CN112573612A - Method for simultaneously adsorbing Sudan red I-IV by using imine covalent organic framework and application - Google Patents

Method for simultaneously adsorbing Sudan red I-IV by using imine covalent organic framework and application Download PDF

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CN112573612A
CN112573612A CN202011370313.8A CN202011370313A CN112573612A CN 112573612 A CN112573612 A CN 112573612A CN 202011370313 A CN202011370313 A CN 202011370313A CN 112573612 A CN112573612 A CN 112573612A
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sudan red
organic framework
covalent organic
imine
solution
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CN112573612B (en
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邓启良
孙蕊
陈玉洁
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Tianjin University of Science and Technology
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Tianjin University of Science and Technology
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    • 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
    • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
    • 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
    • C02F2101/38—Organic compounds containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/16—Regeneration of sorbents, filters
    • 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 relates to a method for simultaneously adsorbing Sudan red I-IV by utilizing an imine covalent organic framework and application thereof, wherein the imine covalent organic framework is placed in a Sudan red solution; separating the solution in the system after adsorption from the imine covalent organic framework, and determining the content of the Sudan red; collecting and drying the imine covalent organic framework adsorbed with the Sudan red, adding an eluent, and oscillating at room temperature; centrifuging the oscillated solid-liquid mixture, removing supernatant, washing the obtained solid with methanol, performing suction filtration, drying to obtain a dry covalent organic framework, and repeating the adsorption-desorption experiment. The imine covalent organic framework is used as an adsorption material of the Sudan red for the first time, can be recycled for at least 5 times, can be used for removing the Sudan red in a complex system, can simultaneously adsorb the Sudan red I-IV, has a good adsorption effect on the Sudan red, can realize recycling, and simultaneously widens the application range of the imine covalent organic framework.

Description

Method for simultaneously adsorbing Sudan red I-IV by using imine covalent organic framework and application
Technical Field
The invention belongs to the technical field of dye adsorption, and particularly relates to a method for simultaneously adsorbing Sudan red I-IV by using an imine covalent organic framework and application thereof.
Background
Sudan red is an important industrial dye, is widely applied to various products as a coloring agent, has high stability, and causes ecological pollution if industrial wastewater containing the Sudan red is discharged. In addition, sudan red is not a food additive, but some food manufacturers add sudan red to make the food appearance more bright and beautiful, and since sudan red contains aromatic rings and azo structures, oral administration or transdermal absorption may cause chromosome damage, thyroid tumor, allergy and asthma reaction in the human body, and thus, research on sudan red has attracted great attention. The selection of the adsorption material is an important part in the enrichment and separation of the sudan red, so that the research on the adsorption material of the sudan red is of great significance for researching and removing the sudan red in a complex system.
The materials used for the adsorption of the sudan red at present are various, and the materials comprise activated carbon, modified peanut shells, magnetic carbon nanotubes, magnetic silica nanoparticles, metal organic frameworks, covalent organic polymers and silane modified bentonite, which are widely used for the separation and enrichment of the sudan red.
As a novel porous material, the covalent organic framework has the advantages of various structural compositions, large specific surface area, high porosity, good thermal stability and small density, and the characteristics of adjustable pore size, designability of structure and functionalization, and is often used as an adsorbent to remove or enrich and separate analytes.
Through searching, no patent publication related to the present patent application has been found.
Disclosure of Invention
The invention aims to overcome the defects of environmental stress in the prior art and provides a method for adsorbing Sudan red I-IV simultaneously by utilizing an imine covalent organic framework and application thereof.
The technical scheme adopted by the invention for solving the technical problems is as follows:
an application of imine covalent organic framework in adsorption of Sudan red.
Moreover, the application is the application of the imine covalent organic framework in the aspect of simultaneously adsorbing Sudan red I-IV.
Furthermore, the imine-type covalent organic framework is prepared by the following steps:
will contain amino-NH2The monomer (a) and the monomer containing the aldehyde-CHO are placed in a reaction vessel, and 1, 4-dioxane and 1,3, 5-trimethylbenzene are added into the vessel; the mixture is subjected to ultrasonic treatment at room temperature until the solid is completely dissolved; adding distilled water and acetic acid into a reaction system and carrying out ultrasonic treatment;
degassing the solution for three times by a freezing-pump-unfreezing circulation method, sealing an ampoule bottle, placing the ampoule bottle in a 120 ℃ oven, and reacting for 4 days; transferring the precipitate from the ampoule bottle to a centrifuge tube, adding methanol, centrifuging, discarding the supernatant, and repeating the steps for 3-4 times until the supernatant is colorless; and transferring the precipitate into a watch glass, and drying in an oven at 120 ℃ for 12h to obtain yellow solid powder, namely the imine covalent organic framework COFs.
And, said amino-containing group-NH2The monomer of (a) is 1,3, 5-tri (4-aminophenyl) benzene, and the monomer containing aldehyde-CHO is 4, 4' -biphenyldicarboxaldehyde.
Furthermore, the imine-type covalent organic framework is prepared by the following steps:
will contain amino-NH2The monomer (a) and the monomer containing aldehyde-CHO are placed in a reaction vessel, and 1, 4-dioxane and 1,3, 5-trimethylbenzene are sequentially added into the reaction vessel; wherein the ratio of mg to mL of the amino-containing monomer, the aldehyde-containing monomer, 1, 4-dioxane and 1,3, 5-trimethylbenzene is 27-29:22-24:0.4-0.6: 0.4-0.6;
subjecting the solid-liquid mixture to ultrasonic treatment at room temperature for 10-15min until the solid is completely dissolved, adding 0.1mL distilled water into each 1.0mL solution, subjecting to ultrasonic treatment for 10min, and adding 0.1mL 3mol L into each 1.1mL reaction solution-1Performing ultrasonic treatment for 15 min; degassing for three times by a freezing-pump-unfreezing circulation method, sealing the reaction container, and placing the reaction container in a 120 ℃ oven for reaction for 4 days; transferring the precipitate from the reaction container to a centrifuge tube, adding methanol, centrifuging in a centrifuge at 10000rpm for 10min, discarding the supernatant, and repeating the step for 3-4 times; transferring the precipitate into a watch glass, and drying in an oven at 120 deg.C for 12h to obtain yellow solid powder, i.e. imine covalent organic frameworkCOFs。
A method for simultaneously adsorbing Sudan red I-IV by using an imine covalent organic framework comprises the following steps:
the preparation method comprises the steps of putting an imine covalent organic framework into a Sudan red solution, and oscillating at room temperature to enable the imine covalent organic framework to fully react;
separating the solution in the system after adsorption from an imine covalent organic framework adsorbed with the Sudan red, and measuring the content of the Sudan red in the solution when the detection wavelength is 515nm by using high performance liquid chromatography;
thirdly, collecting and drying the imine covalent organic framework adsorbed with the Sudan red, adding an eluant into the dried imine covalent organic framework adsorbed with the Sudan red, and oscillating at room temperature; centrifuging the oscillated solid-liquid mixture by a centrifugal machine, removing supernatant liquid, and obtaining eluted imine covalent organic framework solid; washing the obtained solid with methanol, performing suction filtration, drying the obtained filter residue to obtain a dry covalent organic framework, and repeating the adsorption-desorption experiment.
The Sudan red solution in the step is prepared by using absolute ethyl alcohol.
The Sudan red solution in the step is a mixed solution of a Sudan red I solution, a Sudan red II solution, a Sudan red III solution, a Sudan red IV solution and Sudan red I-IV;
or, the specific condition of oscillation in the step is that the oscillation time is 3-1440min in a room-temperature environment.
And the method for separating the solution in the system after adsorption from the imine covalent organic framework adsorbed with the Sudan red is centrifugation or the mixed solution passes through a nylon membrane, and specifically comprises the following steps: at room temperature, centrifuging the mixed solution at 10000rpm of a centrifuge for 10min, taking out supernatant, and separating the imine covalent organic framework adsorbed with the Sudan red from the adsorbed Sudan red IV solution, or passing the mixed solution through a nylon membrane of 0.22 μm to separate the imine covalent organic framework adsorbed with the Sudan red from the adsorbed Sudan red IV solution.
Moreover, the eluent in the step three is acetone;
or, the eluent in step three: the proportion of the dried imine-type covalent organic framework adsorbed with sudan red mL: mg is 2-10 per time: 2-5, the oscillation time is 3-60 min;
or, the number of times of eluting the material by the eluent in the step three is 1-10;
or, collecting the imine covalent organic framework adsorbed with the Sudan red in the step three, and drying to obtain the imine covalent organic framework adsorbed with the Sudan red, collecting the obtained imine covalent organic framework in a surface dish, and placing the surface dish in an oven at 60 ℃ for 12 hours.
The invention has the advantages and positive effects that:
1. the imine covalent organic framework is used as an adsorption material of the Sudan red for the first time, can be recycled for at least 5 times, can be used for removing the Sudan red in a complex system, can simultaneously adsorb the Sudan red I-IV, has a good adsorption effect on the Sudan red, can realize recycling, and simultaneously widens the application range of the imine covalent organic framework.
2. The imine covalent organic framework has the advantages of large specific surface area, uniform pore distribution, good dispersibility, high thermal stability and good biocompatibility, has good adsorption performance on Sudan red, can be repeatedly utilized for at least five times, saves the production cost and has wide application prospect.
3. The imine covalent organic framework selected by the invention is used as an adsorbent, and is used for adsorbing Sudan red by utilizing the pi-pi conjugated interaction of the imine covalent organic framework and the Sudan red.
4. The imine covalent organic framework selected by the invention has good adsorption selectivity on Sudan red.
Drawings
FIG. 1 is a graph showing the adsorption selectivity of an imine-type covalent organic framework selected for use in the present invention to Sudan red IV; wherein, 1-7 respectively represent acid orange 7, acid yellow 23, neutral red, basic orange 2, nile red, calcein and Sudan red IV; the adsorption results of the covalent organic framework on 7 substances are shown in the figure, and it can be obviously seen that under the same experimental conditions, the imine covalent organic framework has better adsorption performance on Sudan red IV;
FIG. 2 is a graph of the adsorption capacity of selected imine-type covalent organic frameworks for simultaneous adsorption of Sudan red I-IV in accordance with the present invention; wherein, 1-4 respectively represent Sudan red I, Sudan red II, Sudan red III and Sudan red IV;
FIG. 3 is a graph showing the results of the recycling performance of the imine-type covalent organic framework selected for use in the present invention while adsorbing Sudan red I-IV; the adsorption amount becomes smaller with the increase of the cycle number, but the change is slight, which indicates that the material has good stability and reusability in the cycle experiment of adsorbing Sudan red IV and shows the potential in practical application.
Detailed Description
The following detailed description of the embodiments of the present invention is provided for the purpose of illustration and not limitation, and should not be construed as limiting the scope of the invention.
The raw materials used in the invention are conventional commercial products unless otherwise specified; the methods used in the present invention are conventional in the art unless otherwise specified.
An application of imine covalent organic framework in adsorption of Sudan red.
Preferably, the application is the application of an imine covalent organic framework in the aspect of simultaneously adsorbing Sudan red I-IV.
Preferably, the imine-type covalent organic framework is prepared by the following steps:
will contain amino-NH2The monomer (a) and the monomer containing the aldehyde-CHO are placed in a reaction vessel, and 1, 4-dioxane and 1,3, 5-trimethylbenzene are added into the vessel; the mixture is subjected to ultrasonic treatment at room temperature until the solid is completely dissolved; adding distilled water and acetic acid into a reaction system and carrying out ultrasonic treatment;
degassing the solution for three times by a freezing-pump-unfreezing circulation method, sealing an ampoule bottle, placing the ampoule bottle in a 120 ℃ oven, and reacting for 4 days; transferring the precipitate from the ampoule bottle to a centrifuge tube, adding methanol, centrifuging, discarding the supernatant, and repeating the steps for 3-4 times until the supernatant is colorless; and transferring the precipitate into a watch glass, and drying in an oven at 120 ℃ for 12h to obtain yellow solid powder, namely the imine covalent organic framework COFs.
Preferably, the amino-containing group-NH2The monomer of (a) is 1,3, 5-tri (4-aminophenyl) benzene, and the monomer containing aldehyde-CHO is 4, 4' -biphenyldicarboxaldehyde.
Preferably, the imine-type covalent organic framework is prepared by the following steps:
will contain amino-NH2The monomer (a) and the monomer containing aldehyde-CHO are placed in a reaction vessel, and 1, 4-dioxane and 1,3, 5-trimethylbenzene are sequentially added into the reaction vessel; wherein the ratio of mg to mL of the amino-containing monomer, the aldehyde-containing monomer, 1, 4-dioxane and 1,3, 5-trimethylbenzene is 27-29:22-24:0.4-0.6: 0.4-0.6;
subjecting the solid-liquid mixture to ultrasonic treatment at room temperature for 10-15min until the solid is completely dissolved, adding 0.1mL distilled water into each 1.0mL solution, subjecting to ultrasonic treatment for 10min, and adding 0.1mL 3mol L into each 1.1mL reaction solution-1Performing ultrasonic treatment for 15 min; degassing for three times by a freezing-pump-unfreezing circulation method, sealing the reaction container, and placing the reaction container in a 120 ℃ oven for reaction for 4 days; transferring the precipitate from the reaction container to a centrifuge tube, adding methanol, centrifuging in a centrifuge at 10000rpm for 10min, discarding the supernatant, and repeating the step for 3-4 times; and transferring the precipitate into a watch glass, and drying in an oven at 120 ℃ for 12h to obtain yellow solid powder, namely the imine covalent organic framework COFs.
A method for simultaneously adsorbing Sudan red I-IV by using an imine covalent organic framework comprises the following steps:
the preparation method comprises the steps of putting an imine covalent organic framework into a Sudan red solution, and oscillating at room temperature to enable the imine covalent organic framework to fully react;
separating the solution in the system after adsorption from an imine covalent organic framework adsorbed with the Sudan red, and measuring the content of the Sudan red in the solution when the detection wavelength is 515nm by using high performance liquid chromatography;
thirdly, collecting and drying the imine covalent organic framework adsorbed with the Sudan red, adding an eluant into the dried imine covalent organic framework adsorbed with the Sudan red, and oscillating at room temperature; centrifuging the oscillated solid-liquid mixture by a centrifugal machine, removing supernatant liquid, and obtaining eluted imine covalent organic framework solid; washing the obtained solid with methanol, performing suction filtration, drying the obtained filter residue to obtain a dry covalent organic framework, and repeating the adsorption-desorption experiment.
Preferably, the sudan red solution in the step is prepared by using absolute ethyl alcohol.
Preferably, the Sudan red solution in the step is a mixed solution of Sudan red I solution, Sudan red II solution, Sudan red III solution, Sudan red IV solution and Sudan red I-IV;
or, the specific condition of oscillation in the step is that the oscillation time is 3-1440min in a room-temperature environment.
Preferably, the method for separating the solution in the system after adsorption from the imine covalent organic framework adsorbed with the Sudan red is centrifugation or the mixed solution passes through a nylon membrane, and specifically comprises the following steps: at room temperature, centrifuging the mixed solution at 10000rpm of a centrifuge for 10min, taking out supernatant, and separating the imine covalent organic framework adsorbed with the Sudan red from the adsorbed Sudan red IV solution, or passing the mixed solution through a nylon membrane of 0.22 μm to separate the imine covalent organic framework adsorbed with the Sudan red from the adsorbed Sudan red IV solution.
Preferably, the eluent in the step three is acetone;
or, the eluent in step three: the proportion of the dried imine-type covalent organic framework adsorbed with sudan red mL: mg is 2-10 per time: 2-5, the oscillation time is 3-60 min;
or, the number of times of eluting the material by the eluent in the step three is 1-10;
or, collecting the imine covalent organic framework adsorbed with the Sudan red in the step three, and drying to obtain the imine covalent organic framework adsorbed with the Sudan red, collecting the obtained imine covalent organic framework in a surface dish, and placing the surface dish in an oven at 60 ℃ for 12 hours.
Specifically, the method for simultaneously adsorbing Sudan red I-IV by utilizing an imine covalent organic framework comprises the following steps:
(1) 28.15mg of 1,3, 5-tris (4-aminophenyl) benzene and 23.12mg of 4, 4' -biphenyldicarboxaldehyde were weighed out and placed in an ampoule, and 1, 4-dioxane and 1,3, 5-trimethylbenzene were added to the container. The mixture was sonicated at room temperature until the solid was completely dissolved. Adding distilled water and acetic acid into the reaction system and carrying out ultrasonic treatment for 10-15 min. The solution is degassed three times by a freezing-pump-unfreezing circulation method, then the ampoule bottle is sealed, and the ampoule bottle is placed in an oven with the temperature of 120 ℃ for reaction for 4 days. Transferring the precipitate from the ampoule bottle to a centrifuge tube, adding an appropriate amount of methanol, centrifuging, discarding the supernatant, and repeating the step 3-4 times until the supernatant is colorless. Transferring the precipitate into a watch glass, and drying in an oven at 120 ℃ for 12h to obtain yellow solid powder, namely imine Covalent Organic Frameworks (COFs).
(2) The covalent organic framework material was placed in sudan red solution and shaken at room temperature to allow for full reaction.
(3) Separating the solution in the system after adsorption from the imine covalent organic framework adsorbed with the Sudan red, and measuring the content of the Sudan red of the solution at the detection wavelength of 515nm by using high performance liquid chromatography.
(4) Collecting and drying the imine covalent organic framework adsorbed with the Sudan red, adding an eluent into the dried imine covalent organic framework adsorbed with the Sudan red, and oscillating at room temperature. And collecting the eluted imine covalent organic framework, washing with methanol, drying, and repeating the adsorption-desorption experiment.
More specifically, the relevant preparation examples and tests were as follows:
example 1
A method for selectively adsorbing Sudan red IV by using an imine covalent organic framework comprises the following steps:
(1) 28.15mg of 1,3, 5-tris (4-aminophenyl) benzene and 23.12mg of 4, 4' -biphenyldicarboxaldehyde were weighed out and placed in an ampoule, and 1, 4-dioxane and 1,3, 5-trimethylbenzene were added to the container. The mixture was sonicated at room temperature until the solid was completely dissolved. Adding distilled water and acetic acid into the reaction system and carrying out ultrasonic treatment for 10-15 min. The solution is degassed three times by a freezing-pump-unfreezing circulation method, then the ampoule bottle is sealed, and the ampoule bottle is placed in an oven with the temperature of 120 ℃ for reaction for 4 days. Transferring the precipitate from the ampoule bottle to a centrifuge tube, adding an appropriate amount of methanol, centrifuging, discarding the supernatant, and repeating the step 3-4 times until the supernatant is colorless. Transferring the precipitate into a watch glass, and drying in an oven at 120 ℃ for 12h to obtain yellow solid powder, namely imine Covalent Organic Frameworks (COFs).
(2) Accurately weighing several 2.0mg of the imine-type covalent organic framework material, and dispersing in 5.0mL solution containing 0.10mg mL each of acid orange 7, acid yellow 23, neutral red, basic orange 2, nile red, calcein, and Sudan red IV-1The mixed solution of (4) was shaken at 150rpm for 6 hours at room temperature.
(3) The adsorbed system is centrifuged and passed through a 0.22 μm nylon membrane, the content of each dye in the solution at a detection wavelength of 515nm is measured by high performance liquid chromatography, and the adsorption effects of the imine-type covalent organic framework on 7 substances are calculated and compared. The adsorption results are shown in fig. 1, and it can be clearly seen that the imine-type covalent organic framework shows stronger adsorption performance to sudan red IV under the same experimental conditions.
Example 2
A method for simultaneously adsorbing Sudan red I-IV by using an imine covalent organic framework comprises the following steps:
(1) 28.15mg of 1,3, 5-tris (4-aminophenyl) benzene and 23.12mg of 4, 4' -biphenyldicarboxaldehyde were weighed out and placed in an ampoule, and 1, 4-dioxane and 1,3, 5-trimethylbenzene were added to the container. The mixture was sonicated at room temperature until the solid was completely dissolved. Adding distilled water and acetic acid into the reaction system and carrying out ultrasonic treatment for 10-15 min. The solution is degassed three times by a freezing-pump-unfreezing circulation method, then the ampoule bottle is sealed, and the ampoule bottle is placed in an oven with the temperature of 120 ℃ for reaction for 4 days. Transferring the precipitate from the ampoule bottle to a centrifuge tube, adding an appropriate amount of methanol, centrifuging, discarding the supernatant, and repeating the step 3-4 times until the supernatant is colorless. Transferring the precipitate into a watch glass, and drying in an oven at 120 ℃ for 12h to obtain yellow solid powder, namely imine Covalent Organic Frameworks (COFs).
(2) Dispersing a plurality of accurately weighed 5.0mg COFs materials in Sudan red I, Sudan red II, Sudan red III and Sudan red IV with the concentration of 1.0mg mL respectively-1The Sudan red I-IV mixed solution. The cuvette was placed in a shaker and shaken at 150rpm for 6h at room temperature.
(3) The adsorbed system is passed through a 0.22 μm nylon membrane to separate the adsorbed imine-type covalent organic framework, and the content of each component of Sudan red I-IV is measured by high performance liquid chromatography when the detection wavelength of the solution is 515nm, as shown in figure 2, the imine-type covalent organic framework can adsorb the Sudan red I-IV at the same time.
(4) And respectively collecting the centrifuged precipitates, namely the materials after adsorption, drying, selecting acetone as an eluent, adding the acetone into the dried filter residue, adding 5.0mL of the acetone into the filter residue each time, shaking the mixture at room temperature for 30min, and repeating the steps for 3 to 4 times. The eluted material was collected, washed with methanol, dried, and the adsorption-desorption experiment was repeated. The result is shown in fig. 3, the decrease amount of the covalent organic framework to the adsorption capacity of the sudan red I-IV is slightly changed after multiple adsorption-desorption processes, which indicates that the imine covalent organic framework can be recycled, and also indicates that the imine covalent organic framework has potential application value to the adsorption of the sudan red I-IV.
Although the embodiments of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that: various substitutions, changes and modifications are possible without departing from the spirit and scope of the invention and the appended claims, and therefore the scope of the invention is not limited to the disclosure of the embodiments and the accompanying drawings.

Claims (10)

1. An application of imine covalent organic framework in adsorption of Sudan red.
2. Use according to claim 1, characterized in that: the application is the application of an imine covalent organic framework in the aspect of simultaneously adsorbing Sudan red I-IV.
3. Use according to claim 1 or 2, characterized in that: the preparation steps of the imine covalent organic framework are as follows:
will contain amino-NH2And an aldehydePlacing the monomer of the radical-CHO into a reaction vessel, and adding 1, 4-dioxane and 1,3, 5-trimethylbenzene into the vessel; the mixture is subjected to ultrasonic treatment at room temperature until the solid is completely dissolved; adding distilled water and acetic acid into a reaction system and carrying out ultrasonic treatment;
degassing the solution for three times by a freezing-pump-unfreezing circulation method, sealing an ampoule bottle, placing the ampoule bottle in a 120 ℃ oven, and reacting for 4 days; transferring the precipitate from the ampoule bottle to a centrifuge tube, adding methanol, centrifuging, discarding the supernatant, and repeating the steps for 3-4 times until the supernatant is colorless; and transferring the precipitate into a watch glass, and drying in an oven at 120 ℃ for 12h to obtain yellow solid powder, namely the imine covalent organic framework COFs.
4. Use according to claim 3, characterized in that: said amino-containing group-NH2The monomer of (a) is 1,3, 5-tri (4-aminophenyl) benzene, and the monomer containing aldehyde-CHO is 4, 4' -biphenyldicarboxaldehyde.
5. Use according to claim 3, characterized in that: the preparation steps of the imine covalent organic framework are as follows:
will contain amino-NH2The monomer (a) and the monomer containing aldehyde-CHO are placed in a reaction vessel, and 1, 4-dioxane and 1,3, 5-trimethylbenzene are sequentially added into the reaction vessel; wherein the ratio of mg to mL of the amino-containing monomer, the aldehyde-containing monomer, 1, 4-dioxane and 1,3, 5-trimethylbenzene is 27-29:22-24:0.4-0.6: 0.4-0.6;
subjecting the solid-liquid mixture to ultrasonic treatment at room temperature for 10-15min until the solid is completely dissolved, adding 0.1mL distilled water into each 1.0mL solution, subjecting to ultrasonic treatment for 10min, and adding 0.1mL 3mol L into each 1.1mL reaction solution-1Performing ultrasonic treatment for 15 min; degassing for three times by a freezing-pump-unfreezing circulation method, sealing the reaction container, and placing the reaction container in a 120 ℃ oven for reaction for 4 days; transferring the precipitate from the reaction container to a centrifuge tube, adding methanol, centrifuging in a centrifuge at 10000rpm for 10min, discarding the supernatant, and repeating the step for 3-4 times; transferring the precipitate into a watch glass, and drying in an oven at 120 deg.C for 12 hr to obtain yellow solid powder which is imineCovalent Organic Frameworks (COFs).
6. A method for simultaneously adsorbing Sudan red I-IV by utilizing an imine covalent organic framework is characterized by comprising the following steps: the method comprises the following steps:
the preparation method comprises the steps of putting an imine covalent organic framework into a Sudan red solution, and oscillating at room temperature to enable the imine covalent organic framework to fully react;
separating the solution in the system after adsorption from an imine covalent organic framework adsorbed with the Sudan red, and measuring the content of the Sudan red in the solution when the detection wavelength is 515nm by using high performance liquid chromatography;
thirdly, collecting and drying the imine covalent organic framework adsorbed with the Sudan red, adding an eluant into the dried imine covalent organic framework adsorbed with the Sudan red, and oscillating at room temperature; centrifuging the oscillated solid-liquid mixture by a centrifugal machine, removing supernatant liquid, and obtaining eluted imine covalent organic framework solid; washing the obtained solid with methanol, performing suction filtration, drying the obtained filter residue to obtain a dry covalent organic framework, and repeating the adsorption-desorption experiment.
7. The method for simultaneous adsorption of sudan red I-IV using an imine-type covalent organic framework according to claim 6, wherein: the Sudan red solution is prepared from absolute ethyl alcohol.
8. The method for simultaneous adsorption of sudan red I-IV using an imine-type covalent organic framework according to claim 6, wherein: the Sudan red solution is a mixed solution of Sudan red I solution, Sudan red II solution, Sudan red III solution, Sudan red IV solution and Sudan red I-IV;
or, the specific condition of oscillation in the step is that the oscillation time is 3-1440min in a room-temperature environment.
9. The method for simultaneous adsorption of sudan red I-IV using an imine-type covalent organic framework according to claim 5, wherein: the method for separating the solution in the system after adsorption and the imine covalent organic framework adsorbed with the Sudan red is centrifugation or a nylon membrane through which mixed solution passes, and specifically comprises the following steps: at room temperature, centrifuging the mixed solution at 10000rpm of a centrifuge for 10min, taking out supernatant, and separating the imine covalent organic framework adsorbed with the Sudan red from the adsorbed Sudan red IV solution, or passing the mixed solution through a nylon membrane of 0.22 μm to separate the imine covalent organic framework adsorbed with the Sudan red from the adsorbed Sudan red IV solution.
10. The process for the simultaneous adsorption of sudan red I-IV using imine-type covalent organic frameworks according to any of claims 5 to 9, characterized in that:
the eluent in the step three is acetone;
or, the eluent in step three: the proportion of the dried imine-type covalent organic framework adsorbed with sudan red mL: mg is 2-10 per time: 2-5, the oscillation time is 3-60 min;
or, the number of times of eluting the material by the eluent in the step three is 1-10;
or, collecting the imine covalent organic framework adsorbed with the Sudan red in the step three, and drying to obtain the imine covalent organic framework adsorbed with the Sudan red, collecting the obtained imine covalent organic framework in a surface dish, and placing the surface dish in an oven at 60 ℃ for 12 hours.
CN202011370313.8A 2020-11-30 2020-11-30 Method for simultaneously adsorbing Sudan red I-IV by using imine covalent organic framework and application Active CN112573612B (en)

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