CN114522671B - Adsorption material and preparation method and application thereof - Google Patents
Adsorption material and preparation method and application thereof Download PDFInfo
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- CN114522671B CN114522671B CN202210084546.4A CN202210084546A CN114522671B CN 114522671 B CN114522671 B CN 114522671B CN 202210084546 A CN202210084546 A CN 202210084546A CN 114522671 B CN114522671 B CN 114522671B
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- 239000000463 material Substances 0.000 title claims abstract description 57
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 229910052751 metal Inorganic materials 0.000 claims abstract description 33
- 239000002184 metal Substances 0.000 claims abstract description 33
- 239000002351 wastewater Substances 0.000 claims abstract description 22
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229940072056 alginate Drugs 0.000 claims abstract description 20
- 235000010443 alginic acid Nutrition 0.000 claims abstract description 20
- 229920000615 alginic acid Polymers 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000000926 separation method Methods 0.000 claims abstract description 5
- 239000002131 composite material Substances 0.000 claims abstract description 3
- 125000002524 organometallic group Chemical group 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 17
- 239000003463 adsorbent Substances 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 9
- 239000012266 salt solution Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 7
- 239000012265 solid product Substances 0.000 claims description 5
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052735 hafnium Inorganic materials 0.000 claims description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000002135 nanosheet Substances 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 239000010919 dye waste Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 18
- 239000012621 metal-organic framework Substances 0.000 abstract description 8
- 239000000975 dye Substances 0.000 description 27
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 9
- 238000001878 scanning electron micrograph Methods 0.000 description 8
- 150000001342 alkaline earth metals Chemical class 0.000 description 7
- 235000010410 calcium alginate Nutrition 0.000 description 7
- 239000000648 calcium alginate Substances 0.000 description 7
- 229960002681 calcium alginate Drugs 0.000 description 7
- OKHHGHGGPDJQHR-YMOPUZKJSA-L calcium;(2s,3s,4s,5s,6r)-6-[(2r,3s,4r,5s,6r)-2-carboxy-6-[(2r,3s,4r,5s,6r)-2-carboxylato-4,5,6-trihydroxyoxan-3-yl]oxy-4,5-dihydroxyoxan-3-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylate Chemical compound [Ca+2].O[C@@H]1[C@H](O)[C@H](O)O[C@@H](C([O-])=O)[C@H]1O[C@H]1[C@@H](O)[C@@H](O)[C@H](O[C@H]2[C@H]([C@@H](O)[C@H](O)[C@H](O2)C([O-])=O)O)[C@H](C(O)=O)O1 OKHHGHGGPDJQHR-YMOPUZKJSA-L 0.000 description 7
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 7
- 229940012189 methyl orange Drugs 0.000 description 7
- 238000003917 TEM image Methods 0.000 description 5
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 235000010413 sodium alginate Nutrition 0.000 description 4
- 239000000661 sodium alginate Substances 0.000 description 4
- 229940005550 sodium alginate Drugs 0.000 description 4
- 229910007926 ZrCl Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- -1 alkaline earth metal salt Chemical class 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010908 decantation Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 235000010408 potassium alginate Nutrition 0.000 description 2
- 239000000737 potassium alginate Substances 0.000 description 2
- MZYRDLHIWXQJCQ-YZOKENDUSA-L potassium alginate Chemical compound [K+].[K+].O1[C@@H](C([O-])=O)[C@@H](OC)[C@H](O)[C@H](O)[C@@H]1O[C@@H]1[C@@H](C([O-])=O)O[C@@H](O)[C@@H](O)[C@H]1O MZYRDLHIWXQJCQ-YZOKENDUSA-L 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- AEMOLEFTQBMNLQ-AZLKCVHYSA-N (2r,3s,4s,5s,6r)-3,4,5,6-tetrahydroxyoxane-2-carboxylic acid Chemical compound O[C@@H]1O[C@@H](C(O)=O)[C@@H](O)[C@H](O)[C@@H]1O AEMOLEFTQBMNLQ-AZLKCVHYSA-N 0.000 description 1
- AEMOLEFTQBMNLQ-SYJWYVCOSA-N (2s,3s,4s,5s,6r)-3,4,5,6-tetrahydroxyoxane-2-carboxylic acid Chemical compound O[C@@H]1O[C@H](C(O)=O)[C@@H](O)[C@H](O)[C@@H]1O AEMOLEFTQBMNLQ-SYJWYVCOSA-N 0.000 description 1
- 206010028400 Mutagenic effect Diseases 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 230000003340 mental effect Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000003020 moisturizing effect Effects 0.000 description 1
- 231100000243 mutagenic effect Toxicity 0.000 description 1
- 230000003505 mutagenic effect Effects 0.000 description 1
- WHQSYGRFZMUQGQ-UHFFFAOYSA-N n,n-dimethylformamide;hydrate Chemical compound O.CN(C)C=O WHQSYGRFZMUQGQ-UHFFFAOYSA-N 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910001631 strontium chloride Inorganic materials 0.000 description 1
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
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
- B01J20/22—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 adsorption material and a preparation method and application thereof. An adsorption material is an alginate and organic metal skeleton composite material; the organic metal skeleton is NUS-8. The adsorption material provided by the invention can effectively separate dye in wastewater, and has the advantages of simple adsorption process and easiness in separation from water after adsorption. The preparation method of the adsorption material is simple and convenient to operate. The preparation method of the metal-organic framework is simple, does not need to react at high temperature, and is high in safety, energy-saving and environment-friendly, and the reaction is carried out at room temperature.
Description
Technical Field
The invention relates to the technical field of material preparation, in particular to an adsorption material and a preparation method and application thereof.
Background
The dye brings colorful colors to the life of people and generates great economic benefit, and simultaneously generates a large amount of dye wastewater harmful to the environment, and the dye wastewater is discharged into the environmental water to cause pollution of natural water areas. Certain dyes produce a pronounced color in the body of water being received at lower concentrations, and therefore even small amounts of dye can contaminate large areas of water. With the continuous development of the dye industry, the production wastewater becomes a main water pollution source. Dyes are mostly composed of harmful chemicals such as benzidine, metals, etc., and some dyes have carcinogenic and mutagenic effects, and these waste waters must be treated before being discharged into waters.
The metal organic framework materials (Mental Organic Frameworks, MOFs) are crystal materials with multidimensional periodic network structures formed by self-assembly of multidentate organic connectors (mostly aromatic polyacids and polybasic) containing oxygen, nitrogen and the like and metal ions, and generally take the metal ions as connection points, and organic ligand supports form spatial three-dimensional extension; different metal ions or the same metal ions 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, and the high surface area and adsorption affinity make MOFs have great potential for energy efficient and environmentally friendly separation of mixtures.
Disclosure of Invention
It is an object of the present invention to provide an adsorbent, a method for preparing the adsorbent, a third object of the present invention to provide an application of the adsorbent, and a fourth object of the present invention to provide a method for adsorbing dye in wastewater.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the first aspect of the invention provides an adsorption material, which is an alginate and organic metal framework composite material; the organic metal skeleton is NUS-8.
Preferably, in the adsorbing material, the diameter of the adsorbing material is 1.5-3mm; further preferably, the diameter of the adsorbent material is 1.5-2.5mm; still more preferably, the adsorbent material has a diameter of 1.8-2.0mm.
Preferably, in the adsorption material, the mass ratio of the alginate to the organic metal framework is (4-2500): 1, a step of; further preferably, the mass ratio of the alginate to the organometallic skeleton is (4-100): 1, a step of; still further preferably, the mass ratio of the alginate to the organometallic skeleton is (4-49): 1, a step of; still more preferably, the mass ratio of the alginate to the organometallic 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 adsorption material, the preparation method of the organic metal framework is as follows:
1,3, 5-trimesic acid (H) 3 BTB), metal salt solution and solvent, and reacting at room temperature to obtain the organic metal framework.
Further preferably, in the preparation method of the organic metal skeleton, the metal salt is at least one of a zirconium source and a hafnium source; still further preferred, the metal salt is ZrCl 4 、HfCl 4 At least one of (a) and (b); still more preferably, the metal salt is ZrCl 4 。
Further preferably, the molar mass ratio of 1,3, 5-trimesic acid to metal salt in the preparation method of the organic metal skeleton is 1: (0.8-1.2); still further preferred, the molar mass ratio of 1,3, 5-trimesic acid to metal salt is 1: (0.9-1.1).
Further preferred, the method for preparing the organometallic framework comprises the step of preparing the organometallic framework by using 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, DMF; still more preferably, the volume ratio of DMF, water and acetic acid is 5: (1-2): 1, a step of; in some preferred embodiments of the invention, the volume ratio of DMF, water and acetic acid is 5:1.5:1.
further preferably, the method for producing such an organometallic skeleton comprises reacting 1,3, 5-trimesic acid (H 3 BTB) to solvent molar volume ratio of 1mmol: (2.5-3.5) mL; still further preferred, the molar volume ratio of 1,3, 5-trimesic acid to solvent is 1mmol: (2.8-3.2) mL; still more preferably, the molar volume ratio of 1,3, 5-trimesic acid to solvent is 1mmol:3mL.
Further preferably, the preparation method of the organic metal skeleton comprises the steps of mixing 1,3, 5-trimesic acid, metal salt and a solvent, and reacting for 3-8 days at room temperature; still more preferably, 1,3, 5-trimesic acid, metal salt and solvent are mixed and reacted for 5-7 days at room temperature.
Further preferably, the preparation method of the organic metal framework further comprises a cleaning step, specifically: the solid product obtained is immersed in DMF at room temperature for 2.5-3.5 days, during which the extract is decanted and fresh DMF is added daily; then the solid product is treated with anhydrous methanol for another 2.5 to 3.5 days; performing the process to wash out residual reagent in the gap; after removal of the methanol by decantation, the solid product was dried under vacuum at 110-130 ℃ for 20-26 hours.
Preferably, the surface of the organic metal framework is in a stacked fold shape, and is accompanied by cracks.
The second aspect of the present invention provides a method for preparing such an adsorbent material, comprising the steps of:
mixing the alginate solution with the organic metal framework, and stirring to obtain a mixed solution; and (3) dripping the mixed solution into alkaline earth metal salt solution to obtain a solid product serving as an adsorption material.
Preferably, the preparation method of the adsorption material comprises the step that 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 having a high alpha-L-guluronic acid/beta-D-mannuronic acid ratio.
Preferably, the concentration of the alginate solution in the preparation method of the adsorption material is 1.0-2.0wt%; further preferably, the concentration of the alginate solution is 1.2-1.8wt%; still more preferably, the concentration of the alginate solution is 1.4-1.6wt%.
Preferably, the adsorption material is prepared by stirring an alginate solution into a transparent and viscous solution at 70-90 ℃ before mixing the alginate solution with an organic metal framework.
Preferably, the preparation method of the adsorption material comprises the steps of stirring for 1-3 hours; further preferably, the stirring time is 1.5-2.5 hours; still more preferably, the stirring time is 2 hours.
Preferably, in the preparation method of the adsorption material, after the alginate solution is mixed with the organic metal framework, the stirring temperature is 70-90 ℃; further preferably, the temperature of stirring is 75-85 ℃; still more preferably, the temperature of the stirring is 80 ℃.
Preferably, 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 concentration of alkaline earth metal salt solution in the preparation method of the adsorption material is 1-3wt%; further preferably, the alkaline earth metal salt solution has a concentration of 1.5 to 2.5wt%; still more preferably, the alkaline earth metal salt solution has a concentration of 2wt%.
Preferably, the preparation method of the adsorption material comprises the steps of dripping the mixed solution into alkaline earth metal salt solution and keeping for 12-36 hours; further preferably, the mixed solution is dripped into the alkaline earth metal salt solution and kept for 18 to 30 hours; still further preferably, the mixed solution is dropped into the alkaline earth metal salt solution and maintained 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 for a plurality of times by distilled water and soaked by deionized water for subsequent adsorption experiments.
The invention also provides an application of the adsorption material in adsorbing dyes in wastewater.
Preferably, the adsorption material is applied to the adsorption of methyl orange in wastewater.
The fourth aspect of the present invention also provides a method for adsorbing dye in wastewater, comprising the steps of: mixing the adsorption material with dye wastewater, and carrying out solid-liquid separation to remove dye in the wastewater.
Preferably, in the method for adsorbing the dye in the wastewater, the mass ratio of the organic metal framework to the dye in the adsorbing material is (8-12): 1, a step of; further preferably, the mass ratio of the organic metal framework to the dye in the adsorption material is (9-11): 1, a step of; still further preferably, the mass ratio of the organometallic framework to the dye in the adsorbent material is (9-10): 1.
preferably, the method for adsorbing the dye in the wastewater has the concentration of 5-100mg/L.
Preferably, in the method for adsorbing the dye in the wastewater, the adsorption material is mixed with the dye wastewater and then is kept stand or oscillated.
Preferably, in the method for adsorbing the dye in the wastewater, the mixing time of the adsorbing material and the dye wastewater is 12-28 hours; further preferably, the mixing time of the adsorption material and the dye wastewater is 12-24 hours; still further preferably, the mixing time of the adsorbent material and the dye wastewater is 18-24 hours.
The beneficial effects of the invention are as follows:
the adsorption material has obvious adsorption effect on dye in wastewater.
The adsorption material of the invention has simple separation after adsorption and only needs pouring out or filtering.
The adsorption material of the invention has simple dye adsorption process and only needs to be stood.
The preparation method of the adsorption material is simple and convenient to operate.
The metal organic framework has low preparation environment requirement, does not need to react at high temperature, and is high in safety, energy-saving and environment-friendly under the condition of room temperature.
Drawings
FIG. 1 is a diagram showing the growth process of the organometallic framework prepared in example 1 on days 1 to 7.
FIG. 2 is a TEM image of the organometallic framework prepared in example 1 on day 3 of growth.
FIG. 3 is a TEM image of the organometallic framework prepared in example 1 on day 4 of growth.
FIG. 4 is a TEM image of the organometallic framework prepared in example 1 on days 5-6 of growth.
Fig. 5 is a TEM image of the organometallic framework prepared in example 1 on day 7 of growth.
Fig. 6 is an SEM image of the organometallic framework prepared in example 1 on day 4 of growth.
Fig. 7 is an enlarged SEM image of the organometallic framework prepared in example 1 on day 4 of growth.
FIG. 8 is a SEM image of the organometallic framework prepared in example 1 at 5-6 days of growth.
FIG. 9 is an enlarged SEM image of the organometallic framework prepared in example 1 on days 5-6 of growth.
Fig. 10 is an SEM image of the organometallic framework prepared in example 1 on day 7 of growth.
Fig. 11 is an enlarged SEM image of the organometallic framework prepared in example 1 on day 7 of growth.
FIG. 12 is a schematic diagram of the process for preparing the adsorbent material of example 2.
Fig. 13 is an SEM image of the adsorbent material of example 2.
FIG. 14 is a graph showing the comparison of the adsorption of methyl orange by the adsorption material of example 3.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The starting materials or apparatus used in the examples are all available from conventional commercial sources or may be obtained by methods known in the art unless otherwise specified. Unless otherwise indicated, assays or testing methods are routine 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) 3 BTB,2.2g,5 mmol) and ZrCl 4 (1.2 g,5.3 mmol) in a 20mL glass vial containing 10mL DMF, 5mL deionized water and Acetic Acid (AA) (v/v=3/2);
(2) The vials are placed at room temperature for 1-7 days to obtain crude products, and the physical diagram of the standing process for 1-7 days is shown in figure 1, and the physical diagrams of the standing process for 1-2, 3, 4, 5-6 and 7 days are sequentially shown from left to right.
(3) The crude product was immersed in DMF at room temperature for 3 days during which time the extract was decanted and fresh DMF was added daily, then the sample was treated equally with anhydrous methanol for another 3 days, and the procedure was performed to wash off residual reagents in the gap; after removal of methanol by decantation, the sample was dried under vacuum at 120 ℃ for 24 hours to give the final product NUS-8 as a white powder.
Through the above procedure, the NUS-8 yield was calculated to be 73% based on the total mass of the reactants.
The structure of NUS-8 was analyzed using a Transmission Electron Microscope (TEM) and a Scanning Electron Microscope (SEM), with TEM images shown in FIGS. 2-5 and SEM images shown in FIGS. 6-11. As can be seen from FIGS. 2-11, with the extension of the reaction time, the crystals grow gradually to form a nano lamellar structure, and the thickness of the lamellar is about 30-40nm, which indicates that the preparation of NUS-8 with the extension of the reaction time at room temperature is successful. The surfaces of the nano sheets are in a stacked fold shape and are accompanied by cracks, so that the specific surface area and adsorption sites are increased, and the adsorption capacity is enhanced.
Example 2
Preparation of adsorbent materials
1.5g sodium alginate powder was dispersed in 100mL 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 viscous solution and stirred for 2 hours. The solution was added dropwise to 2wt% CaCl by using a syringe 2 In the solution, NUS-8 (Zr) calcium alginate gel spheres with the diameter of 1.8-2.0mm are obtained. NUS-8 (Zr) calcium alginate gel ball and CaCl 2 The solution was kept in contact for 24 hours, thereby forming stable gel spheres. Finally, washing for several times by distilled water and soaking by deionized water, wherein the whole preparation process of the NUS-8 (Zr) calcium alginate spheres is shown in figure 12, and the scanning electron microscope of the NUS-8 (Zr) calcium alginate spheres is shown in figure 13. The pellets are in a three-dimensional grid structure, and the MOFs are uniformly distributed in the grid, so that the specific surface area of the pellets is greatly increased, namely, adsorption sites of the dye are increased.
Example 3
0.3g of wet NUS-8 (Zr) calcium alginate beads (90 wt%) was added to 5mL of methyl orange solution (10 mg/L), and left to stand; the comparison graph of the adsorption effect of the methyl orange on the NUS-8 (Zr) calcium alginate spheres after 12 hours is shown in FIG. 14, and after the NUS-8 (Zr) calcium alginate spheres adsorb the methyl orange, the color of the spheres is obviously changed into orange, so that the effective adsorption of the methyl orange can be realized; and (3) measuring the concentration of the adsorbed solution, wherein the concentration of the methyl orange after adsorption is less than 5mg/L, and the adsorption rate of the methyl orange is more than 50%.
Claims (4)
1. The application of the adsorption material in adsorbing the dye in the wastewater is characterized in that the adsorption material is an alginate and organic metal framework composite material; the organic metal framework is NUS-8; the preparation method of the adsorption material comprises the following steps:
mixing 1,3, 5-trimesic acid, a metal salt solution and a solvent, and reacting at room temperature to obtain the organic metal framework;
mixing the alginate solution with the organic metal framework, and stirring to obtain a mixed solution; dripping the mixed solution into a calcium chloride solution to obtain a solid product which is the adsorption material;
the mass ratio of the alginate to the organic metal framework in the adsorption material is (4-2500): 1, a step of;
the metal salt is at least one of a zirconium source and a hafnium source;
the NUS-8 is of a nano lamellar structure, and the surfaces of the nano sheets are in a stacked and wrinkled shape and are accompanied by cracks.
2. The use according to claim 1, wherein the adsorbent material has a diameter of 1.5-3mm.
3. The use according to claim 1, wherein the adsorbent material is mixed with dye waste water, solid-liquid separation is performed to remove dye from the waste water.
4. The use according to claim 3, wherein the mass ratio of the organometallic framework to the dye in the adsorbent material is (8-12): 1.
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