CN114380869B - Metal-organic framework material and preparation method and application thereof - Google Patents
Metal-organic framework material and preparation method and application thereof Download PDFInfo
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- CN114380869B CN114380869B CN202210033593.6A CN202210033593A CN114380869B CN 114380869 B CN114380869 B CN 114380869B CN 202210033593 A CN202210033593 A CN 202210033593A CN 114380869 B CN114380869 B CN 114380869B
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- 239000000463 material Substances 0.000 title claims abstract description 158
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 42
- 239000010935 stainless steel Substances 0.000 claims abstract description 42
- 239000002351 wastewater Substances 0.000 claims abstract description 40
- 238000005554 pickling Methods 0.000 claims abstract description 37
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 239000002245 particle Substances 0.000 claims abstract description 16
- 239000011148 porous material Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000011049 filling Methods 0.000 claims abstract description 4
- 238000001514 detection method Methods 0.000 claims description 27
- 239000007864 aqueous solution Substances 0.000 claims description 25
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 17
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- 239000011550 stock solution Substances 0.000 claims description 7
- 238000000825 ultraviolet detection Methods 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 4
- 239000012528 membrane Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- -1 polytetrafluoroethylene Polymers 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 2
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 claims 3
- 230000000274 adsorptive effect Effects 0.000 claims 1
- 238000010998 test method Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 6
- 238000004064 recycling Methods 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 18
- 238000001228 spectrum Methods 0.000 description 15
- 238000001179 sorption measurement Methods 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 238000002441 X-ray diffraction Methods 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 238000003795 desorption Methods 0.000 description 9
- 239000011651 chromium Substances 0.000 description 8
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 150000007522 mineralic acids Chemical class 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000013291 MIL-100 Substances 0.000 description 1
- 239000013177 MIL-101 Substances 0.000 description 1
- 239000013206 MIL-53 Substances 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011707 mineral Chemical class 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000013265 porous functional material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
- C07F15/02—Iron compounds
- C07F15/025—Iron compounds without a metal-carbon linkage
-
- 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]
-
- 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
- B01J20/28054—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 surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28066—Surface area, e.g. B.E.T specific surface area being more than 1000 m2/g
-
- 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
- B01J20/28054—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 surface properties or porosity
- B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
- B01J20/28073—Pore volume, e.g. total pore volume, mesopore volume, micropore volume being in the range 0.5-1.0 ml/g
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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
- B01J20/28054—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 surface properties or porosity
- B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
- B01J20/28076—Pore volume, e.g. total pore volume, mesopore volume, micropore volume being more than 1.0 ml/g
-
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/20—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by using diffraction of the radiation by the materials, e.g. for investigating crystal structure; by using scattering of the radiation by the materials, e.g. for investigating non-crystalline materials; by using reflection of the radiation by the materials
- G01N23/20008—Constructional details of analysers, e.g. characterised by X-ray source, detector or optical system; Accessories therefor; Preparing specimens therefor
- G01N23/2005—Preparation of powder samples therefor
-
- 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
Abstract
The invention belongs to the technical field of preparation methods of metal-organic framework materials and reutilization of stainless steel industrial pickling wastewater, and particularly relates to a metal-organic framework material and a preparation method and application thereof. In order to solve the problem of high cost of the metal-organic framework material in recycling stainless steel pickling wastewater, the material is Fe x Cr 3‑x F y (BTC) z Wherein BTC is trimesic acid, x is 2.0-2.8, y is 0.5-1.0, and z is 1.5-3.0. The material consists of massive particles with the particle size of 0.3-2.0 mu m; BET specific surface area of 1192-1870 m 2 Per gram, the pore volume is 0.6608-1.8323 cm 3 And/g. The material is prepared by using stainless steel pickling wastewater, mixing the stainless steel pickling wastewater and trimesic acid, stirring uniformly at room temperature, then filling the mixture into a polytetrafluoroethylene-lined high-pressure reaction kettle, and reacting at a high temperature.
Description
Technical Field
The invention belongs to the technical field of preparation methods of metal-organic framework materials and reutilization of stainless steel industrial pickling wastewater, and particularly relates to a metal-organic framework material and a preparation method and application thereof.
Background
The processes of smelting, casting, hot rolling, heat treatment, welding and the like in the production process of stainless steel can generate compact oxide skin on the surface of steel, and the subsequent treatment process of the steel needs to keep the surface clean, so that the pickling treatment is needed to remove the oxide skin so as to achieve the aim of surface finish. During the pickling process, about 0.8-2 tons of pickling wastewater is produced per ton of steel, wherein the pickling wastewater contains high-concentration heavy metals such as iron, chromium, nickel and the like in addition to inorganic acids such as nitric acid and hydrofluoric acid. Therefore, the recycling of metals in the pickling wastewater has important practical significance.
At present, the utilization of stainless steel pickling wastewater mainly has two aspects, namely, the recovery of metal is realized by methods of selective precipitation, nanofiltration crystallization and the like, and the problems of high energy consumption, large investment and high operation cost exist although some technologies are already applied to industry. The other method is to prepare functional materials by taking acid washing wastewater as a raw material, but the method is mainly limited to metal oxides or salts, and the preparation of novel materials with high added value is seldom studied.
Metal-organic frameworks (MOFs) are a new class of porous functional materials that have emerged in recent years. Based on the characteristics of regular pore channel structure, ultra-large specific surface area, porosity, low solid density and the like, MOF materials have shown excellent performance in various fields of separation, energy storage, catalysis, biological medicine, sensing and the like, but high cost has become a core problem limiting popularization. The MOF material preparation raw materials comprise a metal source, a ligand, a solvent, other regulators and the like, and the large reduction of the cost of any raw material can possibly promote the mass production process of the MOF material. The stainless steel pickling wastewater contains high-concentration Fe, cr, ni, nitric acid, hydrofluoric acid and the like, and is a raw material for preparing various classical MOF materials, such as MIL-53, MIL-100, MIL-101 and the like. At present, the MOF material with high added value is prepared by taking stainless steel pickling wastewater as a raw material, and is not reported at home and abroad.
The invention utilizes metal ions and inorganic acid in stainless steel pickling wastewater, combines with conventional low-cost organic ligands, prepares the metal-organic framework material by a hydrothermal method, converts industrial wastewater into high-additional products (organic-metal frameworks), and has good value in the fields of stainless steel pickling wastewater reclamation and MOF material large-scale popularization.
Disclosure of Invention
The invention provides a metal-organic framework material prepared by using stainless steel pickling wastewater, a preparation method and application of the prepared metal-organic framework material, and aims to solve the problem of high cost of the metal-organic framework material in recycling the stainless steel pickling wastewater.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the metal-organic framework material is Fe x Cr 3-x F y (BTC) z Wherein BTC is trimesic acid, x is 2.0-2.8, y is 0.5-1.0, and z is 1.5-3.0.
Further, the material consists of massive particles with the particle size of 0.3-2.0 mu m; BET specific surface area of 1192-1870 m 2 Per gram, the pore volume is 0.6608-1.8323 cm 3 And/g. The larger specific surface area and pore volume facilitate adsorption of the guest molecules by the material.
Further, the structure remains stable after the material is immersed in an aqueous solution at ph=1.0 to 12.0 for 10 days. Excellent long-period acid-base stability can ensure the application of the material in complex water environments.
The preparation method of the metal-organic framework material utilizes stainless steel pickling wastewater, and comprises the following steps:
mixing stainless steel acid washing wastewater and trimesic acid, stirring uniformly at room temperature, and then filling into a high-pressure reaction kettle with a polytetrafluoroethylene lining, and reacting at high temperature to obtain the material.
Further, the mass ratio of the trimesic acid to the stainless steel pickling wastewater is as follows: 15-250 g/L.
Further, the stirring time at room temperature is 30min; the temperature of the high-temperature reaction is 180-220 ℃ and the time is 12h.
The application of the metal-organic framework material is applied to the adsorption removal of methylene blue aqueous solution. The adsorption of the dye shows that the dye can effectively treat the printing and dyeing industrial wastewater.
A method of applying a metal-organic framework material comprising the steps of:
step 1, mixing a metal-organic framework material with a methylene blue aqueous solution, and stirring at room temperature;
step 2, after stirring is completed, filtering by using a filter membrane to obtain clear and transparent filtrate;
and step 3, carrying out ultraviolet detection on the filtrate and the stock solution.
Further, the mass of the metal-organic framework material in the step 1 is 20mg; the volume of the methylene blue aqueous solution is 10mL, and the concentration is 100mg/L; the stirring time at room temperature is 720min; the pore size of the filter membrane in the step 2 is 0.22 μm.
A method for testing the stability of a metal-organic framework material, comprising the following steps:
step 1, taking 200mg of metal-organic framework material, respectively adding the metal-organic framework material into aqueous solutions with pH values of 1, 6 and 12, and standing for 10 days at room temperature;
step 2, sucking out supernatant in the solution after being placed for 10 days, placing the solid at the bottom into a drying box, and drying for 12 hours at the temperature of 120 ℃;
and 3, performing XRD detection on the solid obtained by drying.
Compared with the prior art, the invention has the following advantages:
the starting materials for preparing the MOF material include metals, mineral acids, solvents, and organic ligands. At present, raw materials for MOF synthesis are generally from commercial reagents, and the cost is high. In the method, the stainless steel pickling wastewater is utilized to fully utilize metal ions (Fe and Cr), inorganic acid (nitric acid and hydrofluoric acid) and water, so that the material preparation cost can be greatly reduced. Meanwhile, the prepared material has good porosity and dye removal performance and has good practical application value. Can realize the aim of changing waste into valuable and promote the aim of treating waste with waste.
Drawings
FIG. 1 is an XRD pattern of a metal-organic framework material according to example 1 of the present invention;
FIG. 2 is an SEM image of a metal-organic framework material of example 1;
FIG. 3 is a graph showing the adsorption and desorption of nitrogen at 77K for the metal-organic framework material of example 1 of the present invention;
FIG. 4 is an XRD pattern of the metal-organic framework material of example 1 of the present invention after it has been immersed in solutions of different pH for 10 days;
FIG. 5 is an XRD pattern of the metal-organic framework material of example 2 of the present invention;
FIG. 6 is an SEM image of a metal-organic framework material of example 2;
FIG. 7 is a graph showing the adsorption and desorption of nitrogen at 77K for the metal-organic framework material of example 2 of the present invention;
FIG. 8 is an XRD pattern of the metal-organic framework material of example 2 of the present invention after it has been immersed in a solution of different pH for 10 days;
FIG. 9 is an XRD pattern of the metal-organic framework material of example 3 of the present invention;
FIG. 10 is an SEM image of a metal-organic framework material of example 3 of the invention;
FIG. 11 is a graph showing the adsorption and desorption of nitrogen at 77K for the metal-organic framework material of example 3 of the present invention;
FIG. 12 is an XRD pattern of the metal-organic framework material of example 3 of the present invention after it has been immersed in a solution of different pH for 10 days;
FIG. 13 is an XRD pattern of the metal-organic framework material of example 4 of the present invention;
FIG. 14 is an SEM image of a metal-organic framework material of example 4;
FIG. 15 is a graph showing the adsorption and desorption of nitrogen at 77K for the metal-organic framework material of example 4 of the present invention;
FIG. 16 is an XRD pattern of the metal-organic framework material of example 4 of the present invention after it has been immersed in a solution of different pH for 10 days;
FIG. 17 is an XRD pattern of the metal-organic framework material of example 5 of the present invention;
FIG. 18 is an SEM image of a metal-organic framework material of example 5 of the invention;
FIG. 19 is a graph showing the adsorption and desorption of nitrogen at 77K for the metal-organic framework material of example 5 of the present invention;
fig. 20 is an XRD pattern of the metal-organic framework material of example 5 of the present invention after 10 days of immersion in solutions of different pH.
Detailed Description
Example 1
A preparation method of a metal-organic framework material is prepared by stainless steel pickling wastewater, wherein the stainless steel pickling wastewater is from a stainless steel production enterprise in Shanxin, and comprises the following steps:
0.3g of trimesic acid is mixed with 20mL of stainless steel pickling wastewater (solid-liquid ratio: 15 g/L), stirred for 30min at room temperature, and reacted for 12 hours at 180 ℃ in a high-temperature high-pressure reaction kettle to obtain the material.
The material can be used for adsorbing an aqueous solution containing methylene blue, and the specific method is as follows:
step 1, adding 20mg of metal-organic framework material and 10mL of methylene blue aqueous solution with the concentration of 100mg/L into a 20mL reactor, and stirring at room temperature for reaction for 720min;
step 2, after the reaction, a clear and transparent solution was obtained by filtration through a 0.22 μm filter.
And step 3, carrying out ultraviolet detection on the absorbed solution and the stock solution, wherein the removal rate of the methylene blue is 93.2% as a result of detection by an ultraviolet-visible spectrophotometer.
XRD detection is carried out on the prepared material, and the result is shown in figure 1, and the material has characteristic diffraction peaks at 6.4 degrees, 10.4 degrees, 11.2 degrees, 12.7 degrees, 20.2 degrees, 24.2 degrees and 28.2 degrees.
SEM examination of the prepared material showed that the material consisted of bulk particles with a particle size of about 0.3-2. Mu.m.
Carrying out energy spectrum detection on the prepared material, and supposing that main elements of the material are as follows from a scanning energy spectrum detection result: C. o, cr, fe, F, and according to the content, the composition of the materials is determined as follows: fe (Fe) 2.0 Cr 1.0 F 0.5 (BTC) 2.0 。
The nitrogen adsorption and desorption curve of the prepared material at 77K is shown in figure 3, and the BET specific surface area of the material is 1341.0m 2 Per gram, pore volume of 0.8733cm 3 /g。
XRD detection is carried out on samples of the material after the material is soaked in aqueous solutions with different pH values for 10 days, as shown in figure 4, the XRD spectrum of the material is basically unchanged, and good stability of the material is proved.
Example 2
A preparation method of a metal-organic framework material is prepared by stainless steel pickling wastewater, wherein the stainless steel pickling wastewater is from a stainless steel production enterprise in Shanxin, and comprises the following steps:
0.7g of trimesic acid is mixed with 20mL of stainless steel pickling wastewater (solid-liquid ratio: 35 g/L), stirred for 30min at room temperature, and reacted for 12 hours at 180 ℃ in a high-temperature high-pressure reaction kettle to obtain the material.
The material can be used for adsorbing methylene blue in aqueous solution, and the specific method is as follows:
step 1, adding 20mg of metal-organic framework material and 10mL of methylene blue aqueous solution with the concentration of 100mg/L into a 20mL reactor, and stirring at room temperature for reaction for 720min;
step 2, after the reaction, a clear and transparent solution was obtained by filtration through a 0.22 μm filter.
And step 3, carrying out ultraviolet detection on the absorbed solution and the stock solution, wherein the removal rate of methylene blue is 99.2% as a result of detection by an ultraviolet-visible spectrophotometer.
XRD detection was performed on the prepared material, and the result is shown in FIG. 5, and the material has characteristic diffraction peaks at 6.4 degrees, 10.4 degrees, 11.2 degrees, 12.7 degrees, 20.2 degrees, 24.2 degrees and 28.2 degrees.
SEM examination of the prepared material showed that the material consisted of bulk particles with a particle size of about 0.5-1.5. Mu.m.
Carrying out energy spectrum detection on the prepared material, and supposing that main elements of the material are as follows from a scanning energy spectrum detection result: C. o, cr, fe, F, and according to the content, the composition of the materials is determined as follows: fe (Fe) 2.4 Cr 0.6 F 0.8 (BTC) 3.0 。
The nitrogen adsorption and desorption curve of the prepared material at 77K is shown in figure 7, and the material BET specific surface area of 1870.0m 2 Per gram, pore volume of 0.8969cm 3 /g。
XRD detection is carried out on samples of the material after the material is soaked in aqueous solutions with different pH values for 10 days, as shown in figure 8, the XRD spectrum of the material is basically unchanged, and good stability of the material is proved.
Example 3
A preparation method of a metal-organic framework material is prepared by stainless steel pickling wastewater, wherein the stainless steel pickling wastewater is from a stainless steel production enterprise in Shanxin, and comprises the following steps:
1.4g of trimesic acid and 20mL of stainless steel pickling wastewater (solid-liquid ratio: 70 g/L) are mixed, stirred at room temperature for 30min, and reacted in a high-temperature high-pressure reaction kettle at 200 ℃ for 12 hours to obtain the material.
The material can be used for adsorbing methylene blue in aqueous solution, and the specific method is as follows:
step 1, adding 20mg of metal-organic framework material and 10mL of methylene blue aqueous solution with the concentration of 100mg/L into a 20mL reactor, and stirring at room temperature for reaction for 720min;
step 2, after the reaction, a clear and transparent solution was obtained by filtration through a 0.22 μm filter.
And step 3, carrying out ultraviolet detection on the absorbed solution and the stock solution, wherein the removal rate of methylene blue is 91.4% as a result of detection by an ultraviolet-visible spectrophotometer.
XRD detection was performed on the prepared material, and the result is shown in FIG. 9, and the material has characteristic diffraction peaks at 6.4 degrees, 10.4 degrees, 11.2 degrees, 12.7 degrees, 20.2 degrees, 24.2 degrees and 28.2 degrees.
SEM examination of the prepared material showed that the material consisted of bulk particles with a particle size of about 0.3-2.0. Mu.m, as shown in FIG. 10.
Carrying out energy spectrum detection on the prepared material, and supposing that main elements of the material are as follows from a scanning energy spectrum detection result: C. o, cr, fe, F, and according to the content, the composition of the materials is determined as follows: fe (Fe) 2.8 Cr 0.2 F 1.0 (BTC) 2.4 。
Nitrogen adsorption desorption curve of prepared material at 77KThe line is shown in FIG. 11, and the BET specific surface area of the material is 1572m 2 Per gram, pore volume of 0.9255cm 3 /g。
XRD detection is carried out on samples of the material after the material is soaked in aqueous solutions with different pH values for 10 days, as shown in figure 12, the XRD spectrum of the material is basically unchanged, and good stability of the material is proved.
Example 4
A preparation method of a metal-organic framework material is prepared by stainless steel pickling wastewater, wherein the stainless steel pickling wastewater is from a stainless steel production enterprise in Shanxin, and comprises the following steps:
3.0g of trimesic acid is mixed with 20mL of stainless steel pickling wastewater (solid-liquid ratio: 150 g/L), stirred for 30min at room temperature, and reacted in a high-temperature high-pressure reaction kettle at 220 ℃ for 12 hours to obtain the material.
The material can be used for adsorbing methylene blue in aqueous solution, and the specific method is as follows:
step 1, adding 20mg of metal-organic framework material and 10mL of methylene blue aqueous solution with the concentration of 100mg/L into a 20mL reactor, and stirring at room temperature for reaction for 720min;
step 2, after the reaction, a clear and transparent solution was obtained by filtration through a 0.22 μm filter.
And step 3, carrying out ultraviolet detection on the absorbed solution and the stock solution, wherein the removal rate of methylene blue is 97.4% as a result of detection by an ultraviolet-visible spectrophotometer.
XRD detection was performed on the prepared material, and the result is shown in FIG. 13, wherein the material has characteristic diffraction peaks at 6.4 degrees, 10.4 degrees, 11.1 degrees, 12.7 degrees, 20.2 degrees, 24.2 degrees and 28.2 degrees.
SEM examination of the prepared material showed that the material consisted of bulk particles with a particle size of about 0.3-2.0. Mu.m, as shown in FIG. 14.
Carrying out energy spectrum detection on the prepared material, and supposing that main elements of the material are as follows from a scanning energy spectrum detection result: C. o, cr, fe, F, and according to the content, the composition of the materials is determined as follows: fe (Fe) 2.5 Cr 0.5 F 0.8 (BTC) 1.5 。
Prepared materialThe nitrogen adsorption and desorption curve at 77K is shown in FIG. 15, and the BET specific surface area of the material is 1354m 2 Per gram, pore volume of 1.8323cm 3 /g。
XRD detection is carried out on samples of the material after the material is soaked in aqueous solutions with different pH values for 10 days, as shown in figure 16, the XRD spectrum of the material is basically unchanged, and good stability of the material is proved.
Example 5
A preparation method of a metal-organic framework material is prepared by stainless steel pickling wastewater, wherein the stainless steel pickling wastewater is from a stainless steel production enterprise in Shanxin, and comprises the following steps:
5.0g of trimesic acid is mixed with 20mL of stainless steel pickling wastewater (solid-liquid ratio: 250 g/L), stirred for 30min at room temperature, and reacted in a high-temperature high-pressure reaction kettle at 220 ℃ for 12 hours to obtain the material.
The material can be used for adsorbing methylene blue in aqueous solution, and the specific method is as follows:
step 1, adding 20mg of metal-organic framework material and 10mL of methylene blue aqueous solution with the concentration of 100mg/L into a 20mL reactor, and stirring at room temperature for reaction for 720min;
step 2, after the reaction, a clear and transparent solution was obtained by filtration through a 0.22 μm filter.
And step 3, carrying out ultraviolet detection on the absorbed solution and the stock solution, wherein the removal rate of methylene blue is 96.7% as a result of detection by an ultraviolet-visible spectrophotometer.
XRD detection was performed on the prepared material, and the result is shown in FIG. 17, and the material has characteristic diffraction peaks at 6.4 degrees, 10.4 degrees, 11.1 degrees, 12.7 degrees, 20.2 degrees, 24.2 degrees and 28.2 degrees.
SEM examination of the prepared material showed that the material consisted of bulk particles with a particle size of about 0.3-2.0. Mu.m, as shown in FIG. 18.
Carrying out energy spectrum detection on the prepared material, and supposing that main elements of the material are as follows from a scanning energy spectrum detection result: C. o, cr, fe, F, and according to the content, the composition of the materials is determined as follows: fe (Fe) 2.8 Cr 0.2 F 0.5 (BTC) 2.0 。
The nitrogen adsorption and desorption curve of the prepared material at 77K is shown in FIG. 19, and the BET specific surface area of the material is 1192m 2 Per gram, pore volume of 0.6608cm 3 /g。
XRD detection is carried out on samples of the material after the material is soaked in aqueous solutions with different pH values for 10 days, as shown in figure 20, the XRD spectrum of the material is basically unchanged, and good stability of the material is proved.
Claims (7)
1. A metal-organic framework material is characterized in that the material is Fe x Cr 3-x F y (BTC) z Wherein BTC is trimesic acid, x is 2.0-2.8, y is 0.5-1.0, and z is 1.5-3.0;
the material consists of massive particles, the particle size is 0.3-2.0 mu m, and the BET specific surface area is 1192-1870 m 2 Per gram, the pore volume is 0.6608-1.8323 cm 3 /g; after the material is soaked in an aqueous solution with the pH value of 1.0-12.0 for 10 days, the structure is still stable;
the preparation method of the material comprises the following steps:
mixing stainless steel acid washing wastewater and trimesic acid, stirring uniformly at room temperature, and then filling into a high-pressure reaction kettle with a polytetrafluoroethylene lining, and reacting at a high temperature to obtain the material; the mass ratio of trimesic acid to stainless steel pickling wastewater is as follows: 15-250 g/L, wherein the temperature of the high-temperature reaction is 180-220 ℃ and the time is 12h.
2. A method of making a metal-organic framework material of claim 1, using stainless steel acid wash wastewater, comprising the steps of:
mixing stainless steel acid washing wastewater and trimesic acid, stirring uniformly at room temperature, and then filling into a high-pressure reaction kettle with a polytetrafluoroethylene lining, and reacting at a high temperature to obtain the material; the mass ratio of trimesic acid to stainless steel pickling wastewater is as follows: 15-250 g/L, wherein the temperature of the high-temperature reaction is 180-220 ℃ and the time is 12h.
3. The method for preparing a metal-organic framework material according to claim 2, wherein the stirring time at room temperature is 30min.
4. The use of a metal-organic framework material as claimed in claim 1, for the adsorptive removal of methylene blue aqueous solutions.
5. A method of using the metal-organic framework material of claim 1, comprising the steps of:
step 1, mixing a metal-organic framework material with a methylene blue aqueous solution, and stirring at room temperature;
step 2, after stirring is completed, filtering by using a filter membrane to obtain clear and transparent filtrate;
and step 3, carrying out ultraviolet detection on the filtrate and the stock solution.
6. The method of claim 5, wherein the mass of the metal-organic framework material in the step 1 is 20mg; the volume of the methylene blue aqueous solution is 10mL, and the concentration is 100mg/L; the stirring time at room temperature is 720min; and (3) the pore diameter of the filter membrane in the step (2) is 0.22 mu m.
7. A method of testing the stability of a metal-organic framework material of claim 1, comprising the steps of:
step 1, taking 200mg of metal-organic framework material, respectively adding the metal-organic framework material into aqueous solutions with pH values of 1, 6 and 12, and standing for 10 days at room temperature;
step 2, sucking out supernatant in the solution after being placed for 10 days, placing the solid at the bottom into a drying box, and drying for 12 hours at the temperature of 120 ℃;
and 3, performing XRD detection on the solid obtained by drying.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2363399A1 (en) * | 2010-01-20 | 2011-08-02 | Universidad Politécnica De Valencia | Catalyst for selective oxidation of hydrocarbons |
| WO2014114948A1 (en) * | 2013-01-24 | 2014-07-31 | Johnson Matthey Public Limited Company | Method of manufacture |
| CN105254901A (en) * | 2015-11-04 | 2016-01-20 | 中国科学院化学研究所 | Metal organic framework material as well as preparation method and application thereof |
| KR20160054086A (en) * | 2014-11-05 | 2016-05-16 | 국방과학연구소 | A fluorinated metal organic framework powder surface-modified with amphiphilic molecules, a canister having the same and a gas mask having the canister |
| CN106866741A (en) * | 2017-03-03 | 2017-06-20 | 哈尔滨工业大学 | A kind of method of solventless method Fast back-projection algorithm metal-organic framework materials MIL 100 (Cr) |
| CN113773518A (en) * | 2021-10-08 | 2021-12-10 | 南昌航空大学 | Method for preparing metal-organic framework material HKUST-1 from copper-containing industrial wastewater |
-
2022
- 2022-01-12 CN CN202210033593.6A patent/CN114380869B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2363399A1 (en) * | 2010-01-20 | 2011-08-02 | Universidad Politécnica De Valencia | Catalyst for selective oxidation of hydrocarbons |
| WO2014114948A1 (en) * | 2013-01-24 | 2014-07-31 | Johnson Matthey Public Limited Company | Method of manufacture |
| KR20160054086A (en) * | 2014-11-05 | 2016-05-16 | 국방과학연구소 | A fluorinated metal organic framework powder surface-modified with amphiphilic molecules, a canister having the same and a gas mask having the canister |
| CN105254901A (en) * | 2015-11-04 | 2016-01-20 | 中国科学院化学研究所 | Metal organic framework material as well as preparation method and application thereof |
| CN106866741A (en) * | 2017-03-03 | 2017-06-20 | 哈尔滨工业大学 | A kind of method of solventless method Fast back-projection algorithm metal-organic framework materials MIL 100 (Cr) |
| CN113773518A (en) * | 2021-10-08 | 2021-12-10 | 南昌航空大学 | Method for preparing metal-organic framework material HKUST-1 from copper-containing industrial wastewater |
Non-Patent Citations (2)
| Title |
|---|
| MIL-53(Fe,Cr)及其复合物的制备及光催化性能研究;张琰清;《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》;第15-46页 * |
| 新型纳米多孔材料的结构设计与分离性能研究;童敏曼;《中国博士学位论文全文数据库工程科技Ⅰ辑》;第81-92页 * |
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