferably, in the preparation method of the adsorbing material, the alkaline earth metal salt is one of calcium chloride and strontium chloride; further preferably, the alkaline earth metal salt is calcium chloride.
Preferably, the preparation method of the adsorbing material is characterized in that the concentration of the alkaline earth metal salt solution is 1-3 wt%; further preferably, the concentration of the alkaline earth metal salt solution is 1.5-2.5 wt%; still more preferably, the concentration of the alkaline earth metal salt solution is 2 wt%.
Preferably, the preparation method of the adsorbing material is that the mixed solution is dropped into the alkaline earth metal salt solution and kept for 12-36 h; more preferably, the mixed solution is dripped into the alkaline earth metal salt solution and is kept for 18 to 30 hours; more preferably, the mixed solution is dripped into the alkaline earth metal salt solution and is kept for 24 hours; thereby forming a stable spherical adsorbent material.
Preferably, the preparation method of the adsorption material further comprises the steps of washing and moisturizing the adsorption material, and the prepared adsorption material is washed with distilled water for several times and soaked in deionized water for subsequent adsorption experiments.
The third aspect of the invention also provides application of the adsorbing material in adsorbing dye in wastewater.
Preferably, the adsorbing material is applied to adsorbing methyl orange in wastewater.
The fourth aspect of the present invention also provides a method for adsorbing a dye in wastewater, comprising the steps of: and mixing the adsorption material with the dye wastewater, and carrying out solid-liquid separation to remove the dye in the wastewater.
Preferably, in the method for adsorbing the dye in the wastewater, the mass ratio of the organic metal framework in the adsorbing material to the dye is (8-12): 1; further preferably, the mass ratio of the organometallic framework to the dye in the adsorbing material is (9-11): 1; still more preferably, the mass ratio of the organometallic framework to the dye in the adsorbing material is (9-10): 1.
preferably, the concentration of the dye in the wastewater is 5-100 mg/L.
Preferably, in the method for adsorbing the dye in the wastewater, the adsorbing material is mixed with the dye wastewater and then stands or oscillates.
Preferably, in the method for adsorbing the dye in the wastewater, the time for mixing the adsorbing material and the dye wastewater is 12-28 h; further preferably, the mixing time of the adsorption material and the dye wastewater is 12-24 h; still further preferably, the mixing time of the adsorbing material and the dye wastewater is 18-24 h.
The invention has the beneficial effects that:
the adsorbing material has obvious effect of adsorbing the dye in the wastewater.
The adsorption material of the invention has simple separation after adsorption and only needs to be poured out or filtered.
The process of adsorbing the dye by the adsorbing material is simple, and only standing is needed.
The preparation method of the adsorbing material is simple and convenient to operate.
The preparation environment of the metal organic framework is low in requirement, the reaction is carried out at room temperature without high temperature, the safety is high, and the metal organic framework is energy-saving and environment-friendly.
Drawings
FIG. 1 is a physical diagram of the growth process of example 1 for days 1-7 of the preparation of the organometallic framework.
FIG. 2 is a TEM image of the growth day 3 of the organometallic framework prepared in example 1.
FIG. 3 is a TEM image of the 4 th day of the growth of the organometallic framework prepared in example 1.
FIG. 4 is a TEM image of the organometallic frameworks prepared in example 1 grown from 5 to 6 days.
FIG. 5 is a TEM image of the 7 th day of the growth of the organometallic framework prepared in example 1.
FIG. 6 is a SEM photograph of the growth of the organometallic framework obtained in example 1 at day 4.
FIG. 7 is an enlarged SEM photograph of the growth of the organometallic framework prepared in example 1 at day 4.
FIG. 8 is an SEM photograph of the growth days 5-6 of the organometallic frameworks prepared in example 1.
FIG. 9 is an SEM photograph of the growth of organometallic frameworks obtained from the preparation of example 1 at 5-6 days under magnification.
FIG. 10 is an SEM photograph of the growth day 7 of the organometallic framework prepared in example 1.
FIG. 11 is an enlarged SEM photograph of the 7 th day of growth of the organometallic framework prepared in example 1.
FIG. 12 is a schematic diagram of the process for the preparation of the adsorbent material of example 2.
FIG. 13 is an SEM photograph of an adsorbent according to example 2.
FIG. 14 is a comparison graph of the adsorbent of example 3 before and after adsorbing methyl orange.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The starting materials or the apparatuses used in the examples are, unless otherwise specified, either commercially available from conventional sources or can be obtained by methods known in the art. Unless otherwise indicated, the testing or testing methods are conventional in the art.
Example 1
Synthesis and characterization of organometallic frameworks
The synthesis method of NUS-8 is as follows:
(1) 1,3, 5-trimesic acid (H)3BTB, 2.2g, 5mmol) and ZrCl4(1.2g, 5.3mmol) were combined in a 10mL DMF, 5mL 20mL glass vial containing deionized water and Acetic Acid (AA) (v/v. 3/2);
(2) placing the vial at room temperature for 1-7 days to obtain crude product, wherein the physical diagram of the 1-7 day standing process is shown in figure 1, and the physical diagrams of the 1-2, 3, 4, 5-6 and 7 days standing process are sequentially from left to right.
(3) The crude product is soaked in DMF at room temperature for 3 days, during which the extract is decanted and fresh DMF is added daily, and then the sample is treated likewise with anhydrous methanol for a further 3 days, which is carried out to wash off the residual reagents in the gaps; after removal of the methanol by decantation, the sample was dried under vacuum at 120 ℃ for 24 hours to give the final product as white powder of NUS-8.
By the above procedure, a yield of NUS-8 of 73% was calculated based on the total mass of reactants.
The structure of NUS-8 is analyzed by Transmission Electron Microscopy (TEM) and Scanning Electron Microscopy (SEM), wherein TEM image is shown in attached figures 2-5, and SEM image is shown in attached figures 6-11. As can be seen from FIGS. 2 to 11, the crystal grows gradually with the extension of the reaction time to form a nanosheet structure, the thickness of the nanosheet is about 30-40nm, and the extension of the reaction time NUS-8 at room temperature is proved to be successful. The surface of the nano sheet is in a stacking wrinkle shape and is accompanied with cracks, so that the specific surface area and adsorption sites are increased, and the adsorption capacity is enhanced.
Example 2
Preparation of the adsorbent Material
1.5g of sodium alginate powder was dispersed in 100mL of deionized water to give a 1.5% w/v alginate solution. The solution was mixed at 80 ℃ with mechanical stirring until a clear, viscous solution was obtained. Then 0.03g NUS-8 was mixed with the above viscous solution and stirred for 2 hours. The solution was added dropwise to 2 wt% CaCl by using a syringe2Obtaining NUS-8(Zr) calcium alginate gel balls with the diameter of 1.8-2.0mm in the solution. NUS-8(Zr) calcium alginate gel ball and CaCl2The solution was kept in contact for 24 hours, thereby forming stable gel spheres. And finally, washing with distilled water for several times, soaking with deionized water for a subsequent adsorption experiment, wherein the whole preparation process of the NUS-8(Zr) calcium alginate spheres is shown in figure 12, and the scanning electron microscope image of the NUS-8(Zr) calcium alginate spheres is shown in figure 13. The small balls are in a three-dimensional grid structure, and the MOFs are uniformly distributed in the grids, so that the specific surface area of the small balls is greatly increased, namely the adsorption sites of the dye are increased.
Example 3
Adding 0.3g of wet NUS-8(Zr) calcium alginate spheres (90 wt%) to 5mL of methyl orange solution (10mg/L), and standing; the absorption effect of methyl orange on the NUS-8(Zr) calcium alginate spheres after 12 hours is compared with a graph shown in fig. 14, and after the NUS-8(Zr) calcium alginate spheres absorb the methyl orange, the color of the spheres is obviously changed into orange, so that the effective absorption of the methyl orange can be realized; and measuring the concentration of the solution after adsorption, wherein the concentration of methyl orange after adsorption is less than 5mg/L, and the adsorption rate of methyl orange is more than 50%.

Claims (10)

1. The adsorbing material is characterized in that the adsorbing material is an alginate and organic metal framework composite material; the organic metal framework is NUS-8.
2. The adsorbent material according to claim 1, wherein the adsorbent material has a diameter of 1.5-3 mm.
3. The adsorption material according to claim 1, wherein the mass ratio of alginate to the organometallic framework in the adsorption material is (4-2500): 1.
4. the adsorbent material according to any one of claims 1 to 3, wherein the organometallic framework is prepared by the following method:
mixing 1,3, 5-trimesic acid, metal salt solution and solvent, and reacting at room temperature to obtain the organic metal framework.
5. The adsorbent material according to claim 4, wherein the metal salt is at least one of a zirconium source and a hafnium source.
6. The adsorbing material according to claim 4, wherein the molar mass ratio of the 1,3, 5-trimesic acid to the metal salt is 1: (0.8-1.2).
7. A method for the preparation of the adsorbent material according to any of claims 1-3, characterized in that it comprises the following steps:
mixing the alginate solution with the organic metal framework, and stirring to obtain a mixed solution; and dropping the mixed solution into an alkaline earth metal salt solution to obtain a solid product serving as the adsorbing material.
8. Use of an adsorbent material according to any one of claims 1 to 6 for adsorbing dyes in waste water.
9. The method for adsorbing the dye in the wastewater is characterized by comprising the following steps of: mixing the adsorbing material of any one of claims 1 to 6 with dye wastewater, and carrying out solid-liquid separation to remove the dye in the wastewater.
10. The method for adsorbing the dye in the wastewater according to claim 9, wherein the mass ratio of the organic metal framework to the dye in the adsorbing material is (8-12): 1.
CN202210084546.4A 2022-01-25 2022-01-25 Adsorption material and preparation method and application thereof Active CN114522671B (en)

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