CN112111060B - Porous organic framework material, preparation method thereof and application thereof in selective separation of perrhenate - Google Patents

Porous organic framework material, preparation method thereof and application thereof in selective separation of perrhenate Download PDF

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CN112111060B
CN112111060B CN202011036942.7A CN202011036942A CN112111060B CN 112111060 B CN112111060 B CN 112111060B CN 202011036942 A CN202011036942 A CN 202011036942A CN 112111060 B CN112111060 B CN 112111060B
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organic framework
framework material
perrhenate
porous organic
amine
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CN112111060A (en
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王磊
焦韶韶
刘康
李少香
马鼎璇
杜云梅
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Weifang Guanghua Fine Chemical Co ltd
Qingdao University of Science and Technology
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Weifang Guanghua Fine Chemical Co ltd
Qingdao University of Science and Technology
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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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08—Selective adsorption, e.g. chromatography
    • B01D15/26—Selective adsorption, e.g. chromatography characterised by the separation mechanism
    • B01D15/36—Selective adsorption, e.g. chromatography characterised by the separation mechanism involving ionic interaction
    • B01D15/361—Ion-exchange
    • B01D15/363—Anion-exchange
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
    • C08G73/065—Preparatory processes
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Abstract

The invention provides a preparation method of a porous organic framework material, which comprises the following steps: mixing the tri (4-imidazolyl phenyl) amine and cyanuric chloride with a solvent, and carrying out quaternization reaction to obtain the porous organic framework material. The invention adopts tri (4-imidazolyl phenyl) amine TIPA and cyanuric chloride as raw materials to carry out quaternization reaction, so that the prepared porous material has a special structure of a cation framework, free anions such as chloride ions exist in a pore channel, and the porous material is mixed with a solution containing the perrhenate and then is subjected to selective separation of the perrhenate through anion exchange in the pore channel. The experiment result shows that the specific surface area of the porous organic framework material provided by the application is 274m2The adsorption rate is up to 100%, and the maximum adsorption quantity is 442 mg/g.

Description

Porous organic framework material, preparation method thereof and application of porous organic framework material in selective separation of perrhenate
Technical Field
The invention belongs to the field of recycling of rare elements, and particularly relates to a porous organic framework material, a preparation method of the porous organic framework material and application of the porous organic framework material in selective separation of perrhenate.
Background
Rhenium (Re) is the latest important element found in a rare dispersion element (RSE), belongs to a precious rare dispersion metal element, has high hardness, corrosion resistance and wear resistance, has good ductility, and is widely applied to the aspects of national defense, aerospace, ultrahigh temperature emission and the like. Because of the very low content of rhenium in the crust, the price of rhenium and its compounds is highIs expensive, and has more practical value for recycling. In weak acid or weak base solution, rhenium is seven-valent anion ReO4 -In general, ammonium perrhenate, potassium perrhenate, for example, are extracted in the form of anions in hydrometallurgy.
At present, when perrhenate is selectively separated, the perrhenate is usually adsorbed by using a selective adsorption material, for example, patent CN109336998A describes a macroporous resin and an ion exchange device for adsorbing high-concentration rhenium, a macroporous divinylbenzene-methyl acrylate copolymer skeleton is prepared by a suspension polymerization method, and isobutanol and toluene are added to react according to the weight ratio of 1: 1 volume ratio, chloromethylating the prepared divinylbenzene-methyl acrylate copolymer skeleton globule to obtain a chlorine sphere, finally soaking the prepared chlorine sphere in methanol for swelling, adding diaminopropionic acid for amination reaction to obtain the macroporous rhenium ion exchange resin. Although the preparation method can prepare the material with abundant porous and macroporous structures and realize selective separation on the perrhenate, the selective separation effect is not ideal. Therefore, there is a need for improvements in the manufacturing process to produce materials with highly selective separations of perrhenate.
Disclosure of Invention
The invention aims to provide a preparation method of a porous organic framework material. The porous organic framework material prepared by the preparation method provided by the invention can realize high-selectivity separation of perrhenate.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a porous organic framework material, which comprises the following steps:
mixing the tri (4-imidazolyl phenyl) amine and cyanuric chloride with an organic solvent, and carrying out quaternization reaction to obtain the porous organic framework material.
Preferably, the ratio of the amounts of the tris (4-imidazolylphenyl) amine and the cyanuric chloride is (0.6-1.2): (0.4-0.8).
Preferably, the organic solvent is N, N '-dimethylformamide, N' -dimethylacetamide or N-methylpyrrolidone.
Preferably, the temperature of the quaternization reaction is 60-100 DEG C
Preferably, the time of the quaternization reaction is 12-24 h.
Preferably, the quaternization reaction is terminated by benzyl bromide as a terminator.
Preferably, the amount of said substance of benzyl bromide to said tris (4-imidazolylphenyl) amine is (0.4-0.6): (0.6-1.2).
The invention also provides the porous organic framework material prepared by the preparation method in the technical scheme.
The invention also provides application of the porous organic framework material in the technical scheme in selective separation of perrhenate.
Preferably, the porous organic framework material is mixed with a perrhenate-containing solution; the concentration of the perrhenate in the solution containing the perrhenate is 0.5-1 mmol/L.
The invention provides a preparation method of a porous organic framework material, which comprises the following steps: mixing the tri (4-imidazolyl phenyl) amine and cyanuric chloride with an organic solvent, and carrying out quaternization reaction to obtain the porous organic framework material. The invention adopts tri (4-imidazolyl phenyl) amine TIPA and cyanuric chloride as raw materials to carry out quaternization reaction, so that the prepared porous material has a special structure of a cation framework, free anions such as chloride ions exist in a pore channel, and the porous material is mixed with a solution containing the perrhenate and then is subjected to selective separation of the perrhenate through anion exchange in the pore channel. The experiment result shows that the specific surface area of the porous organic framework material provided by the application is 274m2The adsorption rate is up to 100%, and the maximum adsorption quantity is 442 mg/g.
Drawings
FIG. 1 is a structural unit of a porous organic framework material of the present invention;
FIG. 2 is an infrared spectrum of the porous organic framework material prepared in example 1;
FIG. 3 is a solid NMR carbon spectrum of the porous organic framework material prepared in example 1;
FIG. 4 is a plot of nitrogen adsorption and desorption under 77K conditions for the porous organic framework material prepared in example 1;
FIG. 5 is a graph of the adsorption effect of porous organic framework material on perrhenate at different adsorption times for example 7;
FIG. 6 is a graph showing the adsorption effect of the porous organic framework materials on perrhenate in examples 8 to 12.
Detailed Description
The invention provides a preparation method of a porous organic framework material, which comprises the following steps:
mixing the tri (4-imidazolyl phenyl) amine and cyanuric chloride with an organic solvent, and carrying out quaternization reaction to obtain the porous organic framework material.
In the present invention, the ratio of the amounts of tris (4-imidazolylphenyl) amine and cyanuric chloride is preferably (0.6 to 1.2): (0.4 to 0.8), more preferably 1: 1. in the present invention, the ratio of the amounts of the tris (4-imidazolylphenyl) amine and the cyanuric chloride is within the above range, and a sufficient quaternization reaction can be performed.
In the present invention, the organic solvent is preferably N, N '-dimethylformamide, N' -dimethylacetamide, or N-methylpyrrolidone. The amount of the organic solvent used in the present invention is not particularly limited, and the raw materials may be dissolved in the organic solvent.
In the present invention, the mixing of tris (4-imidazolylphenyl) amine and cyanuric chloride with the organic solvent is preferably performed by mixing tris (4-imidazolylphenyl) amine with a part of the organic solvent to obtain a first mixed solution; mixing cyanuric chloride with the rest of organic solvent to obtain a second mixed solution; and mixing the first mixed solution and the second mixed solution. In the present invention, the raw material ligands can be brought into contact with each other more sufficiently by the above-mentioned mixing method, and the reaction can be carried out sufficiently.
In the present invention, it is preferable to mix tris (4-imidazolylphenyl) amine with a part of the organic solvent to obtain a first mixed solution. The sources of the tris (4-imidazolylphenyl) amine and the organic solvent are not particularly limited in the present invention, and commercially available products well known to those skilled in the art may be used. The operation of mixing the tris (4-imidazolyl phenyl) amine with a part of the organic solvent is not particularly limited in the present invention, and the technical scheme for preparing the mixed material, which is well known to those skilled in the art, can be adopted.
In the present invention, cyanuric chloride is preferably mixed with the remaining organic solvent to obtain a second mixed solution. The source of the cyanuric chloride is not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used. The operation of mixing the cyanuric chloride with the residual organic solvent is not particularly limited in the invention, and the technical scheme for preparing the mixed material, which is well known to those skilled in the art, can be adopted.
In the invention, the volume ratio of the partial organic solvent to the residual organic solvent is preferably 1-5, and more preferably 1-2. In the present invention, the volume ratio of the partial organic solvent to the remaining organic solvent is within the above range to dissolve the starting materials tris (4-imidazolylphenyl) amine and cyanuric chloride better.
In the invention, the temperature of the quaternization reaction is preferably 60-100 ℃, and more preferably 80-100 ℃; the time of the quaternization reaction is preferably 12-24 hours, and more preferably 15-24 hours. In the present invention, the temperature and time of the quaternization reaction are within the above ranges to allow the tris (4-imidazolylphenyl) amine and cyanuric chloride to be sufficiently contacted for the reaction.
In the present invention, the quaternary amination reaction is preferably terminated by using a terminator benzyl bromide. In the present invention, benzyl bromide is preferably added after the above-defined quaternization time to continue the quaternization. In the present invention, the amount ratio of the benzyl bromide to the tris (4-imidazolylphenyl) amine is preferably (0.4 to 0.6): (0.6 to 1.2), more preferably 1: 2. in the invention, the terminator benzyl bromide can ensure that the raw materials are fully reacted, by-products are reduced, and the utilization rate of the raw materials is improved.
The invention has no special limitation on the operation of mixing the benzyl bromide and the product obtained by the quaternization reaction, and can adopt the technical scheme for preparing the mixed material which is well known to the technical scheme of the technical personnel in the field. In the invention, the time for continuing the quaternization reaction is preferably 20-48 h, and more preferably 24-40 h; the temperature for the continuous quaternization is preferably 60-120 ℃, and more preferably 80-100 ℃. In the present invention, the time and temperature for continuing the quaternization reaction are within the above-mentioned ranges to ensure complete termination of the reaction.
After the quaternization reaction is finished, the product obtained by the quaternization reaction is preferably washed and dried in sequence to obtain the porous organic framework material. The washing and drying operations are not particularly limited in the present invention, and washing and drying known to those skilled in the art may be employed. In the invention, the washing and drying of the product obtained by the quaternization reaction can ensure that unreacted raw materials and possible generated byproducts are washed clean, and further improve the purity of the porous organic framework material.
The preparation method provided by the invention is simple, and the tri (4-imidazolyl phenyl) amine TIPA and cyanuric chloride are used as raw materials to carry out quaternization reaction, so that the prepared porous material has a special structure of a cation framework, free anions such as chloride ions and the like exist in a pore channel, and after the porous material is mixed with a solution containing perrhenate, the perrhenate is selectively separated through anion exchange in the pore channel.
The invention also provides the porous organic framework material prepared by the preparation method in the technical scheme. In the present invention, the porous organic framework material has a cationic framework structure, wherein one structural unit is shown in fig. 1; and has high selectivity to perrhenate, and can be repeatedly utilized.
The invention also provides application of the porous organic framework material in the technical scheme in selective separation of perrhenate. The present invention preferably combines the porous organic framework material with a perrhenate-containing solution to effect selective separation of the perrhenate. In the invention, the concentration of the perrhenate in the solution containing the perrhenate is preferably 0.5-1 mmol/L, and more preferably 0.55-0.8 mmol/L. In the present invention, the ratio of the mass of the porous organic framework material to the volume of the perrhenate-containing solution is preferably 1 mg: (1-2) mL. In the present invention, when the ratio of the mass of the porous organic framework material to the volume of the perrhenate-containing solution is within the above range, highly selective adsorption of the perrhenate by the porous organic framework material can be achieved.
In the present invention, the perrhenate-containing solution is preferably a perrhenate-containing industrial wastewater; the perrhenate-containing industrial wastewater preferably also comprises competing anions; the competing anion is preferably at least one of chloride, bromide, nitrate, and sulfate. In the invention, the concentration of the competitive anion is preferably 50-150 times, and more preferably 100 times of the concentration of the perrhenate. In the present invention, the concentration of the competing anion above the concentration of perrhenate ensures high selectivity of the porous organic framework material for perrhenate.
In the invention, the time for mixing the porous organic framework material and the solution containing perrhenate is preferably 1-24 h, and more preferably 10-20 h. In the present invention, the concentration of the perrhenate and the time of mixing are within the above ranges to ensure the adsorption of the maximum amount of perrhenate.
According to the invention, the porous organic framework material is applied to the industrial wastewater containing the perrhenate, so that the selective separation of the perrhenate can be realized, and further, the treatment of the industrial wastewater is realized.
In the present invention, the operation of recycling the porous organic framework material is preferably to sequentially separate, soak, wash, centrifuge and dry the used porous organic framework material. In the present invention, the separation is preferably centrifugation. The operation of the centrifugation in the present invention is not particularly limited, and a centrifugation operation known to those skilled in the art may be used. In the invention, the separation can separate the used porous organic framework material from the perrhenate, thereby being beneficial to recycling.
In the present invention, the soaking solution is preferably a 5mol/L metal salt solution; the metal salt is preferably sodium chloride, potassium chloride, calcium chloride, sodium nitrate, potassium nitrate or calcium nitrate. In the invention, the soaking time is preferably 10-30 h, and more preferably 24 h. The washing, centrifuging and drying operations are not particularly limited in the present invention, and may be those known to those skilled in the art.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Weighing 0.355 g of tris (4-imidazolyl phenyl) amine to dissolve in 20ml of N, N' -dimethylformamide solvent to obtain a first solution; weighing 0.148 g of cyanuric chloride, and dissolving the cyanuric chloride in a 20mLN, N' -dimethylformamide solvent to obtain a second solution; the mass ratio of the tris (4-imidazolyl phenyl) amine to cyanuric chloride is 1: 1; then the two solutions are mixed and reacted in an oil bath at 100 ℃ for 24h, 0.0016mol of benzyl bromide is added, and the ratio of the amount of the benzyl bromide to the amount of the substances of the tris (4-imidazolylphenyl) amine is 1: 2, continuing the oil bath reaction at 80 ℃ for 24 hours; and respectively washing the product obtained by the reaction with N, N' -dimethylformamide, acetonitrile and diethyl ether, and drying in vacuum at 60 ℃ for 12h to obtain yellow powder, namely the porous organic framework material, wherein the yield is 60%.
A red light spectrum test is performed on the porous organic framework material prepared in the embodiment, as shown in fig. 2, fig. 2 is an infrared spectrum of the porous organic framework material prepared in the embodiment 1; as can be seen from FIG. 2, 1621cm-1Is attributed to the characteristic peak of cyanuric chloride-C ═ N-bond stretching vibration, 1386cm-1Is attributed to the characteristic peak of cyanuric chloride-C-N-bond stretching vibration, 1072cm-1The porous organic framework material is proved to be obtained due to the quaternary amine-C-N-stretching vibration peak.
Fig. 3 shows a solid nmr test performed on the porous organic framework material prepared in this example, where fig. 3 is a solid nmr carbon spectrum of the porous organic framework material prepared in example 1, and it can be seen from fig. 3 that 100 to 137ppm of the solid nmr carbon spectrum is attributed to carbon atoms in tris (4-imidazolylphenyl) amine, 165 to 190ppm of the solid nmr carbon spectrum is attributed to carbon atoms in cyanuric chloride, and 50 to 80ppm of the solid nmr carbon spectrum is attributed to carbon atoms in bromobenzyl, which proves that the organic framework material is obtained.
The porous organic framework material prepared in this example was tested for nitrogen adsorption and desorption under 77K conditions, and the results are shown in fig. 4, where fig. 4 is a nitrogen adsorption and desorption curve under 77K conditions for the porous organic framework material prepared in example 1. As can be seen from FIG. 4, the prepared organic framework material has porosity and specific surface area of 442m2 g–1。
Example 2
Weighing 0.355 g of tris (4-imidazolyl phenyl) amine, and dissolving the solution in 20mL of N, N' -dimethylformamide solvent to obtain a first solution; weighing 0.148 g of cyanuric chloride, and dissolving the cyanuric chloride in a 20mLN, N' -dimethylformamide solvent to obtain a second solution; the mass ratio of the tris (4-imidazolyl phenyl) amine to cyanuric chloride is 1: 1; then the two solutions are mixed and reacted in an oil bath at 100 ℃ for 24h, 0.0016mol of benzyl bromide is added, and the ratio of the amount of the benzyl bromide to the amount of the substances of the tris (4-imidazolylphenyl) amine is 1: 2, continuing the oil bath reaction at 80 ℃ for 24 hours; and respectively washing the product obtained by the reaction with N, N' -dimethylformamide, acetonitrile and diethyl ether, and drying in vacuum at 60 ℃ for 12h to obtain yellow powder, namely the porous organic framework material, wherein the yield is 52%.
The red light spectrum test of the porous organic framework material prepared in the embodiment proves that the porous organic framework material is obtained.
The solid nuclear magnetic resonance test of the porous organic framework material prepared in this example was performed, and the composition of the porous organic framework material was the same as that of the porous organic framework material, which proved that the organic framework material was obtained.
The porous organic framework material prepared in the embodiment is tested for nitrogen adsorption and desorption under 77K, and it can be seen that the prepared organic framework material has porosity.
Example 3
0.355 g of tris (4-imidazolylphenyl) amine and 0.148 g of cyanuric chloride were weighed out and dissolved in 20mL of N, N' -dimethylformamide solvent, the mass ratio of tris (4-imidazolylphenyl) amine to cyanuric chloride being 1: 1, oil bath reaction at 100 ℃ for 24h, adding 0.0016mol of benzyl bromide, wherein the ratio of the amount of the benzyl bromide to the substance of the tris (4-imidazolyl phenyl) amine is 1: 2, continuing the oil bath reaction at 80 ℃ for 24 hours; and respectively washing the product obtained by the reaction with N, N' -dimethylformamide, acetonitrile and diethyl ether, and drying in vacuum at 60 ℃ for 12 hours to obtain yellow powder, namely the porous organic framework material, wherein the yield is 36%.
The red light spectrum test of the porous organic framework material prepared in the embodiment proves that the porous organic framework material is obtained.
The solid nuclear magnetic resonance test of the porous organic framework material prepared in this example was performed, and the organic framework material was confirmed to be obtained with the same composition as the porous organic framework material.
When the porous organic framework material prepared in this example is tested for nitrogen adsorption and desorption under 77K, it can be seen that the prepared organic framework material has porosity.
Example 4
0.355 g of tris (4-imidazolylphenyl) amine and 0.148 g of cyanuric chloride are weighed out and dissolved in 40mL of N, N' -dimethylformamide solvent, the ratio of the amounts of the substances of tris (4-imidazolylphenyl) amine and cyanuric chloride being 1: 1, oil bath reaction at 100 ℃ for 24h, adding 0.0016mol of benzyl bromide, wherein the ratio of the amount of the benzyl bromide to the substance of the tris (4-imidazolyl phenyl) amine is 1: 2, continuing the oil bath reaction at 80 ℃ for 24 hours; and respectively washing the product obtained by the reaction with N, N' -dimethylformamide, acetonitrile and diethyl ether, and drying in vacuum at 60 ℃ for 12h to obtain yellow powder, namely the porous organic framework material, wherein the yield is 43%.
The red light spectrum test of the porous organic framework material prepared in the embodiment proves that the porous organic framework material is obtained.
The solid nuclear magnetic resonance test of the porous organic framework material prepared in this example was performed, and the organic framework material was confirmed to be obtained with the same composition as the porous organic framework material.
The porous organic framework material prepared in the embodiment is tested for nitrogen adsorption and desorption under 77K, and it can be seen that the prepared organic framework material has porosity.
Example 5
0.355 g of tris (4-imidazolylphenyl) amine and 0.148 g of cyanuric chloride were weighed out and dissolved in 20mL of N, N' -dimethylformamide solvent, the mass ratio of tris (4-imidazolylphenyl) amine to cyanuric chloride being 1: 1, performing oil bath reaction for 24 hours at the temperature of 100 ℃; and respectively washing the product obtained by the reaction with N, N' -dimethylformamide, acetonitrile and diethyl ether, and drying in vacuum at 60 ℃ for 12 hours to obtain yellow powder, namely the porous organic framework material, wherein the yield is 12%.
The red light spectrum test of the porous organic framework material prepared in the embodiment proves that the porous organic framework material is obtained.
The solid nuclear magnetic resonance test of the porous organic framework material prepared in this example was performed, and the organic framework material was confirmed to be obtained with the same composition as the porous organic framework material.
The porous organic framework material prepared in the embodiment is tested for nitrogen adsorption and desorption under 77K, and it can be seen that the prepared organic framework material has porosity.
Example 6
Weighing 2mg of the porous organic framework material prepared in the example 1, adding the weighed material into 4 ml of ammonium perrhenate solution with the concentration of 0.55mmol/L, quickly shaking and uniformly mixing, and then standing for 10 hours, wherein the adsorption rate is 70%.
Example 7
Weighing 2mg of the porous organic framework material prepared in example 1, adding the weighed material into 4 ml of ammonium perrhenate solution with the concentration of 0.55mmol/L, quickly shaking and uniformly mixing, standing for 24h, wherein the adsorption rate is 82%, the adsorption effect graph of the porous organic framework material on the perrhenate under different adsorption times is shown in fig. 5, and as can be seen from fig. 5, the adsorption property of the porous organic framework material on the perrhenate is better along with the prolonging of the adsorption time.
Example 8
Weighing 2mg of the porous organic framework material prepared in the example 1, adding the weighed material into 2 ml of ammonium perrhenate solution with the concentration of 0.55mmol/L, quickly shaking and uniformly mixing, and then standing for 24 hours, wherein the adsorption rate is 100%.
Example 9
In 10mL solution containing perrhenate, the concentration of potassium chloride is 0.5mol/L, the concentration of perrhenate is 0.55mmol/L, 5 mg of the porous organic framework material prepared in the example 1 is weighed and added into the solution, the solution is shaken and mixed evenly by force, the mixture is kept stand for 24h, and the adsorption rate of the perrhenate is 100%.
Example 10
In 10mL solution containing perrhenate, the concentration of potassium bromide is 0.5mol/L, the concentration of perrhenate is 0.55mmol/L, 5 mg of the porous organic framework material prepared in the example 1 is weighed and added into the solution, the solution is shaken and mixed uniformly by force, the mixture is kept stand for 24h, and the adsorption rate of the perrhenate is 100%.
Example 11
The concentration of potassium nitrate in 10mL solution containing perrhenate was 0.5mol/L, the concentration of perrhenate was 0.55mmol/L, 5 mg of the porous organic framework material prepared in example 1 was weighed and added to the solution, mixed well with shaking, and left to stand for 24h, with the adsorption rate of perrhenate being 100%.
Example 12
The concentration of potassium sulfate in 10mL solution containing perrhenate was 0.5mol/L, the concentration of perrhenate was 0.55mmol/L, 5 mg of the porous organic framework material prepared in example 1 was weighed and added to the solution, mixed well with shaking, and left to stand for 24h, with the adsorption rate of perrhenate being 100%.
Fig. 6 is a graph showing the adsorption effect of the porous organic framework material on perrhenate in examples 8 to 12, and it can be seen from fig. 6 that the porous organic framework material prepared by the present invention can achieve high selectivity on perrhenate even in the presence of competitive anions.
Example 13
The solution of the embodiment 10 is centrifuged, the centrifuged material adsorbing perrhenate is collected and soaked in 5mol/L potassium chloride solution, the mixture is sufficiently shaken and uniformly mixed, then the mixture is kept stand for 24 hours, centrifuged, washed and dried to obtain the porous organic framework material, and the porous organic framework material can be repeatedly utilized for 5 times.
Example 14
One of the solutions of example 12 was centrifuged, the centrifuged perrhenate-adsorbed material was collected and soaked in 5mol/L potassium chloride solution, shaken well and mixed, then left to stand for 24h, centrifuged, washed and dried to obtain a porous organic framework material, which was reusable up to 5 times.
From the above examples, it can be seen that the porous organic framework material prepared by the preparation method provided by the invention can realize high-selectivity separation of perrhenate.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (7)

1. A preparation method of a porous organic framework material comprises the following steps:
mixing tri (4-imidazolyl phenyl) amine and cyanuric chloride with an organic solvent, and carrying out quaternization reaction to obtain a porous organic framework material;
the mass ratio of the tris (4-imidazolyl phenyl) amine to cyanuric chloride is (0.6-1.2): (0.4-0.8);
the termination mode of the quaternization reaction is to adopt a terminator benzyl bromide;
the amount ratio of the benzyl bromide to the tris (4-imidazolylphenyl) amine is (0.4-0.6): (0.6-1.2).
2. The method according to claim 1, wherein the organic solvent is N, N '-dimethylformamide, N' -dimethylacetamide, or N-methylpyrrolidone.
3. The method of claim 1, wherein the temperature of the quaternization reaction is 60 to 100 ℃.
4. The method of claim 1 or 3, wherein the quaternization reaction time is 12-24 hours.
5. The porous organic framework material prepared by the preparation method of any one of claims 1 to 4.
6. Use of a porous organic framework material as claimed in claim 5 for selective separation of perrhenate.
7. Use according to claim 6, characterized in that the porous organic framework material is mixed with a perrhenate-containing solution; the concentration of the perrhenate in the solution containing the perrhenate is 0.5-1 mmol/L.
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