CN114106343A - Preparation method of metal organic framework material - Google Patents
Preparation method of metal organic framework material Download PDFInfo
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- CN114106343A CN114106343A CN202010888258.5A CN202010888258A CN114106343A CN 114106343 A CN114106343 A CN 114106343A CN 202010888258 A CN202010888258 A CN 202010888258A CN 114106343 A CN114106343 A CN 114106343A
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- 239000000463 material Substances 0.000 title claims abstract description 96
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 59
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- 238000011069 regeneration method Methods 0.000 claims abstract description 41
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- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 28
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- 238000001914 filtration Methods 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- 239000011148 porous material Substances 0.000 claims description 16
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 12
- 239000000835 fiber Substances 0.000 claims description 12
- 239000013110 organic ligand Substances 0.000 claims description 11
- 238000005374 membrane filtration Methods 0.000 claims description 10
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 10
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- 239000004020 conductor Substances 0.000 claims description 6
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims description 6
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims description 6
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 5
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 5
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- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 39
- 238000006243 chemical reaction Methods 0.000 description 20
- 239000000725 suspension Substances 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
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- 238000001179 sorption measurement Methods 0.000 description 9
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 4
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 description 2
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 238000004847 absorption spectroscopy Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 239000003446 ligand Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
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Images
Classifications
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- 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
-
- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
- C10G25/003—Specific sorbent material, not covered by C10G25/02 or C10G25/03
Abstract
The invention relates to a preparation method of a metal organic framework material, which comprises the following steps: carrying out solid-liquid separation on the waste mother liquor for synthesizing the metal organic framework material to obtain solid and liquid; electrolyzing the liquid to remove nitrate radicals in the liquid to obtain regenerated mother liquid; and using the regeneration mother liquor as a solvent for the synthesis of the metal organic framework material. The method can realize the regeneration and cyclic utilization of the waste mother liquor generated by synthesizing the metal organic framework material, and does not reduce the yield of the metal organic framework material.
Description
Technical Field
The invention relates to a preparation method of a metal organic framework material.
Background
Metal Organic Frameworks (MOFs) are a class of microporous materials with large pore size and high specific surface area. The specific surface area of the material is far larger than that of a molecular sieve with similar pore channels, and the coordination capacity of the ligand can be regulated and changed. In addition, the method has the characteristics of simple synthesis, no need of a template agent, low synthesis temperature, capability of being prepared by directly mixing and reacting metal ions and organic ligands and the like, so the method has good industrial application prospect.
The C8 aromatic hydrocarbon, one of the most important basic raw materials for the production of petrochemicals, contains four isomers, i.e., para-xylene (PX), meta-xylene (MX), ortho-xylene (OX), and Ethylbenzene (EB). Because of the similar structure and the similar boiling point, a special method is needed to realize the separation. Adsorption separation is one of the most important means for separating C8 aromatic hydrocarbon, and it utilizes solid adsorbent with different adsorption capacity to isomer to implement separation. The method has the characteristics of high single-pass yield and low energy consumption, and can obtain a high-purity product. At present, the most commonly used adsorbents are mainly ion exchange X and Y molecular sieves, and the separation effect is good. However, since the adsorption capacity of the adsorbent is close to the theoretical limit of molecular sieves, it is necessary to develop a novel adsorbent having a higher adsorption capacity in order to further improve the separation efficiency. The MOFs material has higher adsorption capacity than X and Y molecular sieves, and if the MOFs material can be used for C8 aromatic hydrocarbon adsorption separation, the MOFs material can possibly become a continuous technology of an ion exchange X and Y molecular sieve, and a new direction is provided for the development of the future adsorption separation technology.
The MOFs are generally synthesized by using a metal source (e.g., aluminum nitrate) and an organic ligand (e.g., terephthalic acid) as raw materials, and performing a chemical reaction in a solvent, such as N, N-Dimethylformamide (DMF), at a certain temperature to generate a network-structured material in which the organic ligand containing oxygen or nitrogen is linked to a metal cluster. Compared with the traditional synthesis of molecular sieves, the method has the advantages of no need of a template agent and the like, and the organic ligand and metal source ions have stronger interaction, so that the effect between a solvent and a material framework can be ensured to be smaller, and the synthesis yield of the MOFs material is greatly improved.
At present, the MOFs material with arene adsorption and separation potential is found to be MIL-53, MOF-5, ZIF-8 and the like, and the MOFs material is synthesized by nitrate and organic ligand. In which MIL-53 is taken as an example, it has better hydrothermal stability and larger adsorption capacity. MIL-53 from MO4(OH)2Octahedron (M ═ Cr)3+、Al3+、Fe3+) The porous structure is constructed with terephthalic acid, nitrate and terephthalic acid are generally used as raw materials, DMF is used as a solvent, and the porous structure is prepared by reacting for 1-72 hours in a closed pressure kettle at 120-250 ℃. The method has the characteristics of easily obtained raw materials, simple reaction, high conversion rate and the like, but a large amount of organic solvent is needed in the reaction process, waste mother liquor is generated, and the method is not environment-friendly. If the synthesis waste mother liquor is directly used in the synthesis, the synthesis yield is seriously influenced, and the yield is reduced from 80 percent of that of using fresh solvent to about 40 percent of that of using waste mother liquor. At present, no patent report on a method for recycling MOFs synthesis waste mother liquor exists in the literature.
Disclosure of Invention
The invention aims to provide a preparation method of a metal organic framework material, which can remove nitrate radicals in waste mother liquor and recover the metal organic framework material remained in the waste mother liquor, realizes the regeneration and cyclic utilization of the waste mother liquor and has no influence on yield.
In order to achieve the above object, the present invention provides a method for preparing a metal organic framework material, the method comprising: carrying out solid-liquid separation on the waste mother liquor for synthesizing the metal organic framework material to obtain solid and liquid; electrolyzing the liquid to remove nitrate radicals in the liquid to obtain regenerated mother liquid; and using the regeneration mother liquor as a solvent for the synthesis of the metal organic framework material.
Through the technical scheme, the method can remove nitrate radicals in the waste mother liquor generated by synthesizing the metal organic framework material, realize the recovery of residual products in the waste mother liquor, obtain the recycled regenerated mother liquor, and does not influence the yield of the metal organic framework material when the regenerated mother liquor is used in the preparation process of the metal organic framework material.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is an SEM photograph (magnification: 10000 times) of an Al-MIL-53 material prepared by using fresh dimethylformamide as a solvent in example 1 of the present invention;
FIG. 2 is an XRD spectrum of an Al-MIL-53 material prepared by using fresh dimethylformamide as a solvent in example 1 of the present invention;
FIG. 3 is an XRD spectrum of Al-MIL-53 prepared by using the regenerated mother liquor as a solvent in example 1 of the present invention.
Detailed Description
The following detailed description of embodiments of the invention refers to the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The invention provides a preparation method of a metal organic framework material, which comprises the following steps: carrying out solid-liquid separation on the waste mother liquor for synthesizing the metal organic framework material to obtain solid and liquid; electrolyzing the liquid to remove nitrate radicals in the liquid to obtain regenerated mother liquid; and using the regeneration mother liquor as a solvent for the synthesis of the metal organic framework material.
The method of the invention realizes the recovery of residual products in the waste mother liquor for synthesizing the metal organic framework material and the removal of nitrate radical therein by adopting a method of combining filtration and electrolysis, so as to obtain the regenerated mother liquor, effectively eliminate the influence of the nitrate radical in the waste mother liquor on the yield, realize the cyclic utilization of the mother liquor, reduce the production cost and realize clean production.
According to the present invention, the solid-liquid separation method is not particularly limited as long as solid matter in the waste mother liquor can be separated. In one embodiment, the solid-liquid separation is selected from filtration and/or centrifugation.
According to the invention, the filtration is a membrane filtration, which is well known to the person skilled in the art, for example the spent mother liquor of a synthetic metal organic framework material can be poured into a funnel covered with a filtration membrane and filtered by applying a vacuum. The pore diameter (hereinafter also referred to as pore diameter) of the filtration membrane of the membrane filtration may vary within a wide range, and may be, for example, 10 to 300nm, preferably 20 to 300 nm.
According to the present invention, the membrane material for membrane filtration is not particularly limited, and may be one or more of polytetrafluoroethylene, nylon, mixed fiber and ceramic, which may be conventionally used by those skilled in the art, and may be selected according to actual needs.
In a specific embodiment, when the membrane material for membrane filtration is mixed fiber, the aperture of the filtration membrane is 20-100 nm; in another specific embodiment, when the membrane material is polytetrafluoroethylene, nylon or ceramic, the aperture of the filter membrane is 100-300 nm.
According to the present invention, the centrifugal separation may be performed by an apparatus conventionally used by those skilled in the art, and may be, for example, a centrifuge. The conditions for centrifugation may include: the rotating speed of the centrifuge is 1000-15000 rpm, the time is 0.1-2 hours, preferably, the rotating speed of the centrifuge is 2000-10000 rpm, and the time is 0.5-1.0 hour.
According to the present invention, the conditions of electrolysis may include: the electrolytic voltage is 2-30V and the time is 0.5-4 hours.
In one embodiment, a method of electrolysis comprises: connecting a first conductive object with the positive electrode of a direct current power supply, connecting a second conductive object with the negative electrode of the direct current power supply, placing the first conductive object and the second conductive object in an electrolytic cell, transferring liquid obtained by solid-liquid separation into the electrolytic cell, and electrolyzing for 0.5-4 hours at a voltage of 2-30V; the first conductive material is a graphite molded body, and the second conductive material is a metal molded body. The dimensions and shapes of the first conductor and the second conductor are not particularly limited, and may be, for example, rod-shaped or plate-shaped, and the dimensions may be selected adaptively according to the size of the electrolytic cell. The material of the metal molded body may be titanium, copper, iron, or the like.
According to the present invention, the concentration of the suspended matter in the waste mother liquor for synthesizing the metal organic framework material may be 800 to 1300mg/L, and the concentration of the nitrate ion may be 400 to 600 mg/L.
According to the invention, the concentration of the suspended matters in the regeneration mother liquor can be 0.5-4.5 mg/L, and the concentration of nitrate ions can be 35.5-71 mg/L; preferably, the concentration of the suspension in the regeneration mother liquor is 0.5-1.0 mg/L, and the concentration of nitrate ions is 35.5-41 mg/L. The content of suspended matters and nitrate ions in the regeneration mother liquor in the method is obviously reduced compared with the content of waste mother liquor, and the yield of the metal organic framework material is not influenced when the regeneration mother liquor is used in the preparation process of the metal organic framework material. The regeneration mother liquor mainly contains solvent, and the unreacted raw materials contained in the regeneration mother liquor can be reused.
The synthesis method of the metal organic framework material according to the present invention is well known to those skilled in the art, and the conditions for the synthesis of the metal organic framework material may include: the temperature is 25-250 ℃, the pressure is 0.1-4.0 MPa, and the time is 1-96 hours.
In a preferred embodiment, the metal-organic framework material is synthesized by reacting an inorganic metal salt and an organic ligand in the presence of a solvent in a heat-resistant closed container at 25 to 150 ℃ and 0.1 to 0.5MPa for 1 to 80 hours. Heat resistant closed vessels are well known to those skilled in the art and may be, for example, autoclaves, stainless steel autoclaves lined with polytetrafluoroethylene. Wherein, the inorganic metal salt, the organic ligand and the solvent are well known to those skilled in the art, for example, the inorganic metal salt can be aluminum nitrate and/or zinc nitrate, the organic ligand can be one or more of terephthalic acid, 2-amino terephthalic acid and 2-methylimidazole, and the solvent can be one or more of dimethylformamide, methanol and N-methylpyrrolidone.
According to the invention, the molar ratio of inorganic metal salt to organic ligand may be 1: (0.5-10), the molar ratio of the solvent to the inorganic metal salt can be (50-1200): 1.
according to the invention, metal-organic framework materials are well known to the person skilled in the art, such as MIL-53 materials, MOF-5 materials or ZIF-8 materials.
In a specific embodiment, after the reaction is finished, taking out solids in a mixture obtained by the reaction to obtain a metal organic framework material and a waste mother liquor, cooling the waste mother liquor to 10-40 ℃, and then performing solid-liquid separation to recover suspended matters in the waste mother liquor. Preferably, the recovered solids can be combined with the metal-organic framework material as a product to further increase the yield of the metal-organic framework material in the process of the invention. The method for removing the solid from the product is not particularly limited, and for example, the mixture obtained by the reaction may be left to stand to precipitate the solid, and the solid may be collected.
The invention is further illustrated by the following examples, but is not to be construed as being limited thereto.
In the examples of the present invention, aluminum nitrate, terephthalic acid, dimethylformamide, zinc nitrate, 2-methylimidazole were commercially available;
the concentration of suspended matters in the waste mother liquor and the regeneration mother liquor is analyzed by a gravimetric method (GB 11901-89); the concentrations of nitrate ions in the waste mother liquor and the regeneration mother liquor are analyzed by adopting a gas phase molecular absorption spectrometry (HJ/T198-2005);
yield of the metal-organic framework material is actual yield/theoretical yield × 100 mass%.
Example 1
(1) Preparation of Metal organic framework materials
So that the molar ratio is 1: 1 in Dimethylformamide (DMF), the molar ratio of dimethylformamide to aluminum nitrate was 82: 1, mixing and stirring for 0.5 hour, transferring the obtained mixed solution into a stainless steel reaction kettle lined with polytetrafluoroethylene, and sealing; heating to 150 ℃ for reaction for 72 hours, wherein the reaction pressure is 0.5 MPa; after the reaction is finished, taking out the reaction kettle and naturally cooling to room temperature; the mixture obtained by the reaction was filtered under reduced pressure to obtain a solid product and a waste mother liquor, and the obtained solid was dried at 80 ℃ for 12 hours to obtain a metal organic framework material (Al-MIL-53 material). The yield of Al-MIL-53 was 81 mass%, and the concentration of the suspension in the waste mother liquor was determined to be 1000mg/L and the concentration of nitrate ion was determined to be 500 mg/L. The SEM photograph of the Al-MIL-53 is shown in figure 1, the grain size is 50-70 nm, and the XRD spectrogram is shown in figure 2.
(2) Treating synthetic waste mother liquor and utilizing it to synthesize metal organic frame material again
Filtering the waste mother liquor by using a mixed fiber filter membrane (filter membrane model: Merck Milipiore, VSWP04700) with the pore diameter of 25nm to obtain solid and filtrate; the filtrate obtained by filtration was poured into an electrolytic cell equipped with an electrolytic device, and nitrate ions in the filtrate were removed by electrolysis. 2 rows of electrodes are placed in an electrolytic cell, each pair of electrodes takes graphite as an anode and a titanium plate as a cathode, electrolysis is carried out for 2 hours under the condition of 5V, regeneration mother liquor is obtained after the electrolysis is finished, and the obtained regeneration mother liquor is sampled and analyzed. The concentration of the suspension in the regeneration mother liquor is 0.5mg/L, the concentration of nitrate ions is 40mg/L, and the purity of the solvent in the regeneration mother liquor is as follows: 98.4% by mass, including unreacted raw materials, was used directly in the secondary reaction. And (2) synthesizing Al-MIL-53 again by using the regenerated mother liquor as a solvent according to the proportioning ratio and the method in the step (1), wherein the yield is 79 mass percent, and an XRD spectrogram of the Al-MIL-53 material synthesized by using the regenerated mother liquor as the solvent is shown in figure 3.
Example 2
(1) Preparation of Metal organic framework materials
So that the molar ratio is 1: 3 in Dimethylformamide (DMF), the molar ratio of dimethylformamide to zinc nitrate was 82: 1, mixing and stirring for 0.5 hour, transferring the obtained mixed solution into a stainless steel reaction kettle lined with polytetrafluoroethylene, and sealing; heating to 110 ℃ for reaction for 10 hours, wherein the reaction pressure is 0.2 MPa; after the reaction is finished, taking out the reaction kettle and naturally cooling to room temperature; the mixture obtained by the reaction was filtered under reduced pressure to obtain a solid product and a waste mother liquor, and the obtained solid was dried at 80 ℃ for 12 hours to obtain a metal organic framework material (MOF-5 material). The yield of MOF-5 was 80% by mass, the concentration of the suspension in the spent mother liquor was determined to be 1100mg/L, and the concentration of nitrate ions was determined to be 600 mg/L.
(2) Treating synthetic waste mother liquor and utilizing it to synthesize metal organic frame material again
Filtering the waste mother liquor by using a mixed fiber filter membrane (filter membrane model: Merck Milipiore, VSWP04700) with the pore diameter of 25nm to obtain solid and filtrate; the filtrate obtained by filtration was poured into an electrolytic cell equipped with an electrolytic device, and nitrate ions in the filtrate were removed by electrolysis. 2 rows of electrodes are placed in an electrolytic cell, each pair of electrodes takes graphite as an anode and a titanium plate as a cathode, electrolysis is carried out for 2 hours under the condition of 5V, regeneration mother liquor is obtained after the electrolysis is finished, and the obtained regeneration mother liquor is sampled and analyzed. The concentration of the suspension in the regeneration mother liquor is 0.8mg/L, the concentration of nitrate ions is 38mg/L, and the purity of the solvent in the regeneration mother liquor is as follows: 97.5% by mass, including unreacted raw materials, was used directly in the secondary reaction. And (3) synthesizing the MOF-5 material again by using the regenerated mother liquor as a solvent according to the proportioning ratio and the method in the step (1), wherein the yield is 78 mass%.
Example 3
(1) Preparation of Metal organic framework materials
So that the molar ratio is 1: respectively dissolving zinc nitrate and 2-methylimidazole of 8 in a methanol solvent, and mixing the two uniformly dissolved solutions, wherein the molar ratio of methanol to 2-methylimidazole is 980: 1 and stirring is continued for 1 hour at 25 ℃ under a reaction pressure of 0.1 MPa. And carrying out centrifugal separation on the obtained mixture to obtain a solid product and a waste mother liquor, and drying the obtained solid at the temperature of 80 ℃ for 12 hours to obtain the metal organic framework material (ZIF-8 material). The yield of ZIF-8 was 82% by mass, and the concentration of the suspension in the waste mother liquor was 1200mg/L and the concentration of nitrate ion was 550mg/L, as measured.
(2) Treating synthetic waste mother liquor and utilizing it to synthesize metal organic frame material again
Filtering the waste mother liquor by using a mixed fiber filter membrane (filter membrane model: Merck Milipiore, VSWP04700) with the pore diameter of 25nm to obtain solid and filtrate; and injecting the filtrate obtained by filtering into an electrolytic cell provided with an electrolytic device, and electrolyzing to remove nitrate ions in the filtrate. 2 rows of electrodes are placed in an electrolytic cell, each pair of electrodes takes graphite as an anode and a titanium plate as a cathode, electrolysis is carried out for 2 hours under the condition of 5V, regeneration mother liquor is obtained after the electrolysis is finished, and the obtained regeneration mother liquor is sampled and analyzed. The concentration of the suspension in the regeneration mother liquor is 0.7mg/L, the concentration of nitrate ions is 36mg/L, and the purity of the solvent in the regeneration mother liquor is as follows: 99.3% by mass, including unreacted raw materials, can be used directly for the secondary reaction. And (2) taking the regenerated mother liquor as a solvent to synthesize the ZIF-8 material again according to the proportioning ratio and the method in the step (1), wherein the yield is 81 mass percent.
Example 4
An Al-MIL-53 material was prepared in the same manner as in example 1, except that, in the step (2), the mixed fiber filter having a pore size of 25nm was replaced with an inorganic ceramic membrane having a pore size of 180nm (filter model: Sanyan environmental protection technologies, Ltd., T19).
The concentration of the suspension in the obtained regeneration mother liquor was 0.6mg/L, the concentration of nitrate ions was 40.5mg/L, and the yield of Al-MIL-53 material re-synthesized using the regeneration mother liquor as a solvent was 76 mass%.
Example 5
Al-MIL-53 material was prepared in the same manner as in example 1, except that in step (2), the mixed fiber filter with a pore size of 25nm was replaced with a Polytetrafluoroethylene (PTFE) filter with a pore size of 220nm (filter model: Merck Millipore, FGLP 04700).
The concentration of the suspension in the obtained regeneration mother liquor was 4.5mg/L, the concentration of nitrate ions was 41mg/L, and the yield of Al-MIL-53 material re-synthesized using the regeneration mother liquor as a solvent was 75 mass%.
Example 6
Al-MIL-53 material was prepared in the same manner as in example 1, except that, in step (2), the mixed fiber filter with a pore size of 25nm was replaced with a nylon filter with a pore size of 200nm (filter model: Merck Millipore, GNWP 04700).
The concentration of the suspension in the obtained regeneration mother liquor was 4.1mg/L, the concentration of nitrate ions was 40.6mg/L, and the yield of Al-MIL-53 material re-synthesized using the regeneration mother liquor as a solvent was 77% by mass.
Example 7
An Al-MIL-53 material was prepared in the same manner as in example 1, except that, in the step (2), the mixed fiber membrane filtration was not performed, and the waste mother liquor was centrifuged at 3000rpm for 0.67 hours using a centrifuge.
The concentration of the suspension in the obtained regeneration mother liquor was 3.9mg/L, the concentration of nitrate ions was 40.8mg/L, and the yield of Al-MIL-53 material re-synthesized using the regeneration mother liquor as a solvent was 76 mass%.
Example 8
An Al-MIL-53 material was produced in the same manner as in example 1, except that in the step (2), the electrolysis voltage was changed to 30V and the electrolysis time was shortened to 0.5 hour.
The concentration of the suspension in the obtained regeneration mother liquor was 0.5mg/L, the concentration of nitrate ions was 70.8mg/L, and the yield of Al-MIL-53 material re-synthesized using the regeneration mother liquor as a solvent was 72 mass%.
Example 9
An Al-MIL-53 material was produced in the same manner as in example 1, except that, in the step (2), the electrolysis voltage was changed to 3V and the electrolysis time was extended to 3 hours.
The concentration of the suspension in the obtained regeneration mother liquor was 0.5mg/L, the concentration of nitrate ions was 55.5mg/L, and the yield of Al-MIL-53 material re-synthesized using the regeneration mother liquor as a solvent was 72 mass%.
Example 10
An Al-MIL-53 material was prepared in the same manner as in example 1, except that, in the step (2), the mixed fiber membrane filtration was not performed, and the waste mother liquor was centrifuged at 10000rpm for 1 hour using a centrifuge.
The concentration of the suspension in the obtained regeneration mother liquor was 3.2mg/L, the concentration of nitrate ions was 35.5mg/L, and the yield of Al-MIL-53 material re-synthesized using the regeneration mother liquor as a solvent was 80 mass%.
The method can remove nitrate radicals in the metal organic framework material synthesis waste mother liquor and recover a small amount of products in the metal organic framework material synthesis waste mother liquor, so that the waste mother liquor generated in the metal organic framework material synthesis process can be recycled, and the yield of the metal organic framework material is not influenced during recycling.
The preferred embodiments of the present invention have been described in detail with reference to the accompanying drawings, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (12)
1. A method of preparing a metal organic framework material, the method comprising: carrying out solid-liquid separation on the waste mother liquor for synthesizing the metal organic framework material to obtain solid and liquid; electrolyzing the liquid to remove nitrate radicals in the liquid to obtain regenerated mother liquid; and using the regeneration mother liquor as a solvent for the synthesis of the metal organic framework material.
2. The method of claim 1, wherein the solid-liquid separation is selected from filtration and/or centrifugation.
3. The method according to claim 2, wherein the filtration is membrane filtration, and the pore diameter of a filtration membrane of the membrane filtration is 10-300 nm.
4. The method according to claim 3, wherein the membrane material of the membrane filtration is selected from one or more of polytetrafluoroethylene, nylon, mixed fiber and ceramic.
5. The method according to claim 4, wherein when the membrane material of the membrane filtration is the mixed fiber, the pore diameter of the filtration membrane is 20-100 nm;
when the membrane material is the polytetrafluoroethylene, the nylon or the ceramic, the pore diameter of the filtering membrane is 100-300 nm.
6. The method of claim 2, wherein the solid-liquid separation is the centrifugation, the conditions of the centrifugation comprising: the rotation speed of the centrifuge is 1000-15000 rpm, and the time is 0.1-2 hours.
7. The method of claim 1, wherein the conditions of electrolysis comprise: the electrolytic voltage is 2-30V and the time is 0.5-4 hours.
8. The method of claim 1, wherein the method of electrolysis comprises: connecting a first conductive object with the positive electrode of a direct current power supply, connecting a second conductive object with the negative electrode of the direct current power supply, placing the first conductive object and the second conductive object in an electrolytic cell, transferring the liquid obtained by solid-liquid separation into the electrolytic cell, and electrolyzing for 0.5-4 hours at a voltage of 2-30V; the first conductive material is a graphite molded body, and the second conductive material is a metal molded body.
9. The method according to any one of claims 1 to 8, wherein the concentration of a suspended matter in the waste mother liquor of the synthetic metal organic framework material is 800 to 1300mg/L, and the concentration of nitrate ions is 400 to 600 mg/L.
10. The method according to any one of claims 1 to 8, wherein the concentration of the suspended matter in the regeneration mother liquor is 0.5 to 4.5mg/L, and the concentration of the nitrate ion is 35.5 to 71 mg/L.
11. The method according to claim 1, wherein the inorganic metal salt used for synthesizing the metal-organic framework material is aluminum nitrate and/or zinc nitrate, and the organic ligand is one or more of terephthalic acid, 2-aminoterephthalic acid and 2-methylimidazole;
the molar ratio of the inorganic metal salt to the organic ligand is 1: (0.5-10), wherein the molar ratio of the solvent to the inorganic metal salt is (50-1200): 1;
the conditions for the synthesis of the metal-organic framework material comprise: the temperature is 25-150 ℃, the pressure is 0.1-0.5 MPa, and the time is 1-80 hours.
12. The method of claim 1 or 11, wherein the metal organic framework material is a MIL-53 material, a MOF-5 material, or a ZIF-8 material.
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